DRAFT
FOR
MISCELLANEOUS CHEMICALS INDUSTRY
f 4T* \
"W
D^IRDWEKTAL PRJ1ECTION AGENCY
FEBRUARY 1975
DRAFT
-------
NOTICE
The attached document is a DRAFT CONTRACTOR'S REPORT. It
includes technical information and recommendations submitted
by the Contractor to the United States Environmental Protection
Agency ("EPA") regarding the subject industry. It is being
distributed for review and comment only. The report is not
an official EPA publication and it has not been reviewed by
the Agency.
The report, including the recommendations, will be undergoing
extensive review by EPA, Federal and States agencies, public
interest organizations, and other interested" groups and per-
sons during the coming weeks. The report and in particular
the contractor's recommended effluent limitations guidelines
and standards of performance is subject to change in any and
all respects.
The regulations to be published by EPA under Section 304 (b)
and 306 of the Federal Water Pollution Control Act, as amended,
will be based to a large extent on the report and the comments
received on it. However, pursuant to Sections 304 (b) and 306
of the Ac", EPA will also consider additional pertinent tech-
nical and economic information which is developed in the course
of review of this report by the public and within EPA. EPA
is currently performing an economic impact analysis regarding
the subject Industry, which will be taken into account as
par', of the review of the report. Upon completion of the
review process, and prior to final promulgation of regulations,
an EPA report will be issued setting forth EPA*s conclusions
concerning the subject industry, effluent limitation guide-
lines and standards of performance applicable to such industry.
Judgments necessary to promulgation of regulations under Sec-
tions 304 (b) and 306 of the Act, of course, remain the responsi-
bility of EPA. Subject to these limitations, EPA is making
this draft contractor's report available in order to encour-
age the widest possible participation of interested persons
in the decision making process at the earliest possible time.
The report shall have standing in any EPA proceeding or court
proceeding only to the extent that it represents the views of
the Contractor who studied the subject industry and prepared the
information and recommendations. It cannot be cited, referenced,
or represented in any respect in any such proceedings as a
statement of EPA's views regarding the subject industry.
U. S. Environmental Protection Agency
Office of Water and Hazardous Materials
Effluent Guidelines Division
Washington, D.C. 20460
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OOOR75011
DRAFT
DEVELOPMENT DOCUMENT FOR
EFFLUENT LIMITATIONS GUIDELINES
AND STANDARDS OF PERFORMANCE
MISCELLANEOUS CHEMICALS INDUSTRY
t
Ul
C9
y
PREPARED BY ROY F. WESTON, INC.
FOR UNITED STATES
ENVIRONMENTAL PROTECTION AGENCY
UNDER CONTRACT NUMBER 68-01- 2932
DATED: FEBRUARY 1975
-------
DRAFT
NOTICE
The attached document Is a DRAFT CONTRACTOR'S REPORT. It Includes tech-
nical information and recommendations submitted by the Con trad or In Ihr
United States Environmental Protection Agency ( EPA ) regarding the sub-
ject industry. It is being distributed for review and comment only. The
report is not an official EPA publication and it has not been reviewed by
the Agency.
The report, including the recommendations, will be undergoing extensive re-
view by EPA, Federal and State agencies, public interest organizations
and other interested groups and persons during the coming weeks. The
report and in particular the contractor's recommended effluent limitations
guidelines and standards of performance are subject to change in any and
all respects.
The regulations to be published by EPA under Sections 304(b) and 306 of the
Federal Water Pollution Control Act, as amended, will be based to a large
extent on the report and the comments received on it. However, pursuant
to Sections 304(b) and 306 of the Act, EPA will also consider additional
pertinent technical and economic information which is developed in the
course of review of this report by the public and within EPA. EPA is cur-
rently performing an economic impact analysis regarding the subject industry,
which will be taken into account as part of the review of the report. Upon
completion of the review process, and prior to final promulgation of regula-
tions, an EPA report will be issued setting forth EPA's conclusions concern-
ing the subject industry, effluent limitations guidelines and standards of
performance applicable to such industry. Judgments necessary to the promulga-
tion of regulations under Sections 30^(b) and 306 of the Act, of course,
remain the responsibility of EPA. Subject to these limitations, EPA is
making this draft contractor's report available in order to encourage the
widest possible participation of interested persons in the decision making
process at the earliest possible time.
The report shall have standing in any EPA proceeding or court proceeding
only to the extent that it represents the views of the Contractor who
studied the subject industry and prepared the information and recommenda-
tions. It cannot be cited, referenced, or represented in any respect in
any such proceedings as a statement of EPA's views regarding the subject
industry.
U.S. Environmental Protection Agency
Office of Air and Water Programs
Effluent Guidelines Division
Washington, D.C. 20460
" A.CE3TCY
i i
-------
ABSTRACT
This document presents the findings of an extensive study of the Miscel-
laneous Chemicals industry by Roy F. Weston, Inc. for the Environmental
Protection Agency, for the purpose of developing effluent limitation
guidelines, Federal standards of performance, and pretreatment standards
for the industry, to implement Sections 3Qh, 306, and 307 of the Federal
Water Pollution Control Act, as amended (33 USC 1251, 131^, and 1316;
86 Stat 816).
Effluent limitation guidelines contained herein set forth the degree of
effluent reduction attainable through the application of the best practi-
cable control technology currently available (BPCTCA), which must be achieved by
existing point sources by July 1, 1977- The degree of effluent re-
duction which must be achieved by July 1, 1983 is attainable by applica-
tion of the best available technology economically achievable (BATEA). The
Standards of Performance for new sources contained herein set forth
the degree of effluent reduction which is achievable through the ap-
pication of the best available demonstrated control technology (BADCT).
The development of data and recommendations in the document relate to
the Miscellaneous Chemicals industry, which is divided into eight in-
dustrial categories and several subcategories on the basis of the char-
acteristics of the manufacturing processes involved. Separate effluent
limitations were developed for each subcategory on the basis of the level
of raw waste load as well as on the degree of treatment achievable by
suggested model systems. These systems include biological and physical/
chemical treatment and systems for reduction in pollutant loads.
Supportive data and the rationale for development of the proposed ef-
fluent limitations guidelines and standards of performance are contained
in this report.
i ii
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
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DRAFT
Section
IV
TABLE OF CONTENTS
ABSTRACT
FIGURES
TABLES
CONCLUSIONS
RECOMMENDATIONS
INTRODUCTION
Purpose and Authority
Scope of Study
Methods Used for Development of the
Effluent Limitations and Standards
for Performance
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
INDUSTRIAL CATEGORIZATION
General
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
i i i
ix
xi i
1-1
11-1
II 1-1
IM-1
111-3
-k
-8
-20
-34
-37
-41
-47
-50
V-1
V-1
V-2
V-36
IV-58
IV-96
IV-113
IV-136
IV-145
IV-155
iv
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TABLE OF CONTENTS
(Continued)
Section Page
V WASTE CHARACTERIZATION V-1
General V-1
A. Pharmaceutical Industry V-2
B. Gum and Wood Chemicals Industry V-25
C. Pesticides and Agricultural Chemicals
Industry V-32
D. Adhesive and Sealants Industry V-52
E. Explosives Industry V-63
F. Carbon Black Industry V-77
G. Photographic Processing Industry V-?8
H. Hospitals . V-80
VI SELECTION OF POLLUTANT PARAMETERS VI-1
General VI-1
Pollutants of Significance VI-1
Pollutants of Limited Significance VI-8
Pollutants of Specific Significance VI-23
A. Pharmaceutical Industry M\-2k
B. Gum and Wood Chemicals Industry VI-26
C. Pesticides and Agricultural Chemicals
Industry VI-28
D. Adhesive and Sealants Industry VI-30
E. Explosives Industry VI-31
F. Carbon Black Industry VI-32
G. Photographic Processing Industry VI-33
H. Hospitals VI-3^
VII CONTROL AND TREATMENT TECHNOLOGIES VI1-1
General VI1-1
A. Pharmaceutical Industry VII-2
B. Gum and Wood Chemicals Industry VI1-20
C. Pesticides and Agricultural Chemicals
Industry VI1-29
D. Adhesive and Sealants Industry VI -36
E. Explosives Industry VI
F. Carbon Black Industry VI
G. Photographic Processing Industry VI -58
H. Hospitals VI -68
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DRAFT
Section
VIII
IX
TABLE OF CONTENTS
(Continued)
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
General
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE (BPCTCA)
General
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE
General
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
VIII-1
VI
VI
VI
VI
VI
VI
VI
VI
VI
-1
-k
-31
-kS
-71
-91
-104
-110
-118
IX-1
IX-1
IX-2
IX-5
IX-9
lx-13
IX-16
lx-19
IX-22
X-1
X-1
X-2
X-5
X-7
X-9
X-12
X-14
X-16
x-18
VI
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XII
.*
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
Industry
D. Adhesive and Sealants Industry
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals
General
A. Pharmaceutical Industry
B. Gum and Wood Chemicals Industry
C. Pesticides and Agricultural Chemicals
XIV ACKNOWLEDGEMENTS
vii
TABLE OF CONTENTS
(Continued)
Section
XI NEW SOURCE PERFORMANCE STANDARDS XI-1
General XI-1
A. Pharmaceutical Industry XI-2
B. Gum and Wood Chemicals Industry XI-4
C. Pesticides and Agricultural Chemicals
Industry XI-6
D. Adhesive and Sealants Industry XI-8
E. Explosives Industry XI-10
F. Carbon Black Industry XI-12
G. Photographic Processing Industry XI-13
H. Hospitals XI-15
PRETREATMENT GUIDELINES XII-1
General *|
A I
XI
XI
XI
XI
XI
XI
XI
-1
-2
-5
-7
-8
-11
-12
-13
XIII PERFORMANCE FACTORS FOR TREATMENT
PLANT OPERATIONS XI I 1-1
XI
XI
XI
Industry XIII-9
D. Adhesive and Sealants Industry XI
E. Explosives Industry
F. Carbon Black Industry
G. Photographic Processing Industry
H. Hospitals XII1-15
XI
XI
XI
-1
-3
-7
-10
-11
-12
-13
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DRAFT
TABLE OF CONTENTS
(Continued)
Section Page
XV BIBLIOGRAPHY XV-1
A. Pharmaceutical Industry XV-1
B. Gum and Wood Chemicals Industry XV-5
C. Pesticides and Agricultural Chemicals
Industry XV-6
0. Adhesive and Sealants Industry XV-10
E. Explosives Industry XV-11
F. Carbon Black Industry XV-19
G. Photographic Processing Industry XV-20
H. Hospitals XV-22
XVI GLOSSARY XVI-1
A. Pharmaceutical Industry XVI-1
B. Gum and Wood Chemicals Industry XVI-7
C. Pesticides and Agricultural Chemicals
Industry XVI-11
D. Adhesive and Sealants Industry XVI-1*t
E. Explosives Industry XVI-16
F. Carbon Black Industry XVI-18
G. Photographic Processing Industry XVI-19
H. Hospitals XVI-20
vi i i
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LIST OF FIGURES
Figures Title
IIA-1 Category A - BPCTCA Effluent Limitations Versus 11-4
Production
IIA-2 Category A - BATEA Effluent Limitations Versus 11-5
Product ion
IIA-3 Category A - BADCT Effluent Limitations Versus 11-6
Product ion
IIIA-1 Shipments of Pharmaceutical Preparations by Census 111-13
Regions, Divisions and States; 196?
MIB-1 Interrelationships of Present Gum and Wood 111-17
Chemicals Industry
IIIC-1 Locations of Pesticides Production Plants 111-33
IIIF-1 U.S. Carbon Black Production by Process 111-45
IVA-1 Typical Fermentation Process IV-13
IVA-2 Typical Fermentation Process IV-14
IVA-3 Typical Vaccine Production Process IV-17
IVA-4 Closed Cooling Water System IV-20
IVA-5 Typical Chemical Synthesis Process IV-22
IVA-6 Typical Chemical Synthesis Process (Antibiotic IV-23
Manufacture)
IVA-? Typical Pharmaceutical Formulation Process IV-26
IVB-1 Char and Charcoal Briquet Manufacturing IV-47
IVB-2 Gum Rosin and Turpentine Production \\l-kS
IVB-3 Wood Rosin, Pine Oil, and Turpentine Production IV-50
via Solvent Extraction
IVB-4 Crude Tall Oil Fractionation and Refining IV-52
ix
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DRAFT
LIST OF FIGURES
(continued)
Figures Title
IVB-5 Distillation and Refining of Essential Oils IV-5^
IVB-6 Rosin Derivatives Manufacture IV-56
IVC-1 General Process Flow Diagram for DDT and Related IV-64
Compounds Production Facilities
IVC-2 General Process Flow Diagram for Halogenated IV-66
Phenol Production Facilities
IVC-3 General Process Flow Diagram of Aryloxyalkanoic IV-67
Acid Production Facilities
IVC-A General Process Flow Diagram for Aldrin-Toxaphene IV-69
Production Facilities
IVC-5 General Process Flow Diagram for Halogenated IV-71
Aliphatic Hydrocarbon Production Facilities
IVC-6 General Process Flow Diagram for Halogenated IV-72
Aliphatic Acid Production Facilities
IVC-7 General Process Flow Diagram for Phosphates and IV-7^
Phosphonates Pesticide Production Facilities
IVC-8 General Process Flow Diagram for Phosphorothioate IV-75
and Phosphorodithioate Production Facilities
IVC-9 General Process Flow Diagram for Aryl and Alkyl IV-78
Carbamate Production Facilities
IVC-10 General Process Flow Diagram for Thiocarbamate IV-79
Production Facilities
IVC-11 General Process Flow Diagram for Amide and Amine IV-81
Production Facilities
IVC-12 General Process Flow Diagram for Urea and Uracils IV-82
Production Facilities
IVC-13 General Process Flow Diagram for S-Triazine IV-84
Production Facilities
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LIST OF FIGURES
(continued)
Figure Title Page
IVC-14 General Process Flow Diagram for Nitro-Type IV-86
Pesticides
IVC-15 General Process Flow Diagram for Arsenic-Type IV-88
Metal Jo-Organic Production
IVC-16 General Process Flow Diagram for Certain IV-90
Dithiocarbamate Metallo-Organic Production
IVC-17 Liquid Formation Unit IV-92
IVD-1 Animal Glue Manufacturing Batch Process Flow Chart IV-106
IVD-2 Animal Glue and Gelatin Flow Chart from Raw IV-108
Materials to Products and By-Products
IVD-3 Batch Adhesive Manufacturing Process Flow Chart IV-109
IVD-4 Formaldehyde-Resin Batch Manufacturing Process IV-110
Flow Chart
IVE-1 Typical Nitroglycerin Production Schematic IV-118
IVE-2 Typical Ammonium Nitrate Production Schematic IV-120
IVE-3 Typical TNT Production Schematic IV-122
IVE-A Typical Schematic for RDX HMX Production IV-124
IVE-5 Nitrocellulose Powder Production Schematic IV-126
IVE-6 Solvent Propellant Production Schematic IV-127
IVE-7 Typical PETN Production and Acetone Recovery IV-131
Schematic
IVE-8 Typical Lead Azide Production Schematic IV-132
IVE-9 Typical Nitromanite or Isosorbide Dinitrate IV-13^
Production Schematic
XI
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DRAFT
LIST OF FIGURES
(continued)
Figures TI11e Page
IVE-10 Typical Lead Mononitroresorcinate Production IV-135
Schematic
IVF-1 Process Flow Sheet - Furnace Black Process IV-1^2
IVF-2 Simplified Flow Sheet - Thermal Black Process IV-lM
IVG-1 Black and White Film Processing IV-U8
IVG-2 Black and White Film Processing IV-1^9
IVG-3 Color Film Processing IV-150
IVG-J* Color Reversal Processing (Incorporated Couplers) IV-152
IVG-5 Color Reversal Processing (Couplers in Developer) IV-15^
VA-1 Category A - BODr Raw Waste Load Vs. Production V-9
VA-2 Category A - COD Raw Waste Load Vs. Production V-10
VA-3 Category A - TOC Raw Waste Load Vs. Production V-11
VA-1* Category A - Pollutant Waste Load Vs. Flow V-1^
Raw Waste Load
VA-5 Category B - Pollutant Waste Load Vs. Flow Raw V-15
Waste Load
VA-6 Category C - Pollutant Waste Load Vs. Flow Raw V-16
Waste Load
VA-7 Category D - Pollutant Waste Load Vs. Flow Raw V-18
Waste Load
VA-8 Category E - Pollutant Waste Load Vs. Flow Raw V-19
Waste Load
VE-1 Subcategory A1 - Explosive Manufacture - Pollutant V-71
RWL Vs. Raw Waste Flow
XI I
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LIST OF FIGURES
(continued)
Figures Title Page
VE-2 Subcategory A2 - Propellant Manufacture - Pollutant V-72
RWL Vs. Raw Waste Flow
VE-2 Subcategory B - Load and Pack - Pollutant RWL Vs. V-73
Raw Waste Flow
VE-4 Subcategory C - Specialty Manufacture - Pollutant \l-Jk
RWL Vs. Raw Waste Flow
VH-1 Pollutant Raw Waste Load Vs. Flow Raw Waste Load V-84
VIIA-1 Barometric Condenser VI1-5
VIID-1 Plywood Plant Glue Washwater Reuse System VI I-39
VIIIA-1 Pharmaceutical Industry - BPCTCA Cost Model VI 11-5
Subcategories A, B, C^ D and E
VIIIA-2 Pharmaceutical Industry - BPCTCA Cost Model - VI I 1-11
Subcategory C«
VIIIA-3 Pharmaceutical Industry - BATEA Cost Model - VI11-15
Subcategories A and C,
VIIIA-4 Pharmaceutical Industry - BADCT Cost Model - VI11-18
Subcategories A, B, C, D, and E
VIIIB-1 Gum and Wood Chemicals Industry - VIII-32
BPCTCA Cost Model
VIIIB-2 Gum and Wood Chemicals Industry - VI I I-36
BATEA Cost Model
VIIIC-1 Pesticides and Agricultural Chemicals Industry VII I-46
BPCTCA Cost Model - Subcategory A
VIIIC-2 Pesticides and Agricultura1 Chemicals Industry Vlll-Uy
BPCTCA Cost Mode? - Subcategory B
VIIIC-3 Pesticides and Agricultural Chemicals Industry VIN-48
BPCTCA Cost Model - Subcategory C
VMIC-4 Pesticides and Agricultural Chemicals Industry VIII-49
BPCTCA Cost Model - Subcategory D
xi i i
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DRAFT
LIST OF FIGURES
(continued)
Figures Title Page
VIIIC-5 Pesticides and Agricultural Chemicals Industry VIII-50
BPCTCA Cost Model - Subcategory E (Water Based)
VIIIC-6 General Wastewater Treatment Cost Model for VIII-57
Multi-Media Filtration and Activated Carbon
Adsorption
VlllC-7 Pesticides and Agricultural Chemicals Industry VI11-59
BPCTCA Cost Model
VIIID-1 Adhesive and Sealants Industry - BPCTCA Cost VIII-72
Model (Subcategory A)
VIIID-2 Adhesive and Sealants Industry - BPCTCA Cost VI I I-77
Model (Subcategories B and C)
VIIID-3 Adhesive and Sealants Industry - BATEA Cost VII1-80
Model (Subcategory A)
VIIID-4 Adhesive and Sealants Industry - BADCT Cost VI11-83
Model (Subcategory A)
VIIIE-1 Cost Model - Explosives Industry - BPCTCA VIII-9^
Waste Treatment Model
VMIE-2 Explosives Industry - BATEA Cost Model VII 1-97
VIIIF-1 Carbon Black Industry - BPCTCA Cost Model VI I I-105
VIIIF-2 BATEA Waste Treatment Model VI I I-106
VIIIF-3 Carbon Black Industry - BADCT Cost Model VII I-107
VIIIG-1 Photographic Processing Industry - BPCTCA VI I I-111
Cost Model
VIIIG-2 Photographic Processing Industry - BATEA Vlll-l!^
Cost Model
VIIIH-1 Hospitals - BPCTCA Cost Model VI I 1-119
VIIIH-2 BADCT and BATEA Cost Model - Hospitals VII I-122
xiv
-------
LIST OF TABLES
™
4) table No. Title Page
IA-1 Summary Table - Pharmaceutical Industry 1-7
IB-1 Summary Table - Gum and Wood Chemicals Industry 1-10
• IC-1 Summary Table - Pesticides and Agricultral 1-13
Chemicals Industry
ID-1 Summary Table - Adhesive and Sealants Industry 1-18
IE-1 Summary Table - Explosives Industry 1-21
*
IF-1 Summary Table - Carbon Black Industry 1-23
IG-1 Summary Table - Photographic Processing Industry 1-26
IH-1 Summary Table - Hospital 1-29
*
IIA-1 BPCTCA Effluent Limitations Guidelines - 11-7
Pharmaceutical Industry
IIA-2 BATEA Effluent Limitations Guidelines - 11-8
Pharmaceutical Industry
IIA-3 BADCT Effluent Limitations Guidelines - 11-9
Pharmaceutical Industry
IIB-1 BPCTCA Effluent Limitations Guidelines - 11-11
Gum and Wood Chemicals Industry
IIB-2 BATEA Effluent Limitations Guidelines - 11-12
Gum and Wood Chemicals Industry
IIB-3 BAOCT Effluent Limitations Guidelines - 11-13
Gum and Wood Chemicals Industry
IIC-1 BPCTCA Effluent Limitations Guidelines - 11-15
Pesticides and Agricultural Chemicals Industry
IIC-2 BATEA Effluent Limitations Guidelines - 11-16
Pesticides and Agricultural Chemicals Industry
IIC-3 BADCT Effluent Limitations Guidelines - 11-17
Pesticides and Agricultural Chemicals Industry
xv
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DRAFT
LIST OF TABLES
(continued)
Table No. Title Page
MD-1 BPCTCA Effluent Limitations Guidelines - Adhesive 11-19
and Sealants Industry
MD-2 BATEA Effluent Limitations Guidelines - Adhesive I 1-20
and Sealants Industry
IID-3 BADCT Effluent Limitations Guidelines - Adhesive 11-21
and Sealants Industry
IIE-1 BPCTCA Effluent Limitations Guidelines - 11-23
Explosives Industry
IIE-2 BATEA Effluent Limitations Guidelines - ll-2*»
Explosives Industry
IIE-3 BADCT Effluent Limitations Guidelines - 11-25
Explosives Industry
IIE-1 BPCTCA Effluent Limitations Guidelines - 11-27
Carbon Black Industry
IIF-2 BATEA and BADCT Effluent Limitations Guidelines - 11-28
Carbon Black Industry
I1G-1 BPCTCA Effluent Limitations Guidelines - M-30
Photographic Processing Industry
IIG-2 BATEA and BADCT Effluent Limitations Guidelines - 11-31
Photographic Processing Industry
IIH-1 BPCTCA, BADCT and BATEA Effluent Limitations 11-33
Guidelines - Hospitals
IIIA-1 Biological Products - SIC 2831 111-9
IIIA-2 Medicinal Chemicals and Botanical Products - 111-10
SIC 2833
IIIA-3 Pharmaceutical Products - SIC 283*» 111-11
1IIB-1 Chemicals Listed Under SIC 2861 111-15
MIB-2 Production and Product Value Gum and Wood 111-19
Chemicals Industry
xv 5
-------
LIST OF TABLES
(continued)
Table No. Title Page
MIC-T Products Covered IM-21
IIIC-2 U.S. Pesticides Production by Classes 111-22
(1969-1972)
MIC-3 Pesticides Classification 111-25
IMC-4 Structural Chemistry of Typical and Major IM-26
Pesticides
MID-1 Standard Industrial Classification of Products 111-35
from the Adhesives and Sealants Industry
MID-2 Production and Product Value Adhesive and 111-36
Sealant Industry
IIIE-1 Explosives Products - SIC 2892 IM-38
IIIE-2 Major Operations at Major Ammunition Plants MI-40
IIIF-1 Domestic Sales of Carbon Black in the United 111-46
States
IIIG-1 Photographic Studies, Portrait - SIC 7221 111-48
IIIG-2 Commercial Photography, Art, and Graphics - 111-48
SIC 7333
IIIG-3 Photofinish ing Laboratories - SIC 7395 111-48
MIG-4 Services Allied to Motion Picture Production - 111-48
sic 7819
IVA-1 Flowsheet of Protein Fractionation of Plasma IV-15
IVB-1 Statistics by Geographical Areas Gum and Wood IV-40
Chemicals Industry
IVB-2 Comparison of Raw Waste Loads by Product Grouping IV-42
IVB-3 Factors Considered for Basis of Gum and Wood IV-43
Chemicals Industry Subcategorization
xvi i
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LIST OK TABLES
(continued)
Table No. Title Page
IVD-1 Principal Raw Materials Used in Adhesive and IV-98
Sealants Manufacturing
IVE-1 Common Ingredients of Dynamites IV-121
IVE-2 Ingredients of Water Gels and Slurries IV-129
VA-1 Pharmaceutical Industry - Raw Waste Loads V-8
VA-2 Comparison of RWL Data - Pharmaceutical Industry V-21
VB-1 Effect of Process Modification V-28
VB-2 Gum and Wood Chemicals - Major BPCTCA Raw V-30
Waste Loads
VD-1 Characterization of Waste Discharge - Adhesive V-5^
and Sealants Industry, Category A
VD-2 Characterization of Waste Discharges - V-55
Subcategory B
VD-3 Characterization of Waste Discharge - V-55
Subcategory C
VD-A Raw Waste Loads - Adhesive and Sealants Industry V-58
VD-5 Raw Waste Loads - Adhesive and Sealants Industry V-59
VD-6 Raw Waste Load Variability - Adhesive and V-61
Sealants, Subcategory B
VE-1 Raw Waste Loads - Explosives Industry V-66
VE-2 Raw Waste Loads - Explosives Industry V-67
VE-3 Concentration of Pollutants - Explosives Industry V-68
VF-1 Raw Waste Loads - Carbon Black Industry V-77
VG-1 Raw Waste Loads - Photographic Processing Industry V-79
VH-1 Raw Waste Loads - Hospitals V-81
xv i i i
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LIST OF TABLES
(continued)
Table No. Title Page
VI-1 Miscellaneous Chemicals Industry VI-2
List of Pollutants to be Examined
VIIA-1 Treatment Technology Survey Pharmaceutical Industry VII-9
VIIA-2 Summary of Statistical Analysis of Historical Vll-11
Treatment Data - Pharmaceutical Industry
VMA-3 Treatment Plant Survey Data - Pharmaceutical VI1-13
Industry
VMA-4 Summary of COD Carbon Isotherm Tests Performed VII-15
on Biological Treatment Plant Effluent -
Pharmaceutical Industry
VIIA-5 Summary of BODj Carbon Isotherm Tests Performed VI1-16
on Biological Treatment Plant Effluent -
Pharmaceutical Industry
VIIA-6 Summary of TOC Carbon Isotherm Tests Performed VI1-17
on Biological Treatment Plant Effluent -
Pharmaceutical Industry
VIIA-7 Results of Filtration Tests on Biological VII-19
Treatment Plant Effluent - Pharmaceutical
Industry
VIIB-1 Treatment Technology Survey - Gum and Wood VII-21
Chemicals Study
VIIB-2 Treatment Plant Survey Data - Gum and Wood VI1-23
Chemicals Industry
VIIB-3 Historic Treatment Plant Performance \l\\-2k
Gum and Wood Chemicals Industry
VIIB-4 Summary of COD Carbon Isotherm Data - Gum and VII-27
Wood Industry
VIIC-1 Treatment Technology Survey - Pesticides and VI1-33
Agricultural Chemicals Industry
VMC-2 Effluent Quality Data From Selected Pesticide VI1-34
Production Facilities - Pesticide and
Agricultural Chemicals Industry
xix
-------
LIST OF TABLES
(continued)
Tab 1e Title Page
VIIC-3 Source of Historical Data - RWL VI1-35
Pesticide and Agricultural Chemicals Industry
VIIE-1 Summary of Treatment Investigations VI1-48
Explosives Industry
VIIF-1 Treatment Technology Survey VI1-55
Carbon Black Industry
VIIF-2 Wastewater Treatment Plant Performance Data VI1-56
Carbon Black Industry
VIIG-1 Summation of Ozonation Results (G-11) VII-65
Photographic Processing Industry
VIIG-2 Feasibility of Treating Photographic Processing VII-66
Chemicals with Activated Carbon (G-11)
Photographic Processing Industry
VIIH-1 Treatment Technology Survey - Hospitals VI1-69
VIIH-2 Summary of Historic Treatment Performance VI1-70
Hospitals
VIIH-3 Survey Data - Wastewater Treatment Plant VI1-71
Hospitals
XX
-------
LIST OF TABLES
Table No. Title Page
VIIIA-1 BPCTCA Waste Treatment Cost Models VI I 1-6
VIIIA-2 BPCTCA Cost Mode) Design Summary
Pharmaceutical Industry
Subcategories A, B, Cj, C2, D and E VI I 1-7
VIIIA-3 BPCTCA End-of-Pipe Treatment System Requirements
Pharmaceutical Industry
Subcategories A, B, Cj, C2> D and E VI I 1-10
VIIIA-4 BPCTCA End-of-Pipe Treatment System
Design Summary
Pharmaceutical Industry
Subcategory C2 VI I 1-12
VIIIA-5 BATEA Cost Model Design Summary
Pharmaceutical Industry
Subcategories A, B, Cj , D and E VI11-16
VIIIA-6 BADCT Treatment System Design Summary
Pharmaceutical Industry
Subcategories A, B, Cj, D and E VI 11-19
VIIIA-7 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory A VI I 1-21
VIIIA-8 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory B VI I 1-22
VIIIA-9 Wastewater Treatment Costs for BPCTCA,
BADCT and Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory Ci VI I 1-23
VIIIA-10 Wastewater Treatment Costs for
BPCTCA, BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory C VIII-2A
xx i
-------
LIST OF TABLES
(Cont inued)
Table No. Title
VIIIA-11 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory D VI I 1-25
VIIIA-12 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pharmaceutical Industry - Subcategory E VI I 1-26
VIIIA-13 Per Gallon Capital and Yearly Operation
and Maintenance Costs for the Pharmaceutical
Industry Model Treatment Plants VI I 1-28
VIIIB-1 BPCTCA Treatment System Design Summary
Gum and Wood Chemicals Industry VI I 1-33
VIIIB-2 BATEA End-of-Pipe Treatment System Design
Summary VI I I-37
VIIIB-3 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Gum Turpentine and Rosin - Subcategory B VI I 1-39
VIIIB-4 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Wood Turpentine and Rosin - Subcategory C VI11-40
VIIIB-5 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Tall Oil Fractionation - Subcategory D VI I 1-42
VIIIB-6 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Essential Oil - Subcategory E VI11-43
XXI I
-------
LIST OF TABLES
(Continued)
Table No. Title Page
VIIIB-7 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Rosin Derivatives - Subcategory F VIII-M
VIIIC-1 BPCTCA Treatment System Design Summary
Pesticides and Agricultural Chemicals Industry VI I 1-51
VIIIC-2 BATEA Treatment System Design Summary VI 11-58
VIIIC-3 BADCT Treatment System Design Summary VI 11-60
VIIIC-4 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry -
Halogenated Organic Subcategory: Typical
Small Plant VI11-63
VIIIC-5 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry -
Halogenated Organic Subcategory: Typical
Large Plant VI I 1-64
VIIIC-6 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Chemicals Industry
Organo Phosphorus Subcategory: Typical
Small Plant VI I 1-65
VIIIC-7 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry
Organo Phosphorus Subcategory: Typical
Large Plant VI I 1-66
VIIIC-8 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticide and Agricultural Chemicals Industry
Organo Nitrogen Subcategory: Typical
Smal1 Plant VI I 1-67
XX I I I
-------
LIST OF TABLES
(Continued)
Table No. Title
VIIIC-9 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry -
Organo Nitrogen Subcategory: Typical
Large Plant VI I 1-68
VIMC-10 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry -
Metallo-Organic Subcategory VI I 1-69
VIIIC-11 Wastewater Treatment Costs for BPCTCA,
BADCT and BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Pesticides and Agricultural Chemicals Industry -
Formulators/Packagers Subcategory VI I 1-70
VIIID-1 BPCTCA Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A VII1-73
VIIIB-2 BPCTCA Treatment System Design Summary
Adhesive and Sealants Industry
Subcategories B and C VI I 1-78
VIIID-3 BPCTCA End-of-Pipe Treatment System Require-
ments - Adhesives and Sealants Industry
Subcategories B and C VI I 1-79
VIIID-4 BATEA Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A VI I 1-81
VIMD-5 BATEA End-of-Pipe Treatment System Require-
ments - Adhesives and Sealants Industry
Subcategory A VI I 1-82
VIIID-6 BADCT Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A VII I-84
XXI V
-------
LIST OF TABLES
(continued)
Table Title Page
VIIID-7 BADCT End-of-Pipe Treatment Systems Requirements VI I I-85
Adhesives and Sealants Industry
Subcategory A
VIIID-8 Wastewater Treatment Costs for BPCTCA, BADCT and VI11-87
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Adhesive and Sealants Industry
Subcategory A
VIIID-9 Wastewater Treatment Costs for BPCTCA, BADCT and VII 1-88
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Adhesive and Sealants Industry
Subcategory B
VMID-10 Wastewater Treatment Costs for BPCTCA, BADCT and VIII-89
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Adhesive and Sealants Industry
Subcategory C
VIIIE-1 BPCTCA Treatment System Design Summary VI11-92
Explosives Industry
VIIIE-2 BATEA and BADCT Treatment System Design Summary VI11-96
Explosives Industry
VIIIE-3 Wastewater Treatment Costs for BPCTCA, BADCT and VII I-100
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Explosive Industry
Subcategory Aj
VIIIE-4 Wastewater Treatment Costs for BPCTCA, BADCT and VI11-101
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Explosive Industry
Subcategory A£
VIIIE-5 Wastewater Treatment Costs for BPCTCA, BADCT and VIM-102
BATEA Effluent Limitations (ENR 1780 - August,
1972 Costs)
Explosive Industry
Subcategory B
xxv
-------
LIST OF TABLES
(continued)
Table . Title Page
«
VIIIE-6 Wastewater Treatment Costs for BPCTCA, BADCT and VI I 1-103
BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Explosive Industry
Subcategory C
VIIIF-1 Wastewater Treatment Costs for BPCTCA, BADCT and VI I 1-109
BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Carbon Black Industry
Subcategory B
VIIIG-1 Wastewater Treatment Costs for (BPCTCA, BADCT and VI11-116
BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Photographic Processing Industry
VIIIH-1 BPCTCA Treatment Systems Design Summary VI 11-120 •
Hospitals
VIIIH-2 BADCT Treatment System Design Summary VII I-123
Hospitals ^^
VIIIH-3 Wastewater Treatment Costs for BPCTCA, BADCT and VIII-12^ •
BATEA Effluent Limitations
(ENR 1780 - August, 1972 Costs)
Hospitals
XXVI
-------
LIST OF TABLES
(continued)
Table Title
IXA-1 BPCTCA Effluent Limitations Guidelines IX-3
Pharmaceutical Industry
IXB-1 BPCTCA Effluent Limitations Guidelines IX-8
Gum and Wood Chemicals Industry
IXC-1 BPCTCA Effluent Limitations Guidelines IX-11
Pesticides and Agricultural Chemicals
IXD-1 BPCTCA Effluent Limitations Guidelines IX-15
Adhesive and Sealants Industry
IXE-1 BPCTCA Effluent Limitations Guidelines IX-18
Explosives Industry
IXF-1 BPCTCA Effluent Limitations Guidelines IX-20
Carbon Black Industry
IXG-1 BPCTCA Effluent Limitations Guidelines IX-23
Photographic Processing
IXH-1 BPCTCA Effluent Limitations Guidelines IX-25
Hospitals
XA-1 BATEA Effluent Limitations Guidelines X-U
Pharmaceutical Industry
XB-1 VATEA Effluent Limitations Guidelines X-6
Gum and Wood Chemicals Industry
XC-1 BATEA Effluent Limitations Guidelines X-8
Pesticides and Agricultural Chemicals Industry
XD-1 BATEA Effluent Limitations Guidelines X-11
Adhesive and Sealants Industry
XE-1 BATEA Effluent Limitations Guidelines X-12
Explosives Industry
XF-1 BATEA Effluent Limitations Guidelines X-15
Carbon Black Industry
xxv i i
-------
LIST OF TABLES
(continued)
Table Title Page
XG-1 BATEA Effluent Limitations Guidelines X-17
Photographic Processing Industry
XH-1 BATEA Effluent Limitations Guidelines X-19
Hospi tals
XIA-1 New Source Performance Standards XI-3
Pharmaceutical Industry
XIB-1 New Source Performance Standards XI-5
Gum and Wood Chemicals Industry
XIC-1 New Source Performance Standards XI-7
Pesticides and Agricultural Chemicals Industry
XID-1 New Source Performance Standards XI-9
Adhesive and Sealants Industry
XIE-1 New Source Performance Standards XI-11
Explosives Industry
XIF-1 New Source Performance Standards XI-12
Carbon Black Industry
XIG-1 New Source Performance Standards XI-14
Photographic Processing Industry
XIH-1 New Source Performance Standards XI-16
Hospi tals
XIIA-1 Pretreatment Unit Operations XI1-4
Pharmaceutical Industry
XIIB-1 Pretreatment Unit Operations XI1-6
Gum and Wood Chemical Industry
XIID-1 Pretreatment Unit Operations XI 1-10
Adhesive and Sealants Industry
XIIH-1 Pretreatment Unit Operations XII-15
Hospitals
XXVI I I
-------
LIST OF TABLES
(cont inued)
Table Title
XIIIA-1 Exemplary Biological Treatment Plant Performance XI I I-k
Pharmaceutical Industry
XIIIA-2 Average Ratios of Probabilities of Occurrence XIII-5
Pharmaceutical Industry
XIIIH-1 Effluent Variation of Activated Sludge Treatment XI I 1-16
Plant Effluents -
Hospitals
XXIX
-------
SFCTION I
CONCLUSIONS
General
The Miscellaneous Chemicals industry encompasses eight industries,
grouped together for administrative purposes. Each industry differs
from the others in raw materials used, manufacturing processes employed,
and the final products. Water usage and subsequent wastewater discharges
also vary considerably from industry to industry. Consequently, for the
purpose of the development of the effluent limitations guidelines and
corresponding BPCTCA (Best Practicable Control Technology Currently
Available), New Source, and BATEA (Best Available Technology Eco-
nomically Achievable) requirements, each industry is treated inde-
pendent ly.
The Miscellaneous Chemicals industry was defined by EPA for the purpose
of this study to include those commodities listed under the following
Standard Industrial Classifications (SIC):
SIC 2831 - Biological Products
SIC 2833 - Medicinal Chemicals and Botanical Products
SIC 2834 - Pharmaceutical Preparations
SIC 2861 - Gum and Wood Chemicals
SIC 2879 - Agricultural Chemicals (Formulations)
SIC 2879 - Pesticides £- Agricul tural Chemicals
SIC 2891 - Adhesive and Sealants
SIC 2892 - Explosives
SIC 2895 - Carbon Black
SIC 2899 - Chemicals and Chemical Preparation, Not Elsewhere
Classified
SIC 7221 - Photographic Studios, Portrait
SIC 7333 - Commercial Photography, Art and Graphics
SIC 7395 - Photofinishing Laboratories
SIC 7819 - Developing and Printing of Commercial Motion
Picture Film
SIC 8062 - General Medical and Surgical Hospitals
SIC 8063 - Psychiatric Hospitals
SIC 8069 - Specialty Hospitals
The diversity of products and manufacturing operations to be covered
indicates the need for separate effluent limitations guidelines for
different industries, and these are presented in the following sections.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
It should be emphasized that the proposed mode] technology be used
only as a guideline and may not be applicable In c-vcry C.IM-. The cost
models for BPCTCA, BATEA and BADCT were developed only to f.ici I I tntr
the economic analysis and should not be construed as the only technology
capable of meeting the effluent limitations guidelines and standards of
performance presented in this draft development document. There are many
alternative systems which, taken either singly or in combination, are
capable of attaining the effluent limitations guidelines and standard of
performance recommended in this draft development document. These alter-
native choices include:
1. Various types of end-of-pipe wastewater treatment.
2. Various in-plant modifications and installation of at-
1
source pollution control equipment.
3. Various combinations of end-of-pipe and in-plant technologies.
The complexity of the Miscellaneous Chemicals Industry dictated the use
of only one treatment model for each subcategory for each effluent level.
It is the intent of this study to allow the individual manufacturer within
the Miscellaneous Chemicals Industry to make the ultimate choice of what
specific combination of pollution control measures is best suited to his
situation in complying with the limitations and standards of perform-
ance presented in this draft development document.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-2
-------
A. Pharmaceutical Industry
The Pharmaceutical industry produces hundreds of medicinal chemicals
by means of many increasingly complex manufacturing technologies.
Water usage and subsequent wastewater discharges are closely related
to these products and production processes. Any rational approach
to effluent limitations guidelines based on production must recognize
these complexities.
For the purpose of establishing effluent limitations guidelines and
standards of performance, the Pharmaceutical industry has been
divided on the basis of manufacturing techniques, product type, raw
materials, and wastewater characteristics into five separate sub-
categories. Factors such as plant size, plant age, geographic
location, and air pollution control equipment were also considered
but did not justify further subcategorization of the industry.
Each of these factors and impact thereof on categorization is dis-
cussed in detail in Section IV. The five subcategories are:
A. Fermentation Product Manufacturers. The production of
fermentation products (antibiotics and steroids) is re-
stricted to a few of the larger pharmaceutical firms.
Most antibiotics are produced in batch fermentation
tanks in the presence of a particular fungus or bacterium.
B. Biological and Natural Extraction Product Manufacturers.
Biological and natural extraction products include various
blood fractions, vaccines, serums, animal bile derivatives,
and plant tissue derivatives. These products are produced
in laboratories on a much smaller scale than most pharma-
ceutical products.
C. Chemical Synthesis Production. The production of chemical
synthesis products is very similar to fine chemicals pro-
duction. Chemical synthesis reactions generally are batch
types which are followed by solvent extraction of the prod-
uct. Subcategory C has been further divided into sub-
categories C1 and C . Subcategory ^2 includes those plants
which manufacture antibiotics by chemical synthesis; C
covers all the other chemical synthesis plants.
D. Mixing/Compounding or Formulation Production. The manu-
facturing operations for formulation plants may be either
dry or wet. Dry production involves dry mixing, tableting
or capsuling, and packaging. Process equipment is gener-
ally vacuum-cleaned to remove dry solids and then washed
down. Wet production includes mixing, filtering, and
bottling. Process equipment is washed down between pro-
duction batches.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
E. Microbiological. Biological, and Chemical Research. Research
is another important part of the Pharmaceutical industry.
Although such facilities do not produce specific marketable
products, they do generate wastewaters. These originate
primarily from equipment and vessel washings and animal
cage washwaters.
Pharmaceutical plants operate throughout the year. Production processes
are primarily batch operations, with significant variations in pollutional
characteristics over any typical operating period. The characteristics
of wastewaters vary from plant to plant according to the products and
processes used. Depending on the product mix and the manufacturing pro-
cess, hourly variations in wastewater volume and loading may occur as a
result of certain batch operations (filter washing, crystallization,
solvent extraction, etc.).
The Pharmaceutical industry uses water extensively both in processing
and for cooling. The plant wastewater collection systems are
generally segregated to permit separate collection of process waste-
waters and relatively clean noncontact cooling waters. The process
wastewaters are usually discharged to a common sewerage system for
treatment and disposal.
The major sources of wastewaters in the Pharmaceutical industry are
product washings, extraction and concentration procedures, and equip-
ment washdown. Wastewaters generated by this industry can be charac-
terized as containing high concentrations of Biochemical Oxygen Demand
(BOD), Chemical Oxygen Demand (COD), Total Suspended Solids (TSS), and
solvents. Wastewaters from some chemical synthesis and fermentation
operations may contain metals (Fe, Cu, Ni, Ag, etc.), cyanide, or anti-
bacterial constituents which may exert a toxic effect on biological
waste treatment processes. Pretreatment at-source to remove these
constituents may be required.
Existing control and treatment technology, as practiced by the industry,
includes in-plant abatement as well as end-of-pipe treatment. Recovery
and reuse of expensive solvents and catalysts are widely practiced in
the Pharmaceutical industry for obvious economic reasons. Current end-
of-pipe wastewater treatment technology involves biological treatment,
physical/chemical treatment, thermal oxidation, or liquid evaporation.
Biological treatment includes activated sludge, trickling filters, and
aerated lagoon systems.
The effluent limitations guidelines proposed herein are based solely on the
contaminants in the contact wastewaters associated with the processes pre-
viously discussed in the subcategory descriptions. No specific limitations
are proposed for pollutants associated with noncontact wastewaters such as
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
boiler and cooling tower blowdown. Effluent limitations guidelines for
these two streams are developed in a separate set of guidelines for the
Steam and Noncontact Cooling Water Industries.
Since both the raw waste loads (RWL) and the related of fluent limitation'*
guidelines developed for the Pharmaceutical industry are based solely on
contact process wastewater, it follows that other noncontact wastewaters
(including sanitary wastes) will not be included in the effluent
limitations guidelines.
Separate effluent limitations guidelines are presented for each of the
five subcategories. The wastewater parameters selected are: Biochemical
Oxygen Demand (BODr), Chemical Oxygen Demand (COD), and Total Suspended
Solids (TSS). The choice of these parameters reflects the fact that organic
oxygen-demanding material is the major contaminant in wastewaters gen-
erated by the Pharmaceutical industry. Ammonia, and organic nitrogen
and phosphorus were found in significant quantities; however, in the
absence of economically feasible technology for their removal, the
best approach to control appears to be in-plant measures or at-source
treatment in those special cases where excessive discharge of ammonia,
organic nitrogen, or phosphorus is encountered.
Because of extensive in-plant recovery and recycle operations, as described
in Section VII, metals and other toxic materials were not found in sig-
nificant quantities in pharmaceutical plant wastewaters. Other possible
RWL parameters (phenol, chlorinated hydrocarbons, various metals, etc.)
were considered during the study but were found to be unrelated to pro-
duction and/or were present in concentrations substantially lower than
those which would require specialized end-of-pipe treatment for the entire
i ndust ry.
It was concluded that the model BPCTCA wastewater treatment technology
for subcategories A, B, C , D and E should consist of equalization fol-
lowed by a biological treatment system with sludge handling and treatment
facilities. The sludge disposal system would generally consist of sludge
thickening, aerobic digestion, vacuum filtration, and ultimate disposal
via land-fill. In addition, neutralization facilities preceding the
biological system would generally be required for those plants falling
in subcategories A and C • For subcategory C , thermal oxidation was
selected for the BPCTCA, BADCT and BATEA mode? wastewater treatment
technologies. Wastewaters from this subcategory have been characterized
as low-flow and high-strength. It should be emphasized that the proposed
model technology should be used only as a guideline and may not be appli-
cable in every case. Biological treatment models have been developed
only to facilitate the economic comparisons and the indicated treatment
is not to be thought of as the only technology capable of meeting the
effluent limitations guidelines and standards of performance presented
in this draft development document. Each manufacturing facility should
be evaluated separately to determine the unit operations needed to meet
wastewater effluent limitations guidelines applicable for that plant.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-5
-------
The model BATEA treatment facility for subcategories A and C., consists
of BPCTCA technology followed by dual-media filtration and activated
carbon adsorption. BATEA effluent limitations guidelines for sub-
categories B, D, and E are based on the addition of dual-media filtration
to the proposed BPCTCA treatment technology. The treatment technology
suggested to meet the proposed New-Source Performance Standards (BADCT)
for subcategories A, B, C,, D, and E consists of the BPCTCA treatment
system plus dual-media filtration.
The data required to compute effluent limitations for specific cases
include the identity of the specific manufacturing process and the actual
production rate. This information is sufficient to subcategorize the
process and subsequently compute the appropriate effluent limitations,
based on the pollutant RWL specified for that subcategory.
It should be noted that the actual effluent limitations guidelines would be
applied directly only to a plant whose manufacturing processes fall within
a single subcategory. For multi-process plants, the effluent pollutant
limitations would be equal to the sum of the individual effluent limi-
tations applied to each of its processes. This value represents the
long-term average dally discharge value for the plant. An appropriate
performance factor can then be applied to obtain maximum average of daily
values for any period of thirty consecutive days or maximum daily pol-
lutant discharge rate. These performance factors allow for fluctuations
in treatment plant performance and sampling frequency, and are necessary
for a meaningful basis for subsequent spot checking and future enforce-
ment action by EPA. These performance factors are developed for the
Pharmaceutical industry from historical operations data from several
exemplary end-of-pipe biological treatment plants.
Table IA-1 summarizes the contaminants of interest, raw waste loads, and
recommended treatment technologies for BPCTCA, BATEA, and BADCT for each
subcategory of the Pharmaceutical industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-6
-------
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-------
B. Gum and Wood Chemicals Industry
For the purpose of developing recommended effluent limitations guide-
lines and new-source performance standards for the Gum and Wood
Chemicals industry, the industry has been subcategorized as follows:
A. Char and charcoal briquet manufacture by carbonization of
hardwood and softwood scraps.
B. Gum rosin and turpentine manufacture by steam distillation
of crude gum (exudate) from living longleaf pine and slash
pine trees.
C. Wood rosin, turpentine, and pine oil manufacture by solvent
extraction-steam distillation of old resinous wood stumps
from cut-over pine forests.
D. Tall oil rosin, pitch, and fatty acids manufacture by
fractionation of crude tall oil, a by-product of the Kraft
(sulfate) pulping process.
E. Essential oils manufacture by steam distillation of scrap
wood fines from select lumbering operations.
F. Rosin-based derivatives (specifically, rosin esters and
modified rosin esters) manufacture by the chemical reaction
of gum, wood, or tall oil rosins.
The criteria used for establishing the above subcategorization were the
impact of the following factors on the above groupings:
1. Production processes.
2. Product types and yields.
3. Raw material sources.
4. Wastewater quantities, characteristics, control and treatment.
The wastewater parameters of significance in the Gum and Wood Chemicals
industry are BOD,., COD, TOC, oils and grease, and pH. In addition, for
subcategory F phenol was found to be a significant parameter.
Complete elimination of discharge of process wastewater pollutants should
be achievable for subcategory A. Individual effluent limitations guide-
lines were recommended for subcategories B through F for BODV and COD.
Limitations on TSS effluent concentrations are recommended for BPCTCA,
BADCT, and BATEA technology levels.
Other RWL parameters were considered during the study, and specific
products or pollutants which might be inhibitory or incompatible with
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
I-8
-------
BPCTCA treatment technology are cited in Section VI. It was concluded
that the model BPCTCA wastewater treatment technology for this indus-
trial category should consist of a biological treatment system. Typical
exemplary processes are activated sludge or aerated lagoons with clari-
fication. These systems may require pH control and equalization in order
to control variable waste loads, and phosphorus and nitrogen nutrient
addition to insure maintenance of an activated sludge with desirable
performance and handling characteristics. These systems do not preclude
the use of equivalent physical-chemical systems such as activated carbon
in a suitable situation where the significant land area that would
otherwise be required (for activated sludge or aerated lagoon) is not
available. Additionally, in-process controls are recommended to control
those pollutants which may be inhibitory to the biological waste treat-
ment system, as well as segregation of noncontact cooling waters and
boiler blowdowns.
End-of-process wastewater treatment technology for new sources utilizing
the best available demonstrated control technology (BADCT) is a biological
treatment system with suspended solids removal by means of dual-media
filtration. In addition, exemplary in-process controls are also recom-
mended, particularly where biologically inhibitory pollutants must be
control led.
Best available technology economically achievable (BATEA - 1983 Standard)
is based upon the addition of filtration and activated carbon to BPCTCA
treatment. This technology is based upon substantial reductions of dis-
solved organics which are biorefractory as well as those which are bio-
degradable.
In conclusion, effluent limitations guidelines were derived on the basis
of the maximum for any one day and the maximum average of daily values
for any period of thirty consecutive days. Since no long-term data for
exemplary treatment were uncovered in the Gum and Wood Chemicals in-
dustry during this study, the factors used in deriving these time-
based limitations guidelines were derived from long-term performance
data from the systems evaluated by EPA for the Petroleum refining
industry.
Table IB-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA, and BADCT for
each subcategory of the Gum and Wood Chemicals industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
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NOT ICC; THESE ARE TENTATIVE RECONHENOATIONS BASED UPON INFORMATION
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-------
C. Pesticides and Agricultural Chemicals Industry
There ore five major groupings in the pesticides segment ol 1 he:
Miscellaneous Chemicals industry which this report encompasses.
These subcategories include:
A. Halogenated Organic Pesticides.
B. Organo-Phosphorus Pesticides.
C. Organo-Nitrogen Pesticides.
D. Metallo-Organic Pesticides.
E. Formulators and Packagers.
Process wastewaters evolved from facilities within the Halogenated
Organ ic pesticide subcategory are primarily due to wet scrubbing,
caustic soda scrubbing, and contact cooling systems. Organic load-
ings are the result of decanting, distillation, and stripping
operations. Other significant process wastewater streams include
spillage, washdowns and runoff.
To be controlled and treated, process wastewaters must be isolated
from nonprocess wastewaters such as utility discharges and uncontam-
inated storm runoff. BPCTCA treatment of the process wastewaters
includes equalization, neutralization, skimming of separable organics
and biological treatment. Incineration or contract disposal of strong
or toxic wastes may be necessary.
The Organo-Phosphorus pesticides facilities produce wastewaters with
high organic loadings from decanter units, distillation towers, over-
head collectors, and solvent strippers. Caustic scrubbing and con-
tact cooling are the major contributors to total flow, and highly
alkaline wastes result from caustic scrubbing, hydrolyzing, and
product washing.
The BPCTCA technologies necessary to control and treat wastewaters
from this category include isolation of process streams, separation
of insoluble organics, alkaline hydrolysis, equalization, neutraliza-
tion, and biological treatment. Incineration or contract disposal
may be required for very strong or toxic wastes.
Scrubbing operations are the major contributor to the tota? effluent
flow rate for facilities producing pesticides of the Organo-Nitrogen
subcategory. Nitrogen loadings are due primarily to decanting opera-
tions and extractor/precipitator units. Organic loadings are due to
solvent stripping and various purification steps. High organic and
solids loadings can result from accidental spillage, equipment clean-
out, and area washdowns.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-11
-------
Treatment of process wastewnters from Ortj,ino-NI t rot|r>n |>t".i l< hlf
facilities includes neutralization, separable organic s srpnrnlIon,
equalization, and biological treatment. Inclncrnt Ion or conlr.-ut
disposal of very strong or toxic wastes is required in some crises.
Process wastewaters produced by facilities within the Metallo-Orqanic
subcategory may contain significant ammonia nitrogen concentrations.
Solids loadings are due for the most part to various product washing
steps. These washing steps also contribute a large portion of the
flow. Spillage, rinses, and washdowns are a source of organic and
sol ids loadings.
BPCTCA control and treatment of process wastewaters in this sub-
category include metals precipitation, equalization, neutralization
and biological treatment. Incineration or contract disposal of very
strong toxic wastes may be necessary for some facilities.
Formulators and packagers can be divided into two subcategories:
dry-solvent-based and water based. Water-based formulations are
the only type of operation that produce process wastewaters. Wash-
ing and cleaning operations are the primary source of organic and
solids loadings. Air emission control devices also account for sus-
pended and dissolved solids loadings.
Since formulators and packagers can handle any of the above-mentioned
subcategories, technologies necessary to control and treat the waste-
waters can be a combination of those previously discussed. In general,
BPCTCA treatment includes sedimentation and hydrolysis, neutralization
and biological treatment.
Solvent-based and dry formulated and packaged products generate low
volumes of contaminated waste which can be drummed and handled
adequately by disposal contractors.
Table IC-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA and BADCT
for each subcategory of the Pesticides and Agricultural Chemicals
industry.
BATEA treatment technology for all subcategories includes dual-media
filtration plus activated carbon adsorption with BPCTCA technology.
Control technology for BADCT includes dual-media filtration in
addition to BPCTCA technology for all subcategories.
In conclusion, effluent limitations guidelines were derived on the
basis of the maximum for any one day and the maximum average of daily
values for any period of thirty consecutive days. Since no long-term
data for exemplary treatment were uncovered in the pesticides and agri-
cultural chemicals industry during this study, the factors used in de-
riving these time-based limitations guidelines were derived from long-
term performance data from the exemplary systems evaluated in the
Pharmaceutical industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-12
-------
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D. Adhesive and Sealants Industry
The Adhesive and Sealants industry is one in which a wide variety of
chemicals are used as raw material. The water usage and subsequent
wastewater discharges of this industry are as diverse as its mix of prod-
ucts. Any rational approach to effluent limitations guidelines based on
production must take the complexity of the industry into account. The
diversity of its products indicates the need for separate limitations
for different segments of the Industry.
For the purpose of developing recommended effluent limitations guide-
lines and new source performance standards for the Adhesive and Sealants
Industry, the Industry has been subcategorlzed as follows:
A. Water-based animal glue and gelatins.
B. Water-based adhesive solutions containing synthetic
and natural materials.
C. Solvent solution adhesives and cements generating con-
taminated wastewaters.
D. Solvent solution adhesives and cements generating
noncontact cooling water only.
E. Solid and semi-solid hot melt thermoplastic adhesives.
F. Dry-blended adhesive materials.
The criteria used for establishing the above subcategorization were
the impacts of the following factors of the foregoing groupings:
1 . Product types.
2. Raw material sources.
3. Wastewater quantities and characteristics.
^. Production processes.
The effluent limitations guidelines proposed herein are based on the
dissolved organic contaminants and suspended solids in the contact waste-
waters associated with the processes listed in the various subcategories.
No specific limitations are proposed for pollutants associated with
noncontact wastewaters, such as boiler and cooling tower blowdown.
These pollutants will be covered by effluent limitations guidelines
for the Steam Supply and Noncontact Cooling Water industries, now
being developed.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED-UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-15
-------
The wastewater parameters of significance in the Adhesive and Seal-
ants industry are BOD,-, COD, TOC, and TSS. Their significance reflects
the fact that dissolved organic oxygen-demanding material and sus-
pended solids are the major contaminants in the production operations
of the Adhesive and Sealants industry. Separate limitations for these
parameters are presented for each subcategory.
Other RWL parameters were considered during the study, and specific
products or pollutants which might be inhibitory or Incompatible with
biological treatment technology are discussed in Section VI.
It was concluded that the model BPCTCA wastewater treatment technology
should consist of a biological treatment for subcategory A, and double-
effect liquid evaporation for subcategories B and C. The biological
system may require equalization in order to control variable waste loads.
The evaporation treatment system will also require equalization in
order to control variable wastewater flows. Other treatment schemes
applicable to these types of wastewaters include activated carbon and
liquid incineration. No discharge of process pollutants is recommended
for subcategories E and F.
Best Available Technology Economically Achievable (BATEA - 1983
Standard) is based upon the addition of second-stage biological treat-
ment and dual-media filtration to the BPCTCA treatment for subcategory
A. BPCTCA and BATEA treatments for subcategories B and C are the same.
End-of-process wastewater treatment technology for new sources utiliz-
ing the Best Available Demonstrated Control Technology (BADCT) is the
same as BPCTCA for subcategories B and C and the addition of filtration
to BPCTCA for subcategory A. In addition, in-plant controls and/or
pretreatment are also applicable for the control of those pollutants
which may be inhibitory to a biological waste treatment system.
It should be emphasized that the proposed treatment models are selected
only to facilitate the economic analysis and are not to be thought of
as the only technology capable of meeting the effluent limitations guide
lines and standards of performance presented in this draft development
document. The same results could be achieved by other end-of-pipe
treatment technology or solely by in-plant measures or any combination
of in-plant measure and end-of-pipe treatment technology.
It should be noted that the actual effluent limitations guidelines would
be applied directly only to a plant whose manufacturing processes fall
within a single subcategory. This situation will occur only seldom,
because most plants are usually associated with multi-product
manufacturing. In this case, the effluent limitations guidelines placed
upon a plant would be the sum of the individual effluent limitations
guidelines applied to each of its processes.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-16
-------
In conclusion, effluent limitations guidelines were derived on the basis
of the maximum for any one day and the maximum average of daily values for
any period of thirty consecutive days. Since no long-term data for
exemplary treatment were uncovered in the Adhesive and Sealants industry
during this study, the factors used in deriving these time-based limita-
tions were derived from long-term performance data from the exemplary
systems evaluated in the Pharmaceutical industry.
Table .0-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA and BADCT
for each subcategory of the Adhesive and Sealants industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-17
-------
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1-18
-------
Explosives Industry
For the purposes of developing effluent limitations guidelines iind
standards of performance, the Explosives industry h
-------
End-of-process wastewater treatment technology for new sources
utilizing the Best Available Demonstrated Control Technology (BADCT)
is defined as biological treatment with suspended solids removal via
filtration. In addition, exemplary in-process controls
are applicable, particularly where biologically inhibitory pollutants
must be control led.
Best Available Technology Economically Achievable (BATEA) , the 1983
standard, is based upon the addition of filtration and activated
carbon to BPCTCA treatment. This technology is based upon substan-
tial reductions of dissolved organics which are refractory, as well
as those which are biodegradable.
In conclusion, the effluent limitations guidelines that are developed
are based on averages. The effluent limitations guidelines are derived
on the basis of the maximum for any one day and the maximum average of
daily values for any period of thirty consecutive days, and are
determined using the performance factors developed from long-term
performance from the exemplary systems evaluated in the Explosives
industry.
Table 1E-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA, and BADCT
for each subcategory of the Explosives industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
j-20
-------
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NOTICE THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARt SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW 8V EPA.
-------
F. Carbon Black Industry
For the purpose of developing recommended effluent limitations guide-
lines and new source performance standards for Carbon Black manu-
facture, the industry has been subcategorized by process as follows:
A. Furnace Process
B. Thermal Process
The criteria used for establishing the above subcategorizatipn were
the impact of the following factors on the above groupings:
1 . Production processes
2. Product types and yields
3. Raw material sources
k. Wastewater quantities, characteristics, control
and treatment
The only wastewater parameter of significance in the Carbon Black In-
dustry is TSS.
It was concluded that complete elimination of discharge of process
wastewater pollutants is achievable for subcategory A, and that ef-
fluent limitations guidelines are required in subcategory B for TSS.
It was further concluded that, for subcategory B, limitation of
pollution concentrations was necessary, in addition to effluent
limitations guidelines, in order to prevent the imposition of
excessively stringent effluent limitations guidelines.
End-of-process treatment for the 1977 BPCTCA standard is gravity
settling as typified by exemplary processes: e.g., settling/evap-
oration ponds or mechanical clarification. These systems do not pre-
clude the use of equivalent systems in a situation where the land area
required for the indicated treatment is not available.
End-of-process wastewater treatment technology for new sources utiliz-
ing the Best Available Demonstrated Control Technology (BADCT) is
gravity settling followed by filtration.
Best Available Technology Economically Achievable (BATEA - 1983 Standard)
is the same as BADCT.
Table IF-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA, and BADCT
for each subcategory of the Carbon Black industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-22
-------
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AND FURTHER INTCRNAl REVIEW IV EPA.
1-1}
-------
G. Photographic Processing Industry
The Photographic Processing industry was not subcategorized for the
purpose of effluent limitations guidelines. Subcategorization was
deemed unnecessary because the pollutants in the wastewaters and
the pollutant loadings per unit of production were in a relatively
narrow range in the plants surveyed.
The major sources of wastewater in the Photographic Processing in-
dustry are photoprocessing solution overflows and wash waters. Waste-
waters generated by this industry can be characterized as containing
high concentrations of BOD,., COD, TOC, TDA, silver, and ferrocyanide.
Existing control and treatment technology, as practiced in the in-
dustry, includes primarily in-plant pollutant. reductions for silver
and ferrocyanide through recovery of bleaches and silver which is
widely practiced by the industry for economic reasons. Practically
all photoprocessing plants discharge their wastewaters to municipal
sewer systems; only one plant visited had any end-of-pipe treatment
facility, a 20,000-gpd capacity pilot biological treatment system
to investigate the treatability of its wastewaters.
Effluent limitations guidelines have been established for Biochemical
Oxygen Demand (BODr)• Chemical Oxygen Demand (COD), Total Suspended
Solids (TSS), silver thiosulfate, and ferrocyanide. The choice of
these parameters indicates that organic oxygen-demanding material and
constituents, which can exert a toxic effect on a biological treat-
ment process, are the major contaminants in the photographic
processing wastewaters.
The treatment models recommended to attain each of the three levels
of treatment technology are:
Technology Level End-Of-Pipe Treatment Model
BPCTCA In-plant modifications and
activated biological treatment
BADCT BPCTCA plus filtration
BATEA BPCTCA plus filtration
It is emphasized that in-plant measures to reduce silver and ferro-
cyanide concentrations as well as end-of-pipe treatment methods are
included as part of the recommended treatment technologies.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
\-2k
-------
It should be noted that since separate limitations will be required
for BOD^, COD, TOC, TSS, silver and ferrocyanide, there may be cases
where compliance with one of the limitations will require treating
to levels below the actual limitations for the others. In such
cases, it will be necessary to ascertain the particular character
of the waste and to determine if compliance with all these limita-
tions is reasonable. This decision should be based upon treatability
studies covering both biological systems and physical/chemical systems.
In conclusion, effluent limitations guidelines were derived on the basis
of the maximum for any one day and the maximum average of daily values
for any period of thirty consecutive days. Since no long-term data for
exemplary treatment were uncovered in the Photographic Processing
industry during this study, the factors used in deriving these time-
based limitations were derived from long-term performance data from
the exemplary systems evaluated in the Pharmaceutical industry.
Table IG-1 summarizes the contaminants of Interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA, AND BADCT
for the Photographic Processing industry.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-25
-------
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MOT ICt: THESE AH£ TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT ANO ARE SUBJECT TO CHANGE 8A5EO UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW IV EPA.
1-26
-------
H. Hospitals
It was determined that the Hospitals category of the Miscellaneous
Chemicals industry did not require subcategorlzation for the purpose
of establishing effluent limitations guidelines and standards of per-
formance. Possible basis for subcategorization considered during
the study included hospital size, hospital age, geographic location,
hospital type, nature of wastes generated, and treatability of waste-
waters. It was concluded that hospital wastewater characteristics
are independent of these factors and that further subcategorization
was not justified.
Unlike many industrial plants, sanitary wastes in a hospital are not
segregated from other waste streams. Sanitary wastes make up a large
portion of the total wastewater flow and are discharged to a common
sewer system along with other waste streams. Therefore, since sani-
tary wastes make up a significant portion of a hospital's total waste-
water effluent, it was decided not to exclude them from the raw waste
load (RWL) values, as was done with the other Miscellaneous Chemi-
cals industries. The major sources of wastewaters in a hospital are
patient rooms, laundries, cafeterias, surgical suites, laboratories,
and X-ray departments. Wastewaters generated by hospitals can be
characterized as very similar to normal domestic sewage. Specific
contaminants which may be present include mercury, silver, barium,
and boron. Various anti-bacterial constituents (i.e., disinfectants)
which may exert a toxic effect on biological waste treatment processes
may also be present.
Existing control and treatment technology practiced by hospitals in-
clude some in-house reductions as well as end-of-pipe treatment. Most
hospitals are located in densely-populated areas and discharge their
wastes to municipal sewer systems. However, some do utilize on-site
wastewater treatment systems. Current end-of-pipe wastewater treat-
ment technology involves biological treatment. The most common treat-
ment system used is trickling filters, although activated sludge and
aerated lagoons are also utilized. In-plant pollution abatement measures
include mercury-, barium-, and boron-reduction programs and silver-
recovery systems.
Effluent limitations guidelines have been proposed for two wastewater
parameters: Biochemical Oxygen Demand (BOD-) and Total Suspended
Solids (TSS). The choice of these parameters reflects the fact that
organic oxygen-demanding material is the major contaminant in waste-
waters generated by hospitals. Other possible RWL parameters (mercury,
cyanide, nitrogen, chlorides, etc.) were studied during the project,
but were found to be present in concentrations substantially lower
than those which would require specialized end-of-pipe treatment.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-27
-------
It was concluded that the model BPCTCA waste treatment technology for
the Hospitals category should consist of a biological treatment system
with sludge handling facilities. The sludge disposal system would
generally consist of aerobic digestion, vacuum filtration, and ulti-
mate disposal in a landfill. It is emphasized that the proposed model
technology should be used only as a guide and is not applicable in
every case. The model BADCT and BATEA treatment facility for hospitals
consists of BPCTCA technology followed by filtration.
The only information required to develop a specific pollutant effluent
limitations guideline is the size of the hospital measured in terms of
the number of occupied beds. An individual limitation can then be
established for a hospital by multiplying the size of the facility (in
thousands of occupied beds) by the pollutant effluent limitations guide-
lines specified. Since the effluent limitations guidelines are expressed
in pounds of pollutant per thousand beds occupied, this multiplication
gives the long-term average daily discharge value for the hospital. An
appropriate performance factor can then be applied to obtain maximum
average of daily values for any period of thirty consecutive days and
maximum value for any one day for the effluent limitations guidelines.
These performance factors allow for variation in treatment plant
performance and sampling frequency and are necessary for a meaningful
basis for subsequent spot checking and future enforcement action by EPA.
These performance factors are developed from the historical operation
data from several exemplary end-of-ptpe biological treatment plants
for Hospitals.
Table IH-1 summarizes the contaminants of interest, raw waste loads,
and recommended treatment technologies for BPCTCA, BATEA, and BADCT
for Hospitals.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
1-28
-------
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TFTtTs MPORT MO ME JUIJICT TO CMMM WSIO UPON COMCNTS MCEIVtO
AND FUHTHEK INTCKNAI. MVIIW IV EPA.
1-29
-------
SECTION II
RECOMMENDATIONS
General
The recommendations for effluent limitations guidelines commensurate
with the Best Practicable Control Technology Currently Available
(BPCTCA) and end-of-pipe treatment technology for BPCTCA for each of
the industrial categories are presented in the following text. The
text also Includes effluent limitations guidelines to be attained by
the application of the Best Available Technology Economically Achiev-
able (BATEA) and end-of-pipe treatment technology for BATEA for each
of the industrial categories. Exemplary in-process controls, as
discussed in the later sections of this document, are also applicable
to this technology.
The Best Available Demonstrated Control Technology (BADCT) for new
sources includes the most exemplary process controls. The recommen-
dations for effluent limitations guidelines and end-of-pipe treatment
technology for BADCT for each of the industrial categories are also
given in the following text.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
I 1-1
-------
A. Pharmaceutical Industry
The effluent limitations guidelines commensurate with BPCTCA,
BATEA, and New Source treatment technology proposed for each
subcategory of the Pharmaceutical industry are presented in
Figures IIA-1, IIA-2, IIA-3 and Tables IIA-1, IIA-2 and IIA-3.
The effluent limitations guidelines were derived on the basis
of the maximum average of daily values for 30 consecutive days
and the maximum for any one day, and have been developed on
the basis of performance factors for treatment plant operation,
as discussed in Section XIII of this draft development document.
Process wastewaters subject to these limitations include all
contact process water, but do not include noncontact sources
such as boiler and cooling tower blowdown, water treatment wastes,
sanitary, and other similar flows.
Implicit in the recommended guidelines for the Pharmaceutical
industry is the fact that process wastes can be isolated from
nonprocess wastes such as utility discharges and uncontaminated
storm runoff. Segregation of process sewers is therefore the
first recommended step in the accomplishment of reducing pollutant
loadings to levels necessary to meet the proposed guidelines.
Treatment of process wastewaters collected by a combined process/
nonprocess sewer system is not cost-effective due to dilution by
the relatively large volume of nonprocess wastewaters. It is
further suggested that uncontaminated waters, such as storm
runoff, be segregated from outdoor areas where there is potential
for contamination by chemical spills. This could be accomplished
by roofing or curbing potentially-contaminated areas and by col-
lecting and treating runoff which cannot be isolated from such
areas. In-plant modification which will lead to reductions in
wastewater flow, increased quantity of water used for recycle
or reuse, and improvement in raw wastewater quality should be
implemented, provided that these modifications have minimum im-
pact on processing techniques or product quality. Segregation
of strong and weak waste streams and treating them separately is
recommended from the standpoint of cost effectiveness.
For wastewater containing significant quantities of metals,
cyanide, or anti-bacterial constituents which may exert a toxic
effect on biological treatment processes, pretreatment at-source
is recommended. For those wastewaters which contain significant
quantities of cyanide or ammonia, cyanide destruction or ammonia
removal at-source is recommended. Other in-plant measures such
E: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-2
-------
solvent recovery and incineration of still bottoms and of
solvent streams not economical to recover are practiced by
many Pharmaceutical plants, and are recommended for adoption
by all plants where applicable.
End-of-pipe treatment technologies equivalent to biological
treatment should be applied to the wastewaters from pharmaceutical
subcategories A, B, C^, D, and E to achieve BPCTCA effluent
requirements. For subcategory C^, liquid incineration is re-
commended to achieve BPCTCA, BADCT, and BATEA effluent require-
ments. In addition, to minimize capital expenditures for end-
of-pipe wastewater treatment facilities, BPCTCA technology in-
cludes the maximum utilization of current in-plant pollution
abatement methods presently practiced by the Pharmaceutical
industry.
To meet BATEA requirements, end-of-pipe treatment technologies
equivalent to BPCTCA treatment, followed by multi-media gravity
filtration and activated carbon adsorption, are recommended for
subcategories A and Cj. For subcategories B, D, and E, BPCTCA
treatment followed by dual-media filtration is proposed.
BATEA treatment technology also includes the improvement of
existing in-plant pollution abatement measures and the use of
the most exemplary process controls.
BADCT control and treatment standards, to be applied to new
sources, are equivalent to BPCTCA treatment followed by dual-
media filtration. This is identical to BATEA standards
for subcategories B, 0, and E. Exemplary in-process controls are
also applicable to this technology. The use of activated carbon
adsorption has not been recommended as part of the new source
performance standards, as this advanced wastewater treatment tech-
nology has not been demonstrated in the Pharmaceutical industry
sufficiently to establish operating performance, reliability, and
economics. The treatment, control theory, and effluent limitations
guidelines for the nonprocess wastewaters (boiler blowdown, cooling
tower blowdowns, water treatment plant wastes) generated by the
Pharmaceutical industry should be covered by the Steam Supply and
Noncontact Cooling Water Industry Guidelines and by the water treat-
ment effluent guidelines which are to be published by EPA.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
M-3
-------
FIGURE IIA-1
CATEGORY A BPCTCA EFFLUENT
DRAFT
5.000
§
£
DO
1,000
O
<
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ID
Ul
s
100
LIMITATIONS
VS
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PRODUCTION 1000 UBS/DAY
NOT|CE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
FIGURE IIA-2
CATEGORY A - BATEA EFFLUENT
LIMITATIONS
VS
PRODUCTION
DRAFT
500
§
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10
yCOD
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logy -2.90-1.26 logx
logy -2.66-1.41 togx
\
S
10
PRODUCTION 1000 IBS/DAY
20
THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
INTHIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
H-5
-------
5.000
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FIGURE IIA-3
CATEGORY A • 8ADCT EFFLUENT
LIMITATIONS
VS
PRODUCTION
DRAFT
\
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logy -3.18-1.37 tog*
\
\
\
V tojy -3.59-1.25 togx
\
10
20
PRODUCTION 1000 LBS/DAY
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
II-6
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
M-7
-------
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B. Gum and Wood Chemicals Industry
Implicit in the recommended guidelines for the Gum and Wood
Chemicals industry is the fact that process wastes can be isolated
from uncontaminated wastes such as utility discharges and un-
contaminated storm runoff. Isolation of process wastewater is
generally the first recommended step injaccomplishing the reductions
necessary to meet the proposed guidelines. Treatment of un-
contami nated wastewaters together with contaminated process
wastewaters in a treatment facility is not generally cost-
effective.
Effluent limitations guidelines commensurate with BPCTCA are
presented for each subcategory of the Gum and Wood Chemicals
industry in Table IIB-1. The effluent limitations guidelines
were derived on the basis of the maximum average of daily values
for thirty consecutive days and the maximum for any one day
and have been developed on the basis of the performance factors
for treatment plant operation as discussed in Section XIII of
this draft development document. Process wastewaters subject
to these limitations do not include noncontact sources such as
boiler and cooling water blowdown, sanitary, and other similar
flows. BPCTCA also includes the maximum utilization of appli-
cable in-plant pollution abatement technology to minimize capital
expenditures for end-of-pipe wastewater treatment facilities.
End-of-pipe technology for BPCTCA involves the application of
biological treatment, as typified by activated sludge or aerated
lagoons with sedimentation ponds.
Effluent limitations guidelines to be attained by application of
the BATEA are presented in Table IIB-2. End-of-pipe treatment for
BATEA includes the addition of an activated carbon system to the
BPCTCA treatment processes. Exemplary in-process controls are also
applicable to this technology. It is emphasized that the model
treatment system does not preclude the use of activated carbon
within the plant for recovery of products, by-products, and
catalysts.
The best available demonstrated control technology (BAOCT) for
new sources includes the most exemplary process controls, as
previously enumerated, with biological waste treatment followed
by filtration for removal of suspended solids. Effluent limitations
guidelines for subcategories within the Gum and Wood Chemicals in-
dustry are presented in Table IIB-3.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
M-10
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AND FURTHER INTERNAL REVIEW BY EPA.
11-11
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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AND FURTHER INTERNAL REVIEW BY EPA.
11-12
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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AND FURTHER INTERNAL REVIEW BY EPA.
11-13
-------
C. Pesticides and Agricultural
The effluent limitations guidelines commensurate with BPCTCA, BATEA
and New Source treatment technology proposed for each subcategory
of the Pesticides and Agricultural Chemicals industry are presented
in Tables IIC-1, IIC-2 and MC-3. The effluent limitations guide-
lines were derived on the basis of the maximum average of daily
values for thirty consecutive days and the maximum for any one day,
and on the basis of the performance factors for the treatment plant
operation as discussed in Section XIII of this draft development
document. Process wastewaters subject to these limitations include
all contact process water, but do not include noncontact sources,
such as boiler and cooling water blowdowns, sanitary wastes, and
other similar nonprocess sources.
""Implicit in BPCTCA standards is the segregation of noncontact waste-
waters from process wastewaters and the maximum utilization of ap-
plicable in-plant pollution abatement technologies required to
minimize capital expenditures for end-of-pipe wastewater treatment
facilities. Segregation and incineration of extremely toxic waste-
waters or very strong wastewaters are recommended.
End-of-process technology for BPCTCA involves the application of
biological treatment, preceded by various types of pretreatment,
depending on the particular subcategory. Extensive pretreatment
systems are required due to the toxic nature of many pesticides
wastewaters. Equalization with pH control and oil separation may
be required in order to provide optimal, as well as uniform, levels
of treatment. Chemical flocculation aids, when necessary, should
be added to the clarification system in order to control suspended
solids levels.
End-of-process treatment for BATEA includes the addition of fil-
tration and activated carbon systems to BPCTCA treatment pro-
cesses.
The BADCT for new sources includes in-plant controls with BPCTCA
systems followed by filtration for additional removal of sus-
pended sol ids.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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11-15
-------
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11-16
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-17
-------
D. Adhesive and Sealants Industry
Implicit in the recommended guidelines for the Adhesive and Sealants
industry is the assumption that process wastes can be isolated from
uncontaminated wastes, such as utility discharges and uncontaminated
storm runoff. Isolation of process wastewater is generally the first
recommended step in achieving the reductions called for by the pro-
posed guidelines. Treatment of uncontaminated wastewaters is usually
not cost-effective.
Effluent limitations guidelines commensurate with BPCTCA are presented
by subcategory for the Adhesive and Sealants industry in Table IID-1.
The effluent limitations guidelines are on the basis of the maximum
average of daily values for thirty consecutive days and the maximum
for any one day and are developed using the performance factors for
the treatment plant operation as discussed in Section XIII of this
draft development document.
Process wastewaters subject to these limitations include all contact
process water, but do not include noncontact wastewater sources such
as boiler and cooling water blowdown, sanitary wastewaters, and other
similar flows. BPCTCA guidelines assume a maximum utilization of
applicable in-plant pollution abatement technology to minimize capital
expenditures for end-of-pipe wastewater treatment facilities. End-
of-process technology for BPCTCA involves the application of biological
treatment, as typified by activated sludge for subcategory A and
evaporation for subcategories B and C. The recommended BPCTCA efflu-
ent limitations can be attained by these proposed systems. However, j
these are not the only possible effective wastewater treatment systems !
nor should they be construed as being totally applicable across all j
categories. )
End-of-process technology for BATEA involves the addition of biolog- T
ical treatment and filtration to BPCTCA for subcategory A. BATEA and I
BADCT are the same as BPCTCA for subcategories B and C. Effluent
limitations guidelines to be achieved by this technology are pre-
sented in Table 11D-2.
It must be recognized that, in most cases, in-process modifications
to existing plants are interchangeable with those which can be de-
signed for new ones. The end-of-pipe systems specified can also be :
implemented interchangeable for either new plants or existing plants.
BADCT involves biological treatment followed by filtration for sub-
category A. Effluent limitations guidelines commensurate with this £
technology are presented in Table 11D-3-
Each of the BATEA and BADCT effluent limitations guidelines is attain-
able with the treatment systems indicated; however, each plant should ',
use those treatment systems which are applicable to its wastewater.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA. Ktttivtu
11-18
-------
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11-19
-------
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11-20
-------
PA
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IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-21
-------
E. Explosives Industry
The BPCTCA treatment technology recommended for the Explosives industry
Is a biological treatment system. This treatment system Is designed to
attain the BPCTCA effluent limitations guidelines presented in Table
IIE-1.
BATEA treatment technology is defined as filtration and activated
carbon added on to the BPCTCA treatment system. This treatment system
is designed to attain the BATEA effluent limitations guidelines pre-
sented in Table IIE-2.
New source performance standards (BADCT) can be achieved by filtration
added on to the BPCTCA treatment system. Effluent limitations guide-
lines for BAOCT are shown in Table IIE-3. The effluent limitations
guidelines are on the basis of the maximum average of daily values
for thirty consecutive days and the maximum for any one day and are
developed using the performance factors for the treatment plant oper-
ation as discussed in Section XIII of this draft development docu-
ment.
It is recommended that wastewater from explosives plants be treated
on-site. If municipal treatment is highly advantageous over on-site
treatment, a pretreatment system must be designed to remove potentially
hazardoud explosives wastes. Performance factors for BOD,- and COD
have been computed from historical data. For TSS, performance factors
from the Pharmaceutical industry have been used, and it has been as-
sumed that these data are similar.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-22
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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AND FURTHER INTERNAL REVIEW BY EPA.
11-23
-------
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II-
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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AND FURTHER INTERNAL REVIEW BY EPA.
11-25
-------
F. Carbon Black Industry
Implicit in the recommended effluent limitations guidelines for the
Carbon Black industry is the assumption that process wastes can be
isolated from uncontaminated wastes such as utility discharges and
uncontaminated storm runoff. Isolation of process wastewater is
generally the first recommended step in accomplishing the reductions
necessary to meet the proposed guidelines. Treatment of uncontami-
nated wastewaters in a treatment facility is not generally cost-
effective.
Effluent limitations guidelines commensurate with BPCTCA are presented
for each subcategory of the Carbon Black industry in Table IIF-1.
Process wastewaters subject to these limitations include all contact
process water but do not include noncontact sources such as boiler
and cooling water blowdown, sanitary and other similar flows. Ad-
ditionally, BPCTCA includes the maximum utilization of applicable
in-plant pollution abatement technology to minimize capital expendi-
tures for end-of-pipe wastewater treatment facilities. End-of-process
technology for BPCTCA involves the application of sedimentation/evapora-
tion ponds, or mechanical gravity settlers, where applicable.
The Best Available Demonstrated Control Technology (BADCT) for new
sources includes gravity sedimentation/evaporation ponds, or mechanical
gravity settlers followed by filtration. BADCT effluent limitations
guidelines for subcategories within the Carbon Black industry are pre-
sented in Table IIF-2.
Effluent limitations guidelines to be attained by the application of
BATEA are presented in Table IIF-2 as well. End-of-process treatment
for BATEA includes the addition of filtration to the BPCTCA treatment
processes. It is emphasized that the model treatment system does not
preclude the use of other applicable technology.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-26
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-27
-------
ID
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-28
-------
G. Photographic Processing Industry
The BPCTCA, BATEA, and BADCT effluent 1 imitations proposed for the
Photographic Processing industry are presented in Tables IIG-1 and
IIG-2. These effluent limitations guidelines are on the basis of
the maximum average of daily values for thirty consecutive days
and the maximum for any one day and are developed using the per-
formance factors for the treatment plant operation as discussed in
Section XIII of this draft development document.
Wastewaters subject to these limitations include all contact process
water, but do not include sanitary wastewaters.
Implicit In the recommended guidelines for the Photographic Processing
industry is the use of in-olant measures to reduce silver and ferro-
cyanide. In-plant modifications which will lead to reductions in
wastewater flow, increased quantity of water used for recycle, and
improvement in raw wastewater quality should also be implemented to
make end-of-pipe treatment cost-effective.
End-of pipe treatment technologies equivalent to biological treatment
should be utilized by the Photographic Processing industry to achieve
BPCTCA effluent limitations guidelines.
To meet BATEA and BADCT effluent limitations guidelines end-of-
pipe treatment technologies equivalent to BPCTCA treatment followed
by dual-media filtration Is recommended. Exemplary in-plant pol-
lutant abatement measures are also applicable to these technologies.
Most Photographic Processing plants discharge their effluents to
municipal sewer systems. Although organic material is the predom-
inant pollutant in these wastewaters, certain constituents (i.e.,
silver and ferrocyanide) which could exert toxic effects on a bio-
logical system and various non-biodegradable material may also be
present. Therefore, in-plant measures or pretreatment to reduce the
concentrations of such contaminants to levels acceptable to local
authority should be utilized.
NOTICE; THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-29
-------
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AND FURTHER INTERNAL REVIEW BY EPA.
I 1-30
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1-3!
-------
H. Hospitals
Effluent limitations guidelines commensurate with BPCTCA, BADCT, nnd
BATEA treatment technology are proposed for the Hospitals category and
are presented In Table IIH-1. These effluent limitations guidelines
are on the basis of the maximum average of dally values for thirty
consecutive days and the maximum for any one day and are developed
using the performance factors for the treatment plant operation as
discussed in Section XIII of this draft development document.
Wastewaters subject to these limitations include the total combined
wastewater stream generated by a hospital facility.
End-of-pipe treatment technologies equivalent to biological treatment
should be applied to the wastewaters from hospital facilities to
achieve BPCTCA effluent limitations. In addition, to minimize capital
expenditures for end-of-pipe wastewater treatment facilities, BPCTCA
technology includes the maximum utilization of current In-house pol-
lution abatement methods presently practiced by hospitals.
To meet BADCT and BATEA limitations guidelines, end-of-pipe treatment
technologies equivalent to biological treatment followed by multi-
media filtration is recommended. BADCT and BATEA treatment technologies
also include the use of the most exemplary In-house pollution abate-
ment measures and the improvement of existing In-house measures.
Most hospital facilities discharge their effluents to municipal
sewer systems. Although organic material Is the predominant pollutant
in these wastewaters, mercury, barium, boron, silver, and various
solvents may also be present.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
11-32
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SECTION III
INTRODUCTION
Purpose and Authority
The Federal Water Pollution Control Act Amendments of 1972 (the Act)
made a number of fundamental changes in the approach to achieving clean
water. One of the most significant changes was to shift from a reliance on
water quality related effluent limitations to a direct control of
effluents through the establishment of technology-based effluent limi-
tations to form an additional basis, as a minimum, for issuance of
discharge permits. The permit program under the 1899 Refuse Act was
placed under full control of EPA, with much of the responsibility to
be delegated to the states.
The Act requires EPA to establish guidelines for technology-based
effluent limitations which must be achieved by point sources of dis-
charges into the navigable waters of the United States. Section 301(b)
of the Act requires the achievement by not later than July 1, 1977
of effluent limitations for point sources, other than publicly owned
treatment works, which are based on the application of the Best Prac-
ticable Control Technology Currently Available as defined by the
Administrator pursuant to Section 304(b) of the Act. Section 301(b)
also requires the achievement by not later than July 1, 1983 of
effluent limitations for point sources, other than publicly owned
treatment works, which are based on the application of the Best Avail-
able Technology Economically Achievable which will result in reasonable
further progress toward the national goal of eliminating the discharge
of all pollutants, as determined in accordance with regulations issued
by the Administrator pursuant to Section 30^(b) of the Act. Section 306
of the Act requires the achievement by new sources of a Federal standard
of performance providing for the control of the discharge of pollutants
which reflects the greatest degree of effluent reduction which the
Administrator determines to be achievable through the application of
the Best Available Demonstrated Control Technology, processes, operating
methods, or other alternatives, including, where practicable, a standard
permitting no discharge of pollutants.
Section 304(b) of the Act requires the Administrator to publish regula-
tions providing limitations setting forth the degree of effluent reduction
attainable through the application of the Best Practicable Control Tech-
nology Currently Available and the degree of effluent reduction attainable
through the application of the best control measures and practices achiev-
able including treatment techniques, process and procedure innovations,
operation methods, and other alternatives. The regulations proposed herein
set forth effluent limitations guidelines pursuant to Section 30^(b) of
the Act for the Miscellaneous Chemicals industry.
I 11-1
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Section 3QMc) of the Act requires the Administrator to issue iniorm.it ion
on the processes, procedures, or operatlm] methods whlth irstilt in (\\c
elimination or reduction in the discharge of |>ollut%iMts U> linplrmrnl
standards of performance under Section 306 of the Act. Such inloi 111,11 imi
is to include technical and other data, including costs, as are available
on alternative methods of elimination or reduction of the discharge of
pol1utants.
Section 306 of the Act requires the Administrator, within one year after
a category of sources is included in a list published pursuant to Section
306(b) (1) (A) of the Act, to propose regulations establishing Federal
standards of performances for new sources within such categories. The
Administrator published in the Federal Register of January 16, 1973
(38 F.R. 1624), a list of 27 source categories. Publication of the list
constituted announcement of the Administrator's intention of establish-
ing, under Section 306, standards of performance applicable to new
sources within the Miscellaneous Chemicals industry category, which was
included within the list published January 16, 1973.
Furthermore, Section 307(b) provides that:
1. The Administrator shall, from time to time, publish proposed
regulations establishing pretreatment standards for introduction
of pollutants into treatment works (as defined in Section 212
of this Act) which are publicly owned, for those pollutants
which are determined not to be susceptible to treatment by
such treatment works or which would interfere with the opera-
tion of such treatment works. Not later than ninety days
after such publication, and after opportunity for public hear-
ing, the Administrator shall promulgate such pretreatment stand-
ards. Pretreatment standards under this subsection shall specify
a time for compliance not to exceed three years from the date
of promulgation and shall be established to prevent the discharge
of any pollutant through treatment works (as defined in Section
212 of this Act) which are publicly owned, which pollutant inter-
feres with, passes through, or otherwise is incompatible with
such works.
2. The Administrator shall, from time to time, as control technology,
processes, operating methods, or other alternatives change, re-
vise such standards, following the procedure established by this
subsection for promulgation of such standards.
3. When proposing or promulgating any pretreatment standard under
this section, the Administrator shall designate the category or
categories of sources to which such standard shall apply.
4. Nothing in this subsection shall affect any pretreatment require-
ment established by any State or local law not in conflict with
any pretreatment standard established under this subsection.
I I 1-2
-------
In order to insure that any source introducing pollutants into a publicly
owned treatment works, which source would be a new source subject to
Section 306 if it were to discharge pollutants, will not cause .1 viola-
tion of the effluent limitations established for any such treatment works,
the Administrator shall promulgate pretreatment standards for the cate-
gory of such sources simultaneously with the promulgation of standards
of performance under Section 306 for the equivalent category of new sources,
Such pretreatment standards shall prevent the discharge into such treat-
ment works of any pollutant which may interfere with, pass through,
or otherwise be incompatible with such works.
The Act defines a new source to mean any source the construction of which
is commenced after the publication of proposed requ Kit Ions prt".c:r Ihlwi .1
standard of performance. Construction means any placement, assembly, or
installation of facilities or equipment (including contractual obliga-
tions to purchase such facilities or equipment) at the premises where
such equipment will be used, including preparation work at such premises.
Scope of Study
The Miscellaneous Chemicals industry was defined by EPA for the purpose
of this study to include those commodities listed under the following
Standard Industrial Classification (SIC):
SIC 2831 - Biological Products
SIC 2833 ~ Medicinal Chemicals and Botanical Products
SIC 283^ - Pharmaceutical Preparations
SIC 2861 - Gum and Wood Chemicals
SIC 2879 - Agricultural Chemicals (Formulations)
SIC 2879 - Pesticides & Agricultural Chemicals
SIC 2891 - Adhesive and Sealants
SIC 2892 - Explosives
SIC 2895 - Carbon Black
SIC 2899 - Chemicals and Chemical Preparation, Not Elsewhere
Class i ffed
SIC 7221 - Photographic Studios, Portrait
SIC 7333 ~ Commercial Photography, Art and Graphics
SIC 7395 " Photofinishing Laboratories
SIC 7819 " Developing and Printing of Commercial Motion
P i cture Film
SIC 8062 - General Medical and Surgical Hospitals
SIC 8063 - Psychiatric Hospitals
SIC 8069 - Specialty Hospitals
It must be understood that the Standard Industrial Classifications list
was developed by the United States Department of Commerce and is oriented
toward the collection of economic data related to gross production, sales,
and unit costs. The SIC list is not related to the nature of the industry
111-3
-------
in terms of actual plant operations, production, or considerations as-
sociated with water pollution control. As such, the list does not pro-
vide a realistic or definitive set of boundaries for study of the Mis-
cellaneous Chemicals Industry.
The other commodities/services which could have been considered for
coverage but were not covered under the scope of this study as defined
by EPA are:
SIC 28AA - Cosmetic Preparations
SIC 38^2 - Surgical Supplies
SIC 38^3 - Dental Supplies
SIC 8071 - Medical Laboratories
SIC 8072 - Dental Laboratories
SIC 8081 - Out patient Care Facilities
SIC 8091 - Health and Allied Services, Not Elswhere
Classified
Effluent limitations guidelines need to be developed at a later date to
cover these commodities services not covered under the present study.
Methods Used for Development of the Effluent
Limitations and Standards for Performance
The effluent limitation guidelines and standards of performance proposed
in this document were developed in the following manner. The Miscellaneous
Chemicals industry was first divided into industrial categories, based on
type of industry and products produced. Each industrial category was
further subcategorized to determine whether separate limitations and
standards were appropriate for different segments within an industrial
category. Such subcategorizatjon was based upon raw material used, pro-
duct produced, manufacturing process employed, and other factors.
The raw waste characteristics for each subcategory were then identified.
This included an analysis of: 1) the source and volume of water used in
the process employed and the sources of wastes and wastewaters in the
plant: and 2) the constituents of all wastewaters (including toxic
constituents and other constituents) which result in taste, odor, and
color in water or aquatic organisms. The constituents of wastewaters
which should be subject to effluent limitations guidelines and standards
of performance were identified.
The full range of control and treatment technologies existing within each
subcategory was identified. This included an identification of each dis-
tinct control and treatment technology, including both in-plant and end-
of-pipe technologies, which are existent or capable of being designed
for each subcategory. It also included an identification of the effluent
level resulting from the application of each of the treatment and control
technologies, in terms of the amount of constituents and of the chemical,
physical, and biolgical characteristics of pollutants. The problems,
limitations, and reliability of each treatment and control technology
I I \-k
-------
and the required implementation time were also identified. In addition,
the non-water-quality environmental impacts (such as the effects of the
application of such technologies upon other pollution problems, includ-
ing air, solid waste, and noise) were also identified. The energy
requirements of each of the control and treatment technologies were
identified, as well as the cost of the application of such tech-
nolog ies.
The information, as outlined above, was then evaluated in order to deter-
mine what levels of technology constituted the Best Practicable Control
Technology Currently Available, Best Available Technology Economically
Achievable, and the Best Available Demonstrated Control Technology,
processes, operating methods, or other alternatives. In identifying
such technologies, various factors were considered. These included the
total cost of application of technology in relation to the effluent re-
duction benefits to be achieved from such application, the age of equip-
ment and facilities involved, the process employed, the engineering as-
pects of the application of various types of control techniques, process
changes, non-water-quality environmental impact (including energy re-
quirements), and other factors.
During the initial phases of the study, an assessment was made of the
availability, adequacy, and usefulness of all existing data sources.
Data on the identity and performance of wastewater treatment systems
were known to be included in:
1. NPDES Permit Applications.
2. Self-reporting discharge data from various states.
3. Surveys conducted by trade associations or by agencies under
research and development grants.
A preliminary analysis of these data indicated an obvious need for addi-
tional information.
Refuse Act Permit Applications data are limited to identification of the
treatment system used and reporting of final concentrations (which were
diluted with cooling waters in many cases); consequently, operating per-
formance could not be determined.
Additional data in the following areas were therefore required: 1) pro-
cess RWL (Raw Waste Load) related to production; 2) currently practiced
or potential in-process waste control techniques; and 3) the identity
and effectiveness of end-of-pipe treatment systems. The best source of
information was the manufacturers themselves. New information was ob-
tained from direct interviews and sampling visits to Miscellaneous Chem-
icals production facilities. These additional data were obtained from direct
interviews and from inspection and sampling of Miscellaneous Chemicals
manufacturing and their related wastewater treatment facilities.
111-5
-------
Collection of the data necessary for development of RWL and effluent
treatment requirements within deptimldMn confidence I hulls required
analysis of both production and treatment operations. In a Inw ta^n*-.,
the plant visits were planned so that the production operations of a
single plant could be studied in association with an end-of-pipe
treatment system which receives only the wastes from that production.
The RWL for this plant and associated treatment technology would fall
within a single subcategory. However, wide variety of products
manufactured by most of the industrial plants made this situation rare.
In the majority of cases, it was necessary to visit individual facili-
ties where the products manufactured fell into several subcategories.
The end-of-pipe treatment facilities received combined wastewaters
associated with several subcategories (several products). It was neces-
sary to analyze separately the production (waste generating) facilities
and the effluent (waste treatment) facilities. This required establish-
ment of a common basis, the Raw Waste Load (RWL), for common levels of
treatment technology for the products within a subcategory and for the
translation of treatment technology between subcategories.
The selection of process plants as candidates to be visited was guided
by the trial subcategorization, which was based on anticipated differ-
ences in RWL. Process plants which manufacture only products within
one subcategory were scheduled, as well as those which cover several
subcategories, to insure the development of a dependable data base.
The selection of treatment plants was developed from identifying inform-
ation available in the NPDES Permit Applications, state self-reporting
discharge data, and contacts within the industry. Every effort was made
to choose facilities where meaningful information on both treatment
facilities and manufacturing processes could be obtained.
Survey teams composed of project engineers and scientists conducted the
actual plant visits. Information on the identity and performance of
wastewater treatment systems was obtained through:
1. Interviews with plant water pollution control personnel.
2. Examination of treatment plant design and historical operat-
ing data (flow rates and analyses of influent and effluent).
3- Treatment plant influent and effluent sampling.
Information on process plant operations and the associated RWL was
obtained through:
1. Interviews with plant operating personnel.
I I 1-6
-------
2. Examination of plant design and operating data (original design
specification, flow sheets, day-to-day material balances around
Individual process modules or unit operations where possible).
3. Individual process wastewater sampling and analysis.
The data base obtained in this manner was then utilized by the methodology
previously described to develop recommended effluent limitations and
standards of performance for the Miscellaneous Chemicals industry. All of
the references utilized are included in Section XVI of this report. The
data obtained during the field data collection program are included in
Supplement B.
The following text describes the scope of the study, technical approach
to the development of effluent limitation guidelines, and the scope of
coverage for data base for individual industrial categories.
111-7
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A. Pharmaceutical Industry
Scope of the Study
To establish boundaries for the scope of work for this study, the
Pharmaceutical industry was defined to include all commodities listed
under SIC 2831 (Biological Products), SIC 2833 (Medicinal Chemicals
and Botanical Products), and SIC 283^ (Pharmaceutical Preparations).
Lists of the specific products covered by these Standard Industrial
Classifications are presented in Tables IIIA-1, IIIA-2 and I IIA-3-
It should be noted that the lists as provided in these tables were
developed by the United States Department of Commerce and are oriented
toward the collection of economic data related to gross production,
sales, and unit costs. They are not related to actual plant opera-
tions, production, or considerations associated with water pollution
control, and, as such, they do not provide a set of boundaries which
is completely applicable for this type of study of the Pharmaceutical
industry. Therefore, to establish effluent limitations and treatment
guidelines for this industry, a more definitive set of boundaries was
established. To accomplish this, SIC 2833 was further subdivided
into fermentation products, chemical synthesis products, and natural
extractions products. This additional subdivision was required to
establish a consistent interrelationship between the major manufactur-
ing processes employed by the Pharmaceutical industry and the major
medicinal chemical groups produced by the industry. During the course
of the study, the following four major production areas were identi-
fied for in-depth study:
1. Fermentation processes: used to produce primarily antibiotics
and steroids.
2. Biological products and natural extractions manufacturing
processes: used to produce blood derivitives, vaccines, serums,
animal bile derivatives, and plant tissue derivatives.
3. Chemical synthesis processes: used to produce hundreds of
different products, from vitamins to anti-depressants.
A. Formulation processes: used to convert the products of the
other three manufacturing areas into the final dosage forms
(tablets, capsules, liquids, etc.) marketed to the public.
In addition, since research is such a large and important part of
the Pharmaceutical industry, a fifth study area was established:
5- Research: including microbiological, biological, and chemical
research activities.
I I 1-8
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Table IIIA-1
Biological Products - SIC 2831
Agar culture media
Aggress ins
Allergenic extracts
Al lergens
Ant i gens
Anti-hog-cholera serums
Ant i serums
Antitoxins
Antivenom
Bacterial vaccines
Bacterins
Bacteriological media
Biological and allied products: anti-
toxins, bacterins, vaccines, viruses
Blood derivatives, for human or veteri-
nary use
Culture media or concentrates
Diagnostic agents, biological
Diphtheria toxin
Plasmas
Pollen extracts
Serobacterins
Serums
Tox i ns
Toxoids
Tuberculins
Vaccines
Venoms
Viruses
MI-9
-------
Table I IIA-2
Medicinal Chemicals and Botanical Products - SIC 2833
Adrenal derivatives: bulk, uncom-
pounded
Agar-agar (ground)
Alkaloids and salts
Anesthetics, in bulk form
Antibiotics: bulk uncompounded
Atropine and derivatives
Barbituric acid and derivatives: bulk,
uncompounded
Botanical products, medicinal: ground,
graded, and mi 1 led
Brucine and derivatives
Caffeine and derivatives
Chemicals, medicinal: organic and in-
organic—bulk, uncompounded
Cinchone and derivatives
Cocaine and derivatives
Codeine and derivatives
Dig!toxin
Drug grading, grinding, and milling
Endocrine products
Ephedrine and derivatives
Ergot alkaloids
Fish liver oils, refined and concen-
trated for medicinal use
Gland derivatives: bulk, uncom-
pounded
Herb grinding, grading, andmilling
Hormones and derivatives
Insulin: bulk, uncompounded
Kelp plants
Mercury chlorides, U.S.P.
Mercury compounds, medicinal: or-
ganic and inorganic
Morphine and derivatives
N-methylpiperazine
Oils, vegetable and animal: medicinal
grade--refined and concentrated
Opium derivatives
Ox bile salts and derivatives: bulk,
uncompounded
Penicillin: bulk, uncompounded
Physostigmine and derivatives
Pituitary gland derivatives: bulk,
uncompounded
Procaine and derivatives: bulk,
uncompounded
Quinine and derivatives
Reserpines
Salicylic acid derivatives, medicinal
grade
Strychnine and derivatives
Sulfa drugs
Sulfonamides
Theobromi ne
Vegetable gelatin (agar-agar)
Vegetable oils, medicinal grade: re-
fined and concentrated
Vitamins, natural and synthetic: bulk,
uncompounded
111-10
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Table IIIA-3
Pharmaceutical Products - SIC 283^
Adrenal pharmaceutical preparations
Analges ics
Anesthetics, packaged
Antacids
AntheImint ics
Antibiotics, packaged
Antihistamine preparations
Ant i pyretics
Antiseptics, medicinal
Astringents, medicinal
Barbituric acid pharmaceutical prepa-
rat ions
Belladonna pharmaceutical prepara-
tions
Botanical extracts: powdered, pilular,
sol id , and fluid
Chapst icks
Chlorination tablets and kits (water
pur i ficat ion)
Cold remedies
Cough medicines
Cyclopropane for anesthetic use (U.S.P.
par N.F.) packaged
Dextrose and sodium chloride injection
mixed
Dextrose injection
Digitalis pharmaceutical preparations
D iuret ics
Druggists' preparations (pharmaceuti-
cals)
Effervescent salts
Emulsifiers, fluorescent inspection
Emulsions, pharmaceutical
Ether for anesthetic use
Fever remedies
Galenical preparations
Hormone preparations
Insulin preparations
Intravenous solutions
Iodine, tincture of
Laxat ives
Li niments
Lozenges, pharmaceutical
Medicines, capsuled or ampuled
Nitrofuran preparations
Nitrous oxide for anesthetic use
Ointments
Parenteral solutions
Penicillin preparations
Pharmaceuticals
Pills, pharmaceutical
Pituitary gland pharmaceutical prepa-
rations
Poultry and animal remedies
Powders, pharmaceutical
Procaine pharmaceutical preparations
Proprietary drug products
Remedies, human and animal
Sirups, pharmaceutical
Sodium chloride solution for injection
U.S.P.
Sodium salicylate tablets
Solutions, pharmaceutical
Spirits, pharmaceutical
Suppositories
Tablets, pharmaceutical
Thyroid preparations
Tinctures, pharmaceutical
Tranqui1izers and mental drug prepa-
rations
Vermifuges
Veterinary pharmaceutical prepara-
tions
Vitamin preparations
Water decontamination or purification
tablets
Water, sterile: for injections
Zinc ointment
I I 1-11
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Technical Approach to the Development
of Effluent Limitation Guidelines
The effluent limitations and standards of performance recommended in
this document for the Pharmaceutical industry were developed in the
manner outlined in the section "Methods Used for Develoopment of
Effluent Limitations and Standards of Performance" above.
Scope of Coverage for Data Base
Figure I I IA-1 illustrates the geographical breakdown of the Pharma-
ceutical industry in the continental United States. Most
pharmaceutical manufacturing firms are located in New York, New
Jersey, Pennsylvania, Indiana, Illinois, Michigan, Missouri, Ohio,
and California, with production concentrated in the industrial
areas of the East and the Midwest. In addition, there are approxi-
mately 60 pharmaceutical plants on the island of Puerto Rico. All
but one of the plant surveyed for this study were located in one
of these three high-production geographical areas.
The Pharmaceutical Manufacturers Association (PMA) estimates that
there are between 600 and 700 firms in the United States producing
prescription products. PMA represents 110 manufacturers who annually
produce approximately 95 percent of the prescription products sold
in the United States, and an estimated 50 percent of total free-
world output. Industry-wide market share data compiled by PMA show
that 20 firms account for 75 percent of total sales in the United
States. Five of the nine firms (16 plants) surveyed for this study
are among these top 20. The remaining k firms were smaller companies.
It should be noted that 81 establishments primarily engaged in pro-
duction of commodities listed under codes SIC 2831, 2833 and 283^
have applied for NPDES discharge applications. Of these 81, twenty-
three plants are designated as major dischargers. Eight of these
twenty-three facilities were surveyed during the course of this study.
I 11-12
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SHIPMENTS OF PHARMACEUTICAL PREPARATIONS
BY CENSUS REGIONS, DIVISIONS AND STATES, 1967
SHIPMENTS OF PHARMACEUTICAL
PREPARATIONS, EXCEPT BIOLOGICALS
REGION (MILLIUIMSUh UULLAHS)
NORTHEAST
NFW YORK
NFW.IFRSFY
PFNNSYI VANIA
OTHER
IMDRTH rFNTRAL
OHIO
INDIANA
II I INOIS
MICHIGAN
MISSOURI
OTHER
SOUTH
SOUTH ATLANTIC
FAST SOI ITU TFNTRAI
WFST SOUTH CENTRAL
WEST
CALIFORNIA
OTHER
US. TOTAL
$2r457.7
789 3
887 6
709 0
71 8
1 287 3
0/1 1
jJOr K
OQT 5
100 0
99 fi
C3 c
292 2
177 Q
87 5
268
1042
070
063
$4.143.0
PERCENT
OF U.S.
59.3%
31.1
7.1
2.5
100.0%
PRESECRPTION DRUG INDUSTRY FACT BOOK, PMA, 1973
MI-13
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B. Gum and Wood Chemicals Industry
Scope of the Study
The Gum and Wood Chemicals industry was defined by EPA for the
purpose of this study to include only those kl commodities listed
under SIC (Standard Industrial Classification) 2861, as shown in
Table IIIB-1. The SIC code provides a valuable guideline for divid-
ing United States manufacturing facilities into manageable categories.
It should be noted, however, that the list contains some anomalies
with regard to manufacturing activities in the Gum and Wood Chemicals
industry, including the following:
1. The list contains some 20 natural tanning materials and dye stuffs
which are of minor importance in U.S. manufacturing activities
in terms of production quantities or dollar value added by the
manufacture. The majority of these materials, particularly the
extracts, are imported to the U.S. for distribution, and there-
fore represent little or no manufacturing activity.
2. Many of the products listed represent old technology, particu-
larly hardwood distillation. The products associated with the
recovery and processing of pyroligneous acid have been displaced
from the market, and thus from manufacturing activity, by cheaper
synthetic substitute products. Compounds which are contained in
pyroligneous acid include acetate of lime, acetone, calcium
acetate, ethyl acetate, methyl acetone, and methyl alcohol.
Also, the technology for manufacturing pit charcoal, while still
employed in some parts of the world, is no longer employed in
the United States.
3. Crude tall oil, except skimmings, is a product of the Kraft
(sulfate) wood fiber pulping process. The manufacture of this
material is an integral part of the sulfate process and therefore
the associated wastewater production, if any, would be intricately
contained in Kraft manufacturing's raw waste load (RWL). In
actual practice, crude tall oil is usually shipped to fraction-
action plants which produce tall oil rosin, turpentine and pitch.
It is this fractionation step which is included in this study.
k. Rosins, produced by the distillation of pine gum or pine wood,
have been listed in Table IIIB-1. These rosins have historically
been used with varying success as a principal ingredient of nu-
merous products, such as printing inks, linoleum, varnishes,
electrical insulation, foundry core oils, leather, adhesives,
masonry, and solder fluxes. However, since 19^9, gum rosin
IM-lA
-------
gum: processing but not
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II1-15
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production has decreased and wood rosins markets have been limited
by the competition of tall oil rosin. In addition, most of the
rosins sold in the industry today are either thermally or chemi-
cally modified derivatives which have improved applications both
in older markets and in recently developed markets such as plastic
phenolic resins and derivatives and rubber manufacturing.
It must be understood that the list in Table IIIB-1 was developed by
the United States Department of Commerce and is oriented toward the
collection of economic data related to gross production, sales, and
unit costs. The SIC list is not related to the true nature of the
industry in terms of actual plant operations, production, or con-
siderations associated with water pollution control. As such, the
list does not provide a realistic or definitive set of boundaries
for study of the Gum and Wood Chemicals industry.
A graphic view of the entire industry is provided in Figure IIIB-1.
It should be noted that, even though the study did not concern the
management of forests, timber harvesting, or the production of pulp
via the Kraft pulping process, these areas of endeavor are included
to provide an understanding of the interrelationships of activities
within the industry as well as those which are essential to the
supply of the necessary raw materials to the industry. During the
course of the study, six major production areas were identified for
in-depth study:
1. Char and charcoal briquet manufacturing via carbonization of
hardwood and softwood scraps.
2. Gum rosin and turpentine manufacturing via steam distillation
of gum from long leaf and slash pine trees.
3. Wood rosin, turpentine and pine oil manufacture via the solvent
extraction and steam distillation of resinous material from old
wood stumps obtained from cut over pine forests.
k. Tall oil rosins, fatty acids and pitch production via the
fractionation of crude tall oil, a by-product of the Kraft
pulping process •
5- Essential oils production via steam distillation of coniferous
wood fines from select lumbering operations.
6. Rosin derivatives manufacture via chemical or thermal modifica-
tions of either tall oil, gum, or wood rosins.
111-16
-------
DRAFT
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111-17
-------
Techn I ca I ADD roach to the Deve 1 opmen t of
' < G
The effluent limitations and standards of performance recommended in
this document for Gum and Wood Chemicals industry were developed in
the manner outlined in "Methods Used for Development of Effluent
Limitations and Standards of Performance" at the beginning of Section III
Scope of Coverage for Data Base
According to the 1972 Census of Manufactures, there are 135 estab-
lishments engaged in the primary manufacturing activities of
SIC 2861 products. These establishments were responsible for total
product value shipments totaling $226 million, or 76 percent of the
total $296.3 million worth of gum and wood chemical products. The
remaining products are produced in facilities primarily engaged in
other manufacturing activities. Table IIIB-2 presents a breakdown
of product value shipped by major manufacturing activity as cstnb-
lished by this study. It should be noted that the reported value
of the product shipped does not necessarily represent a level of
manufacturing activity. For example, the $5. A million value for
natural tanning and dyeing materials and chrome tanning mixtures is
more probably representative of a wholesaling operation rather than
actual manufacturing.
In order to help quantify the problem, it should be noted that only
12 of the 135 establishments primarily engaged in production of
commodities listed under SIC 2861 have applied for NPDES discharge
applications. Five of those 12 facilities were surveyed during the
course of this study.
I I 1-18
-------
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111-19
-------
C. Pesticides and Agricultural Chemicals Industry
Scope of the Study
The categories covered by this document in the Pesticides and Agri-
cultural Chemicals industry are in Standard Industrial Classification
(SIC) 2879~Pesticides and Agricultural Chemicals, and establishments en-
gaged in manufacturing agricultural pest control chemicals covered under
SIC group 281 and group 286. List of the specific products covered
in this SIC are presented in Table IIIC-1.
Pesticides have usually been classified according to the target organ-
ism or species, such as insecticides, herbicides or fungicides. Table
IIIC-2 presents U.S. production levels for the various sections of
the industry for the period 1969-1972. Clearly, insecticides and
herbicides are the most important commercially.
Individual^pesticides are referred to by generic or chemical name,
predominant trade name, competitive trade names, or abbreviation (e.g.,
DDT). This, and the fact that over 500 commercially important pesti-
cides are manufactured, make individual references extremely difficult,
and could be a source of confusion in this document. Throughout this
document individual pesticide types will be referred to by their "common
names". In a few instances, the generic or chemical name matches the
common name. The common name is usually: (1) a hybrid of the original
trade name, or (2) an abbreviation based on the chemical structure.
To better understand pesticides nomenclature, refer to the Pesticide
Handbook-Entoma. Volume 1, Pages 110-13**, where a list of common names,
chemical names, and alternative designations are presented. This
list is the basis for the pesticides referencing employed in this
document.
It should be understood that specific pesticide manufacturing opera-
tions are unique, and generally characteristic only of a give facility.
There are very few, if any, pesticide plants which manufacture one
product or use one process. Instead, almost all plants are multi-
product/process facilities, where the final mix of products shipped
is unique to that plant. Some plants (such as batch chemicals com-
plexes) produce hundreds of products, while other facilities manu-
facture only two or three high-volume products. In many instances,
even the product mixes vary from day to day. Furthermore, the pro-
duction quantities associated with the product mix shipped from a plant
are not necessarily a true indication of the extent or type of manu-
facturing activities carried out within that plant. Frequently, pro-
ducts are utilized captively as feedstocks in the manufacture of other
products. These factors must be considered since water usage and
wastewater generation patterns in the Pesticides and Agricultural
Chemicals industry are directly related to the diverse nature of its
manufacturing processes and the availability of essential raw materials.
111-20
-------
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111-21
-------
Table IIIC-2
U.S. Pesticides Production by Classes (1969-1972)'
DRAFT
Pest I ci
1910 l
NA
L.yxj
1.958
2,^00
94 1
45,988
85,607
182,091
(47,077)
56,998
NA
2,771
NA
53k
1,597
30,000
(k,999)
11,626
268,238
423,840
107,311
1,158
123,103
8,611
9,204
20,033
NA
50,572
NA
NA
260,892
1,730
28,768
','),',n\
NA
NA
NA
1,11k
^7,170
50,307
168,470
(43,576)
NA
NA
3,271
30,^54
457
2,016
30,000
NA
12,335
312,132
434,241
88,641
1,144
59,316
NA
4,156
21,047
(132,496)
41,353
15,259
75,884
188,632
1,695
•51. 1 I!'
•'.',, 1 ID
NA
NA
NA
601
50,877
60,875
l80,270
NA
NA
NA
NA
24,476
337
NA
30,000
NA
NA
404,036
458,849
116,264
940
NA
NA
6,168
NA
(138,185)
37,226
NA
100,959
303,261
?,206
?8,o64
I|D ./!',*(
NA
NA
NA
5^7
49,704
49,610
170,569
NA
NA
NA
4,472
30,698
307
NA
30,000
NA
NA
4l6,l4l
481, 618
141,858
900
NA
NA
6,000
24,633
(160,642)
51,076
NA
109,566
236,442
580,884 495,432 564,818 570,475
1,186,815 1,098,143 1,203,937 1,222,662
1 Source: Pesticide Handbook-Entoma, Entomological Society of America, 1974.
NA Data not reported
111-22
-------
DRAFT
Analysis of the manufacturing processes is a logical starting point
for any study whose objective is the development of national effluent
limitations guidelines. In order to develop such process-based ef-
fluent limitations guidelines, it was necessary to try to utilize
some "common denominator" which would relate diverse production activi-
ties (waste generating activities) with wastewater control and treat-
ment technologies. The process raw waste load (RWL) is considered the
best tool for accomplishing this objective.
Unlike some industries where relatively large plants manufacture es-
sentially a single product from a limited number of raw materials (e.g.,
cement plants), the Pesticides and Agricultural Chemicals industry in-
volves a complex mixture of raw materials, processes, product mixes,
and product formulations. To understand this industry completely, it
is necessary to examine selected chemical groupings and product cate-
gorizations in some detail. Of over 500 individual pesticides of
commercial importance, and perhaps as many as 8,000 distinct major
formulated products, the following pesticides product divisions can
be made:
1. Halogenated organic
2. Phosphorus-containing
3. Nitrogen-containing
4. Metallo-organ ic
5. Botanical and microbiological
6. Miscellaneous (not covered in the preceding groups)
This grouping will expedite discussion of the relationships and dif-
ferences among the various chemical groups. Some examples of these
differences are: the prolonged persistence of chlorinated hydrocarbons
versus organophosphates in the environment; the amenability of organo-
phosphates to chemical precipitation; the various physical properties
of pesticides (for example, oily versus crystalline), which may affect
the selection of control and treatment processes; and the amenability
of particular chlorinated hydrocarbons to recovery (for example, by
steam stri pping).
The distribution of the Pesticides and Agricultural Chemicals industry
among the preceding product groups or families is presented in Table
IIIC-3- It can be seen that the nitrogen-containing group is the
most diverse, and that the halogenated, phosphorus-containing, and
metallo-organic families are approximately equal in diversity.
Table IIIC-4 lists the majority of the pesticides manufactured in the
U.S. according to family and chemical structure, and their chemical
configuration, which is also illustrated in the table.
I I 1-23
-------
DRAFT
The halogenated organic group of pesticides Includes many first-
generation organic pesticides, e.g., DDT, and has a broad spectrum
of insecticidal action with prolonged stability and residual activity.
This, along with competition from new products which are more eco-
nomical, less toxic to higher animals, and more environmentally de-
gradable, has caused a decline in their usage since the mid-1960's.
The phosphorus-containing insecticides are among the fastest growing
products in the Pesticides and Agricultural Chemicals industry. Thou-
sands of phosphorus-containing compounds have been evaluated for
pesticidal properties, and current commercially used ones include
insecticides that are marketed in multimi11 ion-pound quantities. The
number of highly toxic phosphorus-containing compounds is virtually
limitless. Their suitability as insecticides, however, depends on
their specific physical and chemical properties, and on how safely
they can be employed. Although they are very toxic, phosphorus-
containing compounds generally are easily hydrolyzed in an alkaline
medium to yield materials of relatively low toxicity. Generally,
these pesticides are also environmentally degradable.
Several classes of nitrogen-containing compounds have been produced
and successfully marketed since 19^5- These have the broadest range
of biological activity and can be applied as selective herbicides,
insecticides and fungicides. Herbicides and fungicides for which
nitrogen-containing compounds have recently been synthesized have
continued to increase their share of the pesticide market, an increase
of M.I percent in 1966, to 57.2 percent in 1970.
Metallo-organic pesticides, which are produced by a relatively limited
number of companies, include the ethylene bisdithiocarbamate class of
fungicides and the sodium methanearsenate herbicides, which are the
production leaders of this group. However, these products tend to
break down into toxic substances, such as ethylene thiourea. New non-
metallic products, such as nonmetallic fungicides which eliminate the
objectionable presence of heavy metals, are expected to take a large
share of future markets.
Three of the botanical and biological insecticides, bacillus thur-
ingienes, rotenone, and the pyrethrins, though quite effective and
useful in insecticide formulations, are nontoxic to mamals, and are
found widely in nature. Since these pesticides must be extracted or
obtained through a fermentation process, however, large-volume pro-
duction (greater than one million pounds per year) is seldom en-
countered.
111-24
-------
DRAFT
Table 11 IC-3
Pesticide Classification
Number of
Major Pesticides
A. Halogenated Organics
DDT and relatives 9
Chlorinated Aryloxyal kanic Acids 12
Aldrin-toxaphene group 16
Halogenated aliphatic hydrocarbons 20
Halogenated aromatic-type compounds, not elsewhere
classified 29
Other chlorinated compounds 12
98
B. Phosphorus-Containing Pesticides
Phosphates and phosphonates 19
Phosphorothioates and phosphonothioates 61
Phosphorus-nitrogen compounds 8
Other phosphorus compounds _5_
93
C. Nitrogen-Containing Pesticides
Aryl and alkyl carbamates and related compounds 35
Thiocarbamates 23
Anilides 13
Amides and amines (without sulfur) 2k
Ureas and uraci Is 20
Triazines Ik
Amines, heterocyclic (sulfur-containing) 12
Nitro compounds 26
Other nitrogen-containing compounds k2
209
D. Metal lo-Organi c Pesticides
Mercury compounds 28
Arsenic compounds 17
Other heavy metal compounds 17
Other inorganic compounds, including cyanides,
phosphides , and related compounds 2k
86
E. Botanical and Microbiological Pesticides 19
F. Organic Pesticides, not elsewhere classified
Carbon compounds 41
Anticoagulants _k_
Total 550
II1-25
-------
DRAFT
Table \\\C-k
c ructural Chemistry of Typical and Major Pesticides
Ha loqenated Organ i cs
X=norma]|y Cl Y=normally CCI, Z=normally H
DDT, ODD, TOE, Perthane*, Methoxychlor, Prolan, Bulan, Delan, Gex,
DIcofol, Chloropropylate, Bromopropylate, Parinol, Chlorobenz i late
MOinated Arxakani Acds
R=normal ly H or CH
X=normally Cl 3
OCHR (CH, )m COOH Y=always Cl
Z=normally H or Cl
X
2,4-D and its derivatives, 2,4,5-T and its derivatives, Silvex,
Dichloroprop, Sesone, Fruitone CPA*, MCPA, MCPB, MCPP, Erbon
Product
= perchlorinated ring
Kepone*, Heptachlor, Mirex, Pentac*, Chlordane, Telodrin, Aldrin,
Dieldrin, Toxaphene, Endrin, Endosulfan, Isodrin, Alodan, Bromodan,
Strobane
HaJ_O£enated_ AJJphat_i£ Hyd_r£ca_rb_o£s
X
I
R — C — X
I
X
X=halogen, H, or 0
R=Alkyl grouping or halogen
TCA and its salts, Dalapon and its salts, Fenac, Methyl Bromide,
Carbon tetrachloride, DBCP, DD*, EDB, Lindane, Glytac*
trademark Ml-26
-------
Table I I \C-k
(Cont inued;
Halogenated^ Aj-pjTiaJ:j_c_Cojnp_ounds
DRAFT
X=C1, and NH ,OCH , H, etc
R=OH, H, CL, RCOOH, ESTER,etc.
B.
Benzene hexachloride, Dichlorobenzenes, Dacthal*, PCP and its salts,
Hexachlorophene, Chloroben, Hexachlorobenzene, Dicamba, Tricamba,
Chlorneb, Probe, Fenac*, Pipe'ralin, 2,3,6-TBA, TCBA, Tiba, Amiben,
Propanil, Bandane, Strobane
Phosphorus-Conta i n i ng
£^ho_s£ha_te_s_and_Phpsphpn_ates_
R0
Dichlovos, Dicrotophos, Ciodrin*, Trichlorfon, Ethephon, Gardona*,
Mevinphos, Naled, Nia 10637, TEPP, Phosphamidon
P_hosp_ho_rothM oates and_ Phos£honothjoat_es_
S
it
(RO), P A (CH)
(I )
)n
Parathion, Me-Parathion, Dicapton, Chlorthion, Fenthion, Ronnel,
Sumithion, Demeton, Diazinon, Dioxathion, Guthion*, Malathion,
Coumaphos, Dasanit*, Phorate, Disulfoton, Ekatin, Abate*, Acetellic*,
Pyrazophos, Akton*, Aspon*, Monocrotophos, Betasan*, Def*, Diraethoate,
Chlopyrifos, Dyfonate*, EPN, Ethion, Folex*, Phentriazophos, Imidan*,
Menazon, Demeton-0-methylsulfoxide, Prophos, Phenthoate, Leptophos,
Pirimiphosethy1, Sumithion*, Supracide*, Surecide*, Dialifor, Carbo-
phenothion, Dichlorofenthion, Zinophos*, Phosalone
*Trademark
II1-2?
-------
DRAFT
Table II 1C -A
(Continued)
Cpmp£imd£
(S)
R 0 n
1 ^ P-R3
R9N^
\
Y
Ruelene, Nellite*, Nemacur*, Orthene*, Cyolane, Cytrolane, Go
phacide*, Monitor*
C . Nitrogen - Containing
and Reated
0 0
R 0 C NH R and £ 0 C NH CH
' 2
Propham (IPC), Chloropropham (CIPC), Barban, Swep, Sirmate*, Azak*,
Isolan, Metacrate*, Carbaryl (Sevin*), Zectran*, Metacil*, Baygon*,
Mesurol*, Temik*, Banol, Meobal*, Landrin*, Betanol*, Asulox*, BUX,
Carbofuran, Lannate*, Osbac*, Pirimicarb, Tandex*, Mobam*
Thiocarbamates
R
R.N C S R
Y
EPTC, SMDC, Vernolate, CDEC, pebulate, Dial late, Trial late, butylate,
Molinate, Cycloate, Bolero*, Eptam*
Amj_des_and_Atnines _(wj_thout: sul£ur)
0
ii
RiC N —R-
I
Y
Pronamide, Alachlor, Dicryl, Solan, Propanil, Diphenamid, Propachlor,
CDAA, Naptalam, Cypromid, CDA, Chlonitralid, Benomyl, Deet, Dimetilan,
Diphenylamine, Hormodin*, Butachlor, Naphthalene acetamide, Vitavax*
^Trademark
I I 1-28
-------
Table I I IC-4
(Continued)
Ureas and UraciIs
and
CH
H
I
-R,
DRAFT
Fenuron, Monuron, Diuron, Fluometuron, Linuron, Metobromuron, Momo-
linuron, Neburon, Siduron, Chloroxuron, Buturon, Chlorbromuron,
Norea, Cycluron, Antu*, Metrobromuron, Monuron TCA, Probe*, Urab*
s-Triazines
R1N
\ »*m R
N
?
Ametryne, Atratone, Atrazine, Simazine, Simetone, Simetryne, Pro-
metone, Prometryne, Propazine, Lambast*, Chlorazine, Bladex*,
Prefox*, Sancap*, Sumitol*, Terbutryn, Dyrene*
Benefin, Dinocap, Dinosep (DNSP), DNOC, Mitral in, PCNB, Trifluralin,
A-820*, Dfnoseb Acetate, Binapacryl, Dinitramine, Fluorodifen,
Isoproplin, Lamprecid*, Nitrofen, Torpedo*, Chloropicrin, DCNA
Othe Ni
These have varied chemical structures
Actellic*, Pyrazophos, Ametrole, Banamite*, Benomyl, Benzomate, Cal-
ixin*, Captan, Carzol*, Chlordimeform, Cycloheximide, Cycocel*,Cyprex*,
Daconil*, Dexon*, Diquat, Fenazaflor, Maleic hydrazide, MGK 264*,
^Trademark
I I 1-29
-------
DRAFT
Table I I IC-4
(Continued)
MGK Repellent 326", Neo-Pynamin*, Paraquat, Thiram, Thiophanate,
Thynon*, Milcurb*, Milstem*, Nia 21844, Nia 21861, Nia 23486,
Nicotine, N-Serve*, Ohric*, Picloram, Piperalin, Plantvax*,
Pyramin*, Ronstar*, Rowtate*, SADH, Sencor*, Sicarol*, Stop
Scald», Streptomycin, Tandex*, Thantte*, Difolatan*, Folpet,
Mertect*, Morestan*, Nia 19873, Niacide*, Ordram*, Terrazole*,
My lone (DMTT)
D. Metallo-Organic
These have varied chemical structures, and therefore, no generalized
formula can be derived.
Brestan*, Cacodylic Acid, CMA, Manzate 200", Copoloid", Copper-8-,
Copper Oleate, DSMA, Du-Ter*, Ferbam, Maneb, MSMA, Nabam, Niacide-,
Plictran*, Zineb, Ziram
E. Botanical and Microbiological
These have varied chemical structuress and, therefore, no generalized
formula can be derived.
Pyrethrins, Bacillus Thuringiensis, Polyhedrus Virus
F. Miscellaneous Pesticides (not elsewhere classified)
These have varied chemical structures, and, therefore, no generalized
formula can be derived.
Cresote, Nicotine, Rotenone, Petroleum oils, Butoxy, Calamite*,
Dexon*, MGK Repellent 8y4*, Omite*, Sulfoxide, TCTP, Tetradifon,
Thi ram
^Trademark
111-30
-------
DRAFT
There are pesticides which do not readily fall into any qroup. Of
these, the rodent i c i do W.irt.irin deserves mention. If. product ion h.r.
exceeded 12 million pounds per ye
-------
DRAFT
Scope of Coverage for Do la Base
The Pesticides and Agricultural Chemicals industry is spread geographi-
cally across the U.S. (See Figure IIIC-1) and is diverse in manufacturing
plant size and operations complexity. Eleven pesticides manufacturing
complexes were visited, encompassing all categories and major subcate-
gories. This included, plants in different locations and of varying
size and complexity. The plant visits included two halogenated or-
ganics, six organo-phosphorus, four organo-nitrogen, one metallo-
organic, and two formulating production facilities. In all, ninety
percent of the Pesticides and Agricultural Chemicals industry was
covered by the plant visits.
111-32
-------
DRAFT
o.
Z
o
T Q
O O
— cc
— a.
aj to
CC ui
01
a.
LL
O
CO
o
O
111-33
-------
DRAFT
D. Adhesive and Sealants Industry
Scope of the Study
The Adhesive and Sealants industry was defined by EPA for the
purpose of this study to include only those commodities listed
under Standard Industrial Classifications 2891 and 2899, as shown
in Table MID-1. The SIC code provides a valuable guideline for
dividing United States manufacturing activities into manageable
categories. The volume of adhesive production in the United
States in 1967 is shown in Table IIID-2.
It must be understood that the list as provided in Table IIID-2
was developed by the United States Department of Commerce and is
oriented toward the collection of economic data related to gross
production, sales, and unit costs. They are not related to actual
plant operations, production, or considerations associated with
water pollution control. As such, they do not provide a realistic
or definitive set of boundaries for study of the Adhesive and
Sealants industry.
The states with the highest concentration of Adhesive and Sealants
industry include: Illinois, New Jersey, California, Massachusetts,
and New York. Chicago has more adhesive and sealants production
facilities than any other city in the United States.
Technical Approach to the Development
of Effluent Limitation Guidelines
The effluent limitations and standards of performance recommended
in this document were developed in the manner outlined in "Methods
Used for Development of the Effluent Limitations and Standards of
Performance" at the beginning of Section III.
I I 1-
-------
DRAFT
Table I IID-1
Standard Industrial Classification of Products from
the Adhesives and Sealants Industry
SIC 2891
Adhes ives
Adhesives, plastic
Calking compounds
Cement (cellulose nitrate
base)
Cement, 1inoleum
Cement, mending
Cement, rubber
Epoxy adhesives
Glue, except dental:
animal, vegetable, fish,
casein, and synthetic
resin
Iron cement, household
SIC 2899
Gelatin: edible, technical, photographic, and pharmaceutical
Laminating Compounds
Mucilage
Paste, adhesive
Porcelain cement, household
Rubber cement
Sealing compounds for pipe
threads and joints
Sealing compounds, synthetic rubber
and plastic
Wax, seal ing
NI-35
-------
in
O
CO
4-1
in
DRAFT
CM
O
«
—
.
0)
^-»
_O
(D
h-
0) >.
3 U
^™ i *
(D i/l
> 3
TO
4-i C
U —
3
TO 4-1
O C
I- IT)
O_ —
to
-a co
c in
to
-a
c c
o to
4-1 (U
u >
3 —
TO
3 \
— in
o -o
> c
3
C O
o a.
4-> C
o o
3 —
T3 —
O —
L_ .-
Q- E
*w*
4-1
(n
3
TO
C
—
1
-3- CO CM LT\ r»-l
,— i -3- «— i \O ~r ro
"~ 1 O
tn •
CM Q
in ••
a. c
5 °
O -t-1
1- CD
CD C
1- -C
O v>
— > <0
L
I/I (U
0) a)
— >
OJ ^.
tr> -co-
4-1 C
0 0
3 —
-D —
O —
> t _.._
Q- E
>•« X
«3
• •• in
CM 3
C
1_ CO
LACTlOOLTVO CV-vLTV (DO
CM «*\ «*\ r^ -f rr\ Q.
r— <4-
• ~ o
^—
»- 3
CO
CO CO
E i-
3 3
•— CQ
O
> 1
0)
O T3
— O
«/><_>---- _
C7\cr\cr\c7^cr> CT^c^l coo
co co oo co oo oooo i- i-
CMCMCMCMCM CMCM 3CO
4-1 E
U E
(D O
>4- O
3
C <4-
Product
^w
tD
u
•«
E
CO
^:
o
(0
3
1—
D>
^^
ID
_E
C
<
CO
3
^-»
CD
CO
-Q
to
4->
CO
CD
a)
>
o
l/l
c
V)
a>
u
u
._
4-1
CO
-C
4-1
c
>-
l/l
1/1
CO
u
4-1
CO
-C
4-1
c
>*
(/) U)
c
-a o
c —
10 4-1
(D
I- C
(U ~
-Q J3
-Q E
3 O
<£. U
u
i_
3
O
0) 01
E *->
4-> C
»- to
CO
U
co
3
C
II1-36
-------
DRAFT
Explosives Industry
The compounds covered by the Explosives industry as designated in
SIC 2892 are shown in Table IIIE-1.
As stated previously in the Conclusions Section, inorganic and organic
acids are not considered as a part of the Explosives industry and have
been excluded from consideration in this document.
In addition, little quantitative information could be gathered for
the process of demilitarization of explosives. (Demilitarization
normally would occur in the Load and Pack subcategory.) This is a
process by which the military scours obsolete or defective munitions
with steam hoses to remove explosives and propellants from their con-
tainers (e.g. projectiles and shell casings). The process is per-
formed so as to save the containers for possible reuse.
The pollution load from the operation of demilitarization can be
very high. It is recommended that this operation be dealt with on
a plant-by-plant basis.
To help clarify the coverage of this document the following are ex-
cluded from the scope of this study.
Metal parts and finishing
- Toxic chemical agents
Illuminants and incendiaries
Liquid propellants
Nuclear explosives
Demilitarization (as noted)
The Explosives industry can be divided into two broad areas: mili-
tary and commercial. Military and commercial plants differ in both
size and product. Ammonium-nitrate-based explosives, dynamite, and
nitroglycerin are considered commercial explosives, while TNT, HMX,
and RDX are generally considered military explosives.
The manufacture of explosives in either area can be viewed primarily
as the nitration of an organic molecule. Most processes use nitric
acid as the nitrate source and employ sulfuric or acetic acid as a
dehydrating agent. Therefore, most wastes in the industry are low
in pH.
Wastewaters in the Explosives industry are of concern because of their
pollutional nature and, in certain cases, their hazardous character.
For example, wastewaters from nitroglycerin manufacture are often
saturated with soluble nitroglycerin, which may become a potential ex-
plosive hazard if concentrated. Other than military publications, in-
formation pertaining to the wastewaters of explosives manufacture and
pollution abatement technology applicable to the Explosives industry
is very 1imi ted.
IM-37
-------
DRAFT
Table I 1 IE-1
Explosives Products - SIC 2892
Amatol (explosive)
Azides (explosives)
Blasting powder and blasting caps
Carbohydrates, nitrated (explosives)
vordeau detonant (explosive)
Cordite (explosive)
Detonating caps for safety fuses
Detonators (explosive compounds)
Dynamite
Explosive cartridges for concussion
forming of metal
Explosive compounds
Explos ives
Fulminate of mercury (explosive com-
pound)
Fuse powder
Fuses, safety
Gunpowder
High explosives
Lead azide (explosive)
Mercury azide (explosive)
Nitrocellulose powder (explosive)
Nitroglycerin (explosive)
Nitromannitol (explosive)
Nitrostarch (explosive)
Pentolite (explosive)
Permissible explosives
Picric acid (explosive)
Powder: pellet, smokeless and
sporting (explosive)
RDX (explosive)
Squibbs, electric
Styphnle acid
Tetryl (explosive)
TNT (trinitrotoluene)
Well shooting torpedoes (explosives)
111-38
-------
DRAFT
Tochr i i ca 1
oTL Tf 1
To prepare effluent limitation guidelines for the Explosives industry
it was necessary to develop a comprehensive scope of work. Each EPA
Regional office was visited, and permit information was gathered.
This enabled Weston to select pertinent plants to visit and sample.
Plant visits were generally made up of two phases. The first took
place in an office, where pertinent data was exchanged. The second
phase consisted of a walk through the plant, viewing each process
previously discussed.
Four commercial and two military explosives plants were visited. Ex-
tensive sampling was performed at each of the commercial plants,
while the military plants were visited for conceptualization, visual
inspection, and verification of already-existing data. The data
existing for the government-owned, contractor-operated munitions plant
were collected and made available by the Army Environmental Hygiene
Association (AEHA) .
The Army operates fifteen munitions plants, the Navy operates six
plants, and the Air Force three. Only the Army is actually engaged
in the manufacture of explosive. Although there are Load and Pack
(LAP) operations at various Navy and Air Force installations, no
meaningful data have yet been assembled. Hence, the Army is the
only usable source of military effluent quality data. Consequently,
it was decided that the focus of the study of the military area of
the Explosives industry would be the Army Ammunition Plants (AAP) .
Excellent representative effluent data for the several AAP ' s were
included in the information provided by AEHA.
Hence, visits with AEHA personnel, investigation of laboratory tech-
niques and equipment, and rationalization of the excellent field pro-
cedures made visits to the Army facilities less important. The size
of the Army installations also contributed to the decision not to
sample any Army Ammunition Plants. Instead, the AEHA reports were
used to their fullest extent. Nevertheless, two AAP ' s , considered the
biggest and most representative, were visited.
When all the Explosives plant visits were completed and the laboratory
analysis of the samples finished, waste load characteristics were
compiled, and each process waste stream was characterized by production-
based water quality parameters. Trial -and-error manipulation of waste
loads produced an acceptable subcategorization of the industry. Ef-
fluent guidelines were determined for each category by summarizing
the removal rates of a treatment facility serving a propel lant plant.
111-39
-------
DRAFT
Table I I IE-2
Major Operations at Major Ammunition Plants
Explosive Propellant Initiator Load and
P1 ant Manufacture Manufacture Manufacture Pack.
ARMY
HoIston AAP +
Radford AAP + + +
Jollet AAP + + +
Badger AAP + +
Lake City + + +
Lonyhorn AAP +
Newport AAP +
Volunteer AAP +
Indiana AAP +
Iowa AAP +
Kansas AAP +
Louisiana AAP +
Lone Star AAP +
Milan AAP +
Twin Cities AAP + +
Sunflower AAP ' + +
NAVY
NAD Indian Head + + +
NAD Yorktown +
NAD Crane + +
NAD McAlester +
NAD Hawthorne +
Navy Magna Plant + +
AIR FORCE
AF Plant 78 +
COMMERCIAL
*«5 + +
46 +
47 +
48 + + +
49 + +
50 + + +
111-40
-------
DRAFT
Corbon Black Industry
Scope of the Study
The term Carbon Black identifies an important family of industrial
carbons used principally as reinforcing agents in rubber and as
black pigments in inks, coatings, and plastics. Carbon black, a
petrochemical, is an extremely fine soot composed principally of
carbon (90 - 99 percent), with some oxygen and hydrogen. Carbon
blacks are differentiated from bulk commercial carbons (such as
cokes and charcoals) by the fact that carbon blacks are particulate
and are composed of spherical particles, quasigraphitic in structure
and of colloidal dimensions. The properties of carbon black are de-
termined primarily by the process by which it is manufactured.
All carbon blacks are produced either by partial combustion or ,lherrn.)l
decomposition of liquid or gaseous hydrocarbons, and are classified
as lamp black, channel black, furnace combustion black, and thermal
black. The Standard Industrial Classification number for the Carbon
Black industry is 2895- Lamp blacks are made by the burning of petro-
leum or coal-tar residues in open shallow pans, channel black by im-
pingement of under-ventilated natural gas flames, and furnace com-
bustion blacks by partial combustion of either natural gas or liquid
hydrocarbons in insulated furnaces. Thermal blacks are produced by
thermal decomposition (cracking) of natural gas. Acetylene black,
which is classified as a thermal black, is produced by the exothermic
decomposition of acetylene. Brief descriptions of these processes
fo11ow:
Lamp Black Manufacture
Lamp black is the ancestor of all carbon blacks. Until the 1870's it
was the only carbon black available commercially. The manufacture of
lamp black was practiced by the Chinese and Egyptians during the pre-
Christian era. Purified resins, fats, and oils were burned beneath
inverted porcelain or pottery cones, and the soot deposited on the
cool surface was carefully brushed off from time to time.
Lamp black manufacturers still follow this basic process. The principal
raw materials used today however, are petroleum and coal tar by-products,
such as creosote and anthracene oils. They are burned in open, shallow
pans with restricted air supply. The resulting carbon smoke is then
conducted to a series of settling chambers, where the flocculated car-
bon deposits are periodically recovered. In a typical operation,
coal-tar distillate or creosote is burned from pans four feet in
diameter and six inches in depth. The smoke from each pan passes
slowly through a series of settling chambers, where most of the black
collects. The remainder is periodically collected by bag filters
-------
DRAFT
1 rom both settling chambers and filter systems by vacuum collectors.
Since the gas velocities are very low, heat Is dissipated in the
chambers without a need for water-spray cooling.
In recent years, this process has undergone some changes and develop-
ments, making it more similar to the oil furnace black processes. These
modified lamp blacks more closely resemble oil and gas furnace blacks
than traditional lamp blacks. Lamp blacks are of large particle size,
possess little reinforcing ability in rubber, and are lower in jet-
ness and coloring power. They are of value as tinting pitments in
certain paints and lacquers. In most applications, however, they
have been replaced by furnace blacks.
Channel Black Manufacture
Channel black is a product of incomplete combustion of natural gas.
Small flames are impinged on cool surfaces, or channels, where carbon
black is deposited and then scraped off as the channel moves back and
forth over a scraper. The properties of channel black are varied by
changes in burner tip design, distances from tip to channel, and the
amount of air made available for combustion. The process is extremely
inefficient chemically. For rubber-reinforcing grades, the yield is
only 5 percent; for finer particle size, higher color blacks, the yield
shrinks to 1 percent. Low yields and rapidly rising gas prices have
motivated the industry to develop other methods of carbon black pro-
duced in the United States was produced by the channel black process.
At present there is only a single channel black plant remaining in
operation in the United States, as compared to 35 plants in 1951.
Furnace Black Manufacture
In the oil furnace black process, liquid hydrocarbons are used. Yields
range from 35 to 65 percent, depending on the grade of black being
produced. The most desirable feedstock for furnace black comes from
near the bottom of the refinery barrel and is similar in many respects
to residual fuel oil. It is low in sulfur and high in aromatics and
olefins. The rising cost of natural gas has been a motivating factor
in the shift to greater use of liquid feedstock and to the decline
in the use of natural gas as a source of carbon. With this incentive,
the oil furnace black process has become very flexible. Oil furnace
blacks have nearly replaced channel blacks in most high-performance
applications, notably passenger-car tire treads. Over the past thirty
years, carbon black technology developments have centered on the oil
furnace black process, and today nearly all carbon black plants use
processes of this type.
111-42
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DRAFT
The gas furnace black process is based on partial combustion of natural
gas is refractory line furnaces. Yields of gas furnace blacks range
from 10 to 30 percent and are lower for the smaller particle si?e
grades. This process is similar to the oil furnace black process.
Approximately 91.5 percent of all carbon black manufactured In the
United States in 1972 was made by the furnace black process.
Thermal Black Manufacture
Unlike channel and furnace blacks, thermal blacks are produced by the
"cracking" of hydrocarbons. Feedstock is generally natural gas. Thermal
furnaces are built in checkerboard brickwork patterns. Two refractory-
lined furnaces, or generators, are used. One generator is heated,
using hydrogen as a fuel, while the other generator is being charged
with natural gas. The natural gas decomposes to produce thermal black
and hydrogen. The hydrogen is collected and used as a fuel for the
generator being heated. Particles from the thermal black process are
primarily large sizes, and yields range from 40 to 50 percent.
Approximately 7-8 percent of all carbon black produced in the United
States in 1972 was made by the thermal black process.
Due to the high cost and lack of natural gas, large-particle furnace
blacks (LPF) may soon replace many of the thermal black applications.
Acetylene blacks, a type of thermal black, are produced by the thermal
decomposition of acetylene. They possess a high degree of structural
or chaining tendency. The particle size is about ^0 millimicrons.
They provide a high elastic modulus and high conductivity in rubber
stocks. At the present time, no acetylene black is produced in the
United States. Most of the acetylene black used in this country is
produced in Canada.
Production and Uses
The United States is the largest producer of carbon black in the world,
producing approximately ^5 percent of the total world output (3.2 out
of a total 7.1 billion pounds in 1972).
Production in the United States has increased steadily since the
rubber industry began using carbon black in rubber in 1912. Figure
IIIF-1 illustrates the United States carbon black production by pro-
cess for the period from 1952 - 1972.
The furnace process is responsible for over 90 percent of the carbon
black produced in this country. At the end of 1974, there were 30
furnace black plants, four thermal black plants, and one channel black
I I I-J»3
-------
DRAFT
plant in operation in the United States. At the end of 1972, the
total carbon black production capacity in the U.S. was approximately
11,400,000 pounds per day. Approximately *»5 percent of this total
capacity was in Texas, 3^» percent in Louisiana, and 22 percent in
other states.
Originally, plants were established in Texas and Louisiana to be
near the natural gas sources, since no cheap means of transporting
this feedstock existed. As emphasis shifted from the channel pro-
cess to the furnace process, it was only natural that furnace facili-
ties would be expanded at these locations. In recent years, with
the emphasis on the furnace process, specifically on liquid hydro-
carbon feedstocks, the economics involved in transporting the feed-
stocks and the product (carbon black) have moved the optimum sites
for construction of new facilities to locations between the source
of the feedstocks (the oil fields) and the major users of the carbon
black (mainly the rubber manufacturers, specifically the tire manu-
facturers) .
Of the total carbon black consumed in the United States, approximately
95 percent is used by the rubber industry. Most of the remainder is
used by the printing ink, paint, paper, and plastics industries.
Table IIIF-1 illustrates the domestic sales of carbon black in the
United States by use from 1973 through 1972.
Technical Approach to the Development
of Effluent Limitation Guidelines
The effluent limitations and standards of performance recommended in
this document for the Carbon Black industry were developed in the
manner outlined in "Methods Used for Development of the Effluent
Limitations and Standards of Performance" at the beginning of
Section III.
Scope of Coverage for Data Base
Most of the Carbon Black industry is located in Louisiana and Texas.
In total, there are 35 carbon black plants in operation in the U.S.
There are thirty furnace black plants, four thermal black plants and
one channel black plant in operation. The plants visits covered
two furnace plants and one thermal plant.
\\\-kk
-------
DRAFT
FIGURE III F-1
U.S. CARBON BLACK PRODUCTION
BY PROCESS
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TOTAL
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-------
DRAFT
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111-46
-------
DRAFT
G. Photo(j raph i c Process i ng I ndust ry
Scope of the J>tu(Jy
For the purposes of this study, the Photographic Processing industry
was defined by EPA to include all film processing activities listed
under SIC 7221 (Photographic Studios, Portrait), SIC 7333 (Commercial
Photography, Art, and Graphics), SIC 7395 (Photofinishing Laboratories),
and SIC 7819 (Developing and Printing of Commercial Motion Picture
Film). Lists of the specific services covered by these standard
industrial classifications are presented in Table IIIG-1.
The Photographic Processing industry is made up of industrial and
commercial laboratories serving both the photographic trade and the
general public in film developing, photoprinting, and enlarging.
Photoprocessing plants vary greatly in size and are subject to
seasonal variations in production.
Technical Approach to the Development
of Effluent Limitation Guidelines
The effluent limitations and standards of performance recommended
in this document for the Photographic Processing industry were
developed as described under the technical approach in the general
section. The technical approach specific to this industry is
described below:
1. Plants were selected for visits on the basis of best repre-
sentation of the industry. The purpose of the plant visists
were threefold. First, the individual processes of black-
and-white and color film and paper within the plants were
investigated for familiarization with process concepts. At
this time, valuable information, otherwise unavailable, was
obtained on the various processes. Secondly, the purpose was
to investigate treatment technology, if any existed. Lastly,
and most importantly, the purpose was to verify existing
plant data on wastewater discharge with our own analytical
data measured in the field.
2. The raw waste loads (RWL) were determined on the basis of
data and field measurements taken on three photographic
processing plants. Data supplied by the Eastman Kodak
Company was also used to substantiate the field survey
data (G-1). There was very strong similarity in the RWL's
determined for the three plants.
111-47
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DRAFT
Table II IG-1
Photographic Studios, Portrait - SIC 7221
Home Photographers
Passport Photographers
Portrait Photographers
School Photographers
Transient Photographers
Table IIIG-2
Commercial Photography, Art, and Graphics - SIC 7333
Commercial Photography
Photographic Studios, Commercial
Table IIIG-3
Photofinish ing Laboratories - SIC 7395
Developing and printing of film, except commercial
motion picture film
Developing and processing of home movies
Film processing, except for the motion picture industry
Photograph developing and retouching
Photographic laboratories (not manufacturing)
Table IIIG-if
Services Allied to Motion Picture Production - SIC 7819
Developing and printing of commercial motion picture film
-------
DRAFT
3. Effluent guidelines were developed by applying an end-of-
pipe treatment model to the raw wastewater. The effluent
guidelines were developed for the industry as a whole with-
out subcategorization because the studies indicated there
was no need to impose different levels of treatment within
the industry. Effluent limitations have been developed
for silver thiosulfate, BODr, and COD based on the re-
moval rate attained by an operating biological system
(G-3, 4), and for ferrocyanide based on the equivalent
form of cyanide which is toxic to biological systems (G-5)•
Scope of Coverage for Data Base
Although there are an estimated 12,500 photprocessing plants in the
United States, only 650 of these facilities are considered major
laboratories with significant wastewater discharges (G-2). In
order to obtain the information required to establish realistic
effluent limitations, sampling surveys were conducted at three photo-
processing plants. Since limited information is available on the
treatment of photoprocessing wastes, one of the plants visited was
selected because it had a pilot biological treatment plant in opera-
tion at the time of the survey. In addition to the field surveys,
supplemental historical data compiled by the Eastman Kodak Company
for approximately 200 photoprocessing plants was acquired and used
(G-1).
111-A9
-------
DRAFT
H. Hospi tals
Scope of the Study
In order to establish boundaries on the scope of work for this
study, the Hospitals category was defined to include all establish-
ments listed under Standard Industrial Classification (SIC) Group
Number 806, This group includes all establishments primarily en-
gaged in providing diagnostic services, extensive medical treatment
including surgical services, and other hospital services, as well
as continuous nursing services. These establishments have an organized
medical staff, inpatients, beds, and equipment and facilities to pro-
vide complete health care.
Descriptions of the specific hospital types included under Group
No. 806 are:
8062 General Medical and Surgical Hospitals
Establishments primarily engaged in providing general
medical and surgical services and other hospital services.
8063 Psychiatric Hospitals
Establishments primarily engaged in providing diagnostic
medical services and inpatient treatment for the mentally
ill, including mental hospitals and psychiatric hospitals.
8069 Specialty Hospitals, Except Psychiatric
Establishments primarily engaged in providing diagnostic
services, treatment, and other hospital services for
patients with specified types of illnesses (except mental),
including:
Children's Hospitals
Hospitals, Specialty
(except Psychiatric)
Chronic Disease Hospitals Maternity Hospitals
Orthepedic Hospitals
Eye, Ear, Nose, and
throat hospitals
Geriatric Hospitals
Tuberculosis Hospitals
111-50
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DRAFT
Technical Approach to the Development
of Effluent Limitation Guidelines
The effluent limitations and standards of performance recommended in
this document for the hospital category were developed in the manner
outlined "Methods Used for Development of the Effluent Limitations
and Standards of Performance" at the beginning of Section III.
Scope of Coverage for Data Base
There are over 7,000 hospitals located throughout the United States.
During this study, data from hospitals in Pennsylvania, New York,
New Jersey, West Virginia, California, Maine, Wyoming, and Georgia
were collected and analyzed. A total of 12 hospital facilities were
studied during the project, three of which were surveyed by field
sampling teams. Data for the remaining nine hospitals were obtained
from the Veteran's Administration. The types of hospitals studied
included general medical and surgical, psychiatric, tuberculosis,
cancer, orthopedic, and research facilities.
111-51
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DRAFT
SECTION IV
INDUSTRIAL CATEGORIZATION
The goal of this study la the mflrit of nfllii«fH limitation miifla
lines For the Miscellaneous Chemicals Industry Ihfll will IIP MHIIIMPM
surate with different levels of in-process waste reduction ami rod of
pipe pollution control technology. These effluent limitations guide-
lines are to specify the quantity of pollutants which will ultimately
be discharged from a specific manufacturing facility and will be re-
lated to a common yardstick for the industry, such as quantity of
production. Recognizing that the industries grouped under the Miscel-
laneous Chemicals category are quite diverse in raw materials used,
in manufacturing processes and products, and in nature of wastewater
generated, each major industry is treated independently as a category
as follows:
Category
A
Industry
Pharmaceutical
D
E
F
Gum and Wood
Pesticides and
Agricultural Chemicals
Adhesive & Sealants
Explos ives
Carbon Black
SIC Codes
SIC 2831 Biological Products
SIC 2833 Medicinal Chemicals and
Botanical Products
SIC 283^ Pharmaceutical Preparations
SIC 2861 Gum and Wood Chemicals
SIC 2879 Pesticides and Agricultural
Chemicals
SIC 2891 Adhesive and Sealants
SIC 2892 Explosives
SIC 2895 Carbon Black
G Photographic Processing SIC 7221 Photographic Studies,
Portrait
SIC 7333 Commerical Photography,
Art and Graphics
SIC 7395 Photofinishing Laboratories
SIC 7819 Printing of Commercial Motion
Picture Film
H Hospitals SIC 8062 General Medical and Surgical
Hospi tals
SIC 8063 Psychiatric Hospitals
SIC 8069 Specialty Hospitals
The diverse range of products and manufacturing processes within each in-
dustry dictates that separate effluent limitation guidelines be designated
for different segments within each industrial category. To this end, a
subcategorization of each individual category covered under the Miscel-
laneous Chemicals industry has been developed and described in the fol-
lowing text.
IV-1
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DRAFT
Pharmaceutical Industry
Discussion of the Rationale
of Categorization
Industry subcategories and sub-subcategories were established for
the Pharmaceutical industry to define those sectors of the industry
where separate effluent limitations and standards should apply. In
the final analysis, the underlying distinctions between the various
subcategories have been based on the wastewater generated, its
quantity, characteristics, and applicability of control and treatment.
The following factors were considered in determining whether such sub-
cateqorizations are justified:
Manufacturing Process
There are six basic processing techniques in common use in the Pharma-
ceutical industry. These techniques, all distinctly different, are:
fermentation, chemical synthesis, formulation, fractionation, natural
extraction, and the growth and isolation of cultures. The first three
of these techniques are by far the most widely used.
Fermentation processes are used extensively in the Pharmaceutical in-
dustry to produce antibiotics. Fermentation plants are large water
users and the basic process steps used at these facilities are similar
throughout the industry. The basic production steps consist of the
initial fermentation step, a separation step (usually vacuum filtration
or centrifugation), and finally a series of extraction and purification
steps. The major wastewater from this processing technique is spent
beers from the initial fermentation step.
Chemical synthesis is another major production process in the Pharma-
ceutical industry. Hundreds of different products are made each year
using chemical synthesis techniques employed by the Pharmaceutical in-
dustry, which include a 1 kylations, carboxylation, esterification, halo-
genation, sulfonation, etc. Chemical snythesis plants are also large
water users.
The third major production process in the Pharmaceutical industry is
formulation. Formulation plants receive bulk chemical and fermentation
products as raw materials and subsequently manufacture the final dosage
forms (tablets, liquids, capsules, etc.). Some of the unit operations
utilized for formulating final products include drying, blending, grind-
ing, grading, mixing, labeling, packaging, etc. Compared to the fer-
mentation and chemical synthesis processes, formulation is a relatively
smal1 water user.
Fractionation, natural extraction, and biological culture growth and
separation processing techniques are used on much smaller production
IV-2
-------
DRAFT
scales than the three previously discussed techniques. Fractionation
techniques consist of a series of centrifugation and chemical extrac-
tion steps. Natural extraction techniques use animal and plant tissues
as product raw material and also consist of various separation and
chemical extraction steps. Biological cultures are another raw ma-
terial of medicinal products. Cultures are grown under optimum con-
ditions and then go through a series of seeding, isolation, incuba-
tion and drying steps. These three processing techniques are generally
conducted in laboratories on a bench-top scale and therefore are very
smal1 water users.
It was concluded that there are essentially four major manufacturing
process areas which could logically be used as subcategories: fer-
mentation, chemical synthesis, formulation, and biological and natural
product processing techniques.
Product
Under the Standard Industrial Classification coding system, the Phar-
maceutical industry is divided into three product areas; Biological
Products (SIC 2831), Medicinal Chemicals and Botanical Products
(SIC 2833), and Pharmaceutical Preparations (SIC 283*0. Within the
Medicinal Chemicals and Botanical Products classification, there are
three additional major product areas: fermentation products, chemical
synthesis products, and natural extraction products. Fermentation pro-
ducts are primarily steroids and antibiotics. Chemical synthesis pro-
ducts include intermediates used to produce other chemical compounds
as well as hundreds of fine chemical products. These chemicals are
used to ultimately produce the gamut of medicinal products, from sup-
positories to anti-depressants. Biological products include vaccines,
serums, and various plasma derivatives. Natural extractions include
such items as animal gland derivatives, animal bile salts and deriva-
tives, and herb tissue derivatives. Formulation products are manu-
factured from the end-products of the other manufacturing areas and
include the merchandise which is finally marketed to the public.
It was concluded that there are basically four product areas which
could be used as a basis for subcategorization: fermentation,
chemical synthesis, formulation, and biological and natural extrac-
tions.
Raw Materials
The Pharmaceutical industry draws upon worldwide sources for the
myriad of raw materials it needs to produce medicinal chemicals.
Fermentation plants require many raw materials falling into general
chemical classifications such as carbohydrates, carbonates, steep
liquors, nitrogen and phosphorus compounds, antifoam agents, and
various acids and bases. These chemicals are used as carbon sources,
nutrient sources, for foam control, and for pH adjustment in the actual
IV-3
-------
DUA! I
fermentation step. Various solvents, acids, and bases are also re-
quired for subsequent extraction and purification steps. Hundreds
of raw materials are required for the many batch chemical synthesis
processes used by the Pharmaceutical industry. These include organic
and inorganic compounds and are used in gas, liquid, and solid forms.
Plant and animal tissues are also used by the Pharmaceutical industry
to produce various biological and natural extraction products. The
raw materials used by pharmaceutical formulation plants are the pro-
ducts of the other manufacturing areas. These include bulk chemicals
from fermentation and chemical synthesis plants as well as such items
as biles, blood fractions, salts, and various derivatives from bio-
logical and natural extraction facilities.
It was concluded that based on raw materials used, the industry could
be divided into four subcategories: fermentation, chemical synthesis,
formulation, and biological and natural products.
Plant Size
From inspection of historical and plant visit data, it was determined
that plant size, measured in terms of production, apparently has no
significant effect on the pounds of pollutant per pound of production
(RWL) generated by those plants in subcategories B, C, D or E. How-
ever, raw waste loads did vary with production levels in the fermenta-
tion industry. It was also observed that there appeared to be no rela-
tionship between plant size, measured in these terms, and the quantity
of wastewater generated by plants in any of the subcategories in the
pharmaceutical Industry.
Plant size, measured in terms of total gross floor area, was used as
the basis for computing raw waste loads for the plants in sub-
category E. This proved to be a more consistent yardstick for this
subcategory than production.
Plant Age
During the study, old and new plants within each subcategory were
visited. Following analysis of actual survey and historical data,
it was concluded that plant age is not a significant factor in deter-
mining the characteristics of a plant's wastewater. The presence
and absence of separate sewer systems for sanitary and process waste-
waters were observed in both old and new plants. The age of a plant
was related more to the location of the plant than to the quantity
or characteristics of the plant's wastewaters. The older plants were
located in urban areas, whereas the newer plants were sited in rural
areas. This will impact the cost of treatment facilities because
of land costs and availability.
-------
DRAFT
Plant Local ion
From inspection and wastewater sampling of plants located in three
geographical areas of the country and from analysis of existing data,
it was concluded that plant location does not affect the quality or
quantity of the process wastewater streams. The geographical areas
surveyed included the Midwest, the Northeast, and the Southeast
(Puerto Rico). Geographical location did affect the management of
non-process streams such as non-contact cooling water. Recirculation
of cooling water was more common in the warm climate areas (where water
conservation was of more concern) than in temperate geographical regions.
Housekeeping
Plant housekeeping was another factor considered when comparing the
various plants visited during the study. The Pharmaceutical industry
has been under a form of pollution control for a number of years. Cer-
tain control standards for cleanliness, sanitation, hygiene and process
control are matters of particular importance to the industry because
of its concern about product quality. As a result of these considera-
tions, the Pharmaceutical industry has, as a matter of course, practiced
unusually good manufacturing and housekeeping procedures as they apply
to both processes and personnel. In addition, the Pharmaceutical in-
dustry has for years been subject to certain manufacturing and oper-
ational restrictions and inspections pertaining to the regulations
of the Federal Food and Drug and Cosmetic Act. Periodically, FDA
personnel will call on a pharmaceutical manufacturer for an unan-
nounced in-plant inspection covering plant housekeeping practices.
Good manufacturing practices regulations promulgated by the FDA have
been in force, with modifications, since 1963- In addition, since
the chemical costs to produce pharmaceutical products are high, in-
ventories are closely watched and checked, inadvertent spills and
batch discharges are closely monitored, and housekeeping practices
are maintained at the optimum. Due to the strict regulations con-
cerning cleanliness enforced by the FDA, the housekeeping practices
observed at all the plants visited were exceptionally good and there-
fore they were not considered as a factor in determining wastewater
quantities and characteristics.
Air Pollution Control Equipment
The type of air pollution equipment employed by a facility can affect
the characteristics and treatability of the process wastewater streams.
The use of both dry and wet pollution control equipment was observed
in several areas of the Pharmaceutical industry. However, these devices
do not significantly impact the treatability of process wastewaters,
and therefore, air pollution control devices do not form a basis for
subcategor i zat ion.
IV-5
-------
DRAFT
Nature of Wastes Generated
Various pharmaceutical manufacturing processes have been examined for
the types of contact process water usage associated with each. Contact
process water is defined as all water which comes in contact with
chemicals within the process, and includes:
1. Water required or produced (in stoichiometric quantities) in the
chemical reaction.
2. Water used as a solvent or as an aqueous medium for the reactions.
3. Water which enters the process with any of the reactants or which
is used as a diluent (including steam).
k. Water used as an absorbent or scrubbing medium for separating cer-
tain chemicals from the reaction mixture.
5. Water introduced as steam for stripping certain chemicals from the
reaction mixture.
6. Water used to wash, remove, or separate chemicals from the reaction
mixture.
7. Water associated with mechanical devices such as steam-jet ejectors
for drawing a vacuum on the process and vacuum pumps.
8. Water used as a quench (including ice) or direct contact coolant,
such as in a barometric condenser.
9. Water used to clean or purge equipment used in batch-type operations.
The type and quantity of contact process water usage are related to the
specific unit operations and chemical conversions within a process. The
term "unit operations" is defined to mean specific manufacturing steps,
such as fermentation, distillation, solvent extraction, crystallization,
purification, chemical synthesis, absorption, etc. The term "chemical
conversion" is defined to mean specific reactions, such as oxidation,
halogenation, alkylation, esterification, etc.
Although the study survey teams were not allowed to sample individual
unit operations, it could be seen from evaluation of all available data
that the characteristics of the wastewaters generated by the different
manufacturing techniques utilized by the Pharmaceutical industry varied
considerably. The wastewaters from fermentation processes consisted
primarily of spent fermentation beers and waste solvents. The many
batch operations used in chemical synthesis operations were a cause
of highly variable wastewaters containing many constitutents. The
wastewater flows from the formulation industry are almost exclusively
equipment wash waters.
IV-6
-------
DRAFT
Biological, natural extraction, and research facilities generate much
less wastewater than the other manufacturing processes. Their waste-
water flows are intermittent, and animal wastes are often found in the
effluents from research buildings.
It was concluded that the nature of the wastewaters generated by the
Pharmaceutical industry formed a basis for subcategorization.
Treatability of Wastewaters
The pollutant loading from plants within the different manufacturing
areas varied widely, and therefore the treatment technologies employed
by companies throughout the industry varied from highly sophisticated
thermal oxidation plants to small biological package plants.
The wastewaters generated by fermentation and chemical synthesis pro-
cesses contain much higher pollutant concentrations than those generated
from the manufacturing of biological and natural extraction products.
Formulation plants generally discharge wastewaters with moderate strengths,
The lowest strength wastes sampled were those attributed to research fa-
cilities. It was concluded that based on treatability of the wastewaters,
five subcategories were required: fermentation, chemical synthesis,
formulation, biological and natural extracts, and research.
Summary of Considerations
It was concluded that, for the purpose of establishing effluent limita-
tions guidelines and standards, the Pharmaceutical industry should be
grouped into five subcategories. This subcategorization was based on
distinct differences in manufacturing processes, raw materials, products,
and wastewater characteristics and treatability. The five subcategories
that have been selected for the Pharmaceutical industry are:
A. Fermentative Product Manufacturers
B. Biological and Natural Extraction Product Manufacturers
C. Chemical Synthesis Production
D. Mixing/Compounding or Formulation Production
E. Research (Microbiological, Biological, and Chemical)
Subcategory C has been further subdivided into subcategories C1 and
C7. These additional subcategorizations were based on manufacturing
processes which are discussed further under the individual subcategory
descriptions.
IV-7
-------
DRAFT
Description of Subcategories
Subcategory A - Fermentative
Product Manufacturers
Fermentation is an important production process in the Pharmaceutical
industry. This is the basic method used for producing most antibiotics
(penicillin, streptomycin, etc.) and many of the steroids (cortisone,
etc.). The product is produced in batch fermentation tanks in the
presence of a particular fungus or bacterium. The culture may be the
product, or it may be filtered from the medium and marketed in cake or
liquid form as animal feed supplement. The product is extracted from
the culture medium through the use of solvents, activated carbon, etc.
The antibody is then washed to remove residual impurities, concentrated,
filtered, and packaged.
The most troublesome waste of the fermentation process, and the one most
likely to be involved in water pollution problems, is spent beer. This
is the fermented broth from which the valuable fraction, antibiotic or
steroid, has been extracted. Spent beer contains a large amount of
organic material, protein, and other nutrients. Although spent beer
frequently contains high amounts of nitrogen, phosphate, and other
plant growth factors, it is also likely to contain salts, like sodium
chloride and sodium sulfate, from the extraction processes.
This subcategory includes the unit operations which follow the fermenta-
tion steps that are used to retrieve the product from the fermentation
broth. These include physical separation steps, such as vacuum filtration
and centrifugation, as well as chemical separation via solvent extraction
and distillation. Fermentation requires extensive quantities of water.
The primary liquid wastes include the fermentation beers; inorganic
solids, such as diatomaceous earth, which are utilized as a pre-coat
or an aid to the filtration process; floor and equipment washings;
chemical wastes such as solvents; and barometric condenser water from
evaporat ion.
Subcategory B - Biological and Natural
Extraction Product Manufacturers
Biological Product Manufacturers produce bacterial and virus vaccines,
toxoids and analogous products (such as allergenic extracts), serums,
plasmas, and other blood derivatives for human or veterinary use. The
primary manufacturing steps in blood fractionation include chemical
precipitation, clarification, extraction, and centrifugation. The
primary wastewater sources are precipitates, supernatants, centrates,
waste alcohols, and tank washings. The precipitates and waste alcohols
can be incinerated or reclaimed, while dilute wastes (supernatants,
centrates, and tank washings) are sewered. The production procedures
for vaccines are generally lengthy and involve numerous batch operations.
Unit operations include incubation, centrifugal ion, staining, freezing,
drying, etc.
IV-8
-------
DRAFT
Liqui.d wastes associated with the process consist primarily of spent
media broth, waste eggs, glassware and vessel washings, animal wastes,
bad batches of production seed and/or final product, and scrubber water
from air pollution control equipment. Spent media broth, bad batches,
waste eggs, animal carcasses, and contaminated feces are normally in-
cinerated. Wastes from small non-infected control animals may be land-
filled. Equipment washings, animal cage washings, and scrubber blow-
downs are usually sewered.
Natural extractions manufacturing includes the processing (grading,
grinding, and milling) of bulk botanical drugs and herbs. Establish-
ments primarily engaged in manufacturing agar and similar products of
natural origin, endocrine products, manufacturing or isolating basic
vitamins, and isolating active medicinal principals such as alkaloids
from botanical drugs a nd herbs are also included in this industry.
The primary wastewater sources include floor washings, residues, equip-
ment and vessel wash waters and spills. To the maximum extent possible,
bad batches are corrected rather than discarded. When bad batches can-
not be corrected, liquids are generally discharged to the plant sewer
system. Solid wastes are usually landfilled or incinerated.
Subcategory C - Chemical
Synthesis Production
The production of chemical synthesis products is very similar to fine
chemicals production, and uses the following major unit processes:
reaction, extraction, concentration, separation, solvent recovery, and
drying. The synthesis reactions are generally batch types which are
followed by extraction of the product. Extraction of the pharmaceutical
product is often accomplished through solvents. The product may then be
washed, concentrated and filtered to the desired purity and dried. The
major wastewater sources include tank washes, equipment washes, spent
cooling water, and condenser dischargers. These wastes are generally
amenable to biological treatment.
Subcategory C has been divided into subcategories C^ and G£: $ub-
cateory G£ includes those plants which manufacture antibiotics by
chemical synthesis, with the remaining plants falling in Subcategory C .
This additional subcategorization was formulated due to RWL-production^
level relationships demonstrated in the survey results.
Subcategory D - Mixing/Compounding
of Formulation Production
Formulation operations for synthesis products may be either dry or wet.
Dry production involves dry mixing, tableting or capsuling, capsule
manufacturing, and packaging. Process equipment is generally vacuum
cleaned to remove dry solids, and then is washed down. Scrubber blowdown
from air pollution control devices may also be a wastewater source,
I V-9
-------
DRAFT
and baghouses (for air pollution control) will generate a solid
waste requiring disposal. Wet production Involves mixing ami
blending in large vats and subsequent bottling and packaging.
The primary wastewater sources include tank and equipment washings
and spi11s.
Subcategory E - Microbiological, Biological
and Chemical Research
Generally, quantities of materials being discharged by a research
operation are relatively small when compared with the volumes generated
by production facilities. However, the problem cannot be measured en-
tirely by the volume of material going to the sewer. Research operations
are frequently erratic as to quantity, quality, and time schedule when
dumping occurs. The most common problem is the disposal of flammable
solvents (especially low-boiling-point solvents like ethyl ether),
which can result in explosions and fires. The most effective approach
to this problem is to require laboratory personnel to dispose of all
waste solvents in special containers available in the laboratories
and to have the material hauled away by a contractor. The effluent
limitations for this subcategory were based on total gross floor
area, since this proved to be a more consistant measure than
production rate. This approach is logical, because research fa-
cilities are not involved in manufacturing a specific product, unlike
industries in the other categories.
Process Descriptions
Subcategory A - Fermentative
Product Manufacturers
Historically, the Pharmaceutical industry has used materials of plant
and animal origin as sources for drugs. The industry also goes a step
further and employs the life processes of plants and animals (especially
from microorganisms) to produce useful medicaments. An excellent example
of this is the fermentation process, in which microorganisms are per-
mitted to grow under controlled conditions to produce valuable and often
complex chemicals. With a few exceptions, notably chloramphenicol and
cycloserine (which are produced by chemical synthesis), all antibiotics
are produced by fermentation. The technique involves growing the micro-
organism on a large scale in total 1 y -end osed tanks ranging in size
from 5,000 to 25,000 gallons under conditions which force the micro-
organism to produce the maximum quantity of the antibiotic. Control
of microorganism activity is achieved by the fol lowing techniques:
1. The culture is grown in a fermentation medium which contains the
various ingredients required by the organism for its nutrition,
e.g., a carbohydrate such as glucose, sucrose, lactose, or starch;
I V-10
-------
DRAFT
a simple nitrogen source, such as urea or ammonium sulfate;
or a more complex nitrogen source, such as soybean meal, corn-
steep liquor, whey, cottonseed meal, or a meat digest. In ad-
dition, various salts may be added to provide the organism with
its nutritional requirements for one or more of the cations
(manganese, magnesium, copper, iron, potassium) and for
one or more of the anions (phosphate, sulfate, and chloride).
Sometimes other materials such as oil or yeast extract are added.
If the organism is aerobic, sterilized air is introduced through
a sparger in the bottom of the vessel and dispersed throughout
the fermenting broth by agitation. It should be emphasized that
the fermentation medium is one which is devised to stimulate maxi-
mum antibiotic production and not necessarily meet the normal nu-
tritional requirements of the organism.
2. The organism is grown under conditions of pure culture, i.e., in
the absence of any competing microorganism. This is achieved; by
sterilizing the medium and the fermentor with heat, usually steam;
by aerating with sterile air, usually obtained by passage through
a filter containing glass wool or carbon; and by preventing the
entrance of foreign microorganisms during the fermentation period
through operation of the vessel under positive pressure and the
use of steam seals on all connecting lines.
3. Close control of the physical environment is achieved: by con-
tinuous mixing of the batch to ensure intimate contact of the
microorganism with the components of the medium; by control
of the batch temperature; and finally by control of the pH.
This latter control may be achieved either by relying on the
metabolism of the organism combined with the proper balance of
medium ingredients to give the desired pH pattern, or by the
addition of acid or bases as needed. Aerated fermentations
often foam excessively, and, as a consequence, a defoamer is
usually added intermittently to keep the batch under control.
The choice of defoamer is influenced by its defoaming ability
and its toxicity to the fermentation. Interference with product
isolation in the refining step, is another factor to be con-
sidered.
k. In a few isolated cases, product formation is stimulated by the
addition, throughout the fermentation, of a compound which the
organism can incorporate into the final product. An example of
this occures in the production of benzylpenici11 in, when pheny-
lacetic acid is added, to be incorporated into the benzyl
side chain. Similarly, phenoxyacetic acid is used to stimulate
the production of phenoxymethyl penicillin.
The antibiotic may be accumulated within the cells of the microorganism
or excreted into the surrounding aqueous medium, or a combination of
the two may occur. Usually, the antibiotic is recovered from the
IV-11
-------
fermentation broth by utilizing techniques basically related to sol-
vent extraction of the filtrate and/or cells, selective ion exchange,
chromatography precipitation, or a combination of these.
In a number of fermentation operations, it is possible to recover the
suspended mycelia and nutrients present in the spent beer. They can
then be concentrated, dried, and sold as an animal feed supplement.
Of course, for these solids to be utilized in such a manner, the
fermentation waste must be free of hazardous components. Landfill ing
is designated by some companies for such solids when reuse is not
feas ible.
Although many antibiotics are produced commercially, the general
fermentation processes used are very similar. Flowcharts for typical
fermentation processes are depicted in Figures IVA-1 and IVA-2. The
major wastewater sources are the spent beer from the fermentation
step and spent solvents from subsequent extraction steps.
Subcategory B - Biological and Natural
Extraction Product Manufacturers
A biological product is any virus or bacterial vaccine, therapeutic
serum, toxin, antitoxin, blood derivative, or analogous product
applicable to the prevention, treatment, or cure of diseases or in-
juries in man. They are created by the action of microorganisms,
and they are used for prophylaxis, treatment, and diagnosis of in-
fections and allergic diseases. Biological products are valuable
for producing immunity to infections and preventing epidemics caused
by contagious diseases. The two major production processes in this
group are blood fractionation and vaccine production.
Numerous refinements of the detailed procedures for blood fractionation
have been made to increase the yield and purity of the various com-
ponents. The principal methods presently in use for large scale
separations are called Method 6, Method 5 H, and Method 9. Method 6
and Method 5 H are used for the main separation of the plasma, whereas
Method 9 is for the subfractionation of precipitate II + III.
Table IVA-1 lists the various plasma fractions produced and indicated
their respective components and ultimate uses.
Method 6 is used for the industrial production of plasma. The plasma
for which this method was developed is obtained from bleedings in which
one unit (500 me) of whole blood is collected in a vessel containing
50 me of *t percent sodium citrate. After separating the cells from the
plasma, the plasma is gently stirred, cooled, and brought to a pH of 7.2.
IV-12
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DRAFT
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Table IVA-1
Flowsheet of Protein FractionatIon of Plasma
Fraction
of Plasma
II + III
Components
antihemophi1ic globulin
I I 1-0 cholesterol: Phosphatides
carotenoids; Vitamin A
estrogens
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globulins and some
6 globulins
I I 1-1 isoagglutinins
I I 1-2 prothrombin (thrombin)
Demonstrated Users
treatment of hemophilia
immune globulins against
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bodies
blood grouping
blood coagulation; hemo
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fibrin foam and film) blood coagulation
plasminogen
a-globulin; cholesterol:
phosphatides; phosphatases
a- and b globulin; esterases
hypertensinogen; some
albumin
protein not precipitated
IV-15
-------
DKAf" I
The plasma then undergoes a series of centrifugation steps. The
resultant supernatant and/or precipitate is chemically treated in
preparation for the next centrifugation, is preserved and stored
for future use, or is discarded.
Several manufacturers now use a simplified version of Method 6.
in this simpler system, the number of fractions is reduced, and
the total volume of the system is smaller. This modified procedure
has been designated as Method 5 H.
The precipitate designated II + III, which is produced in the third
step of Method 6 and in Method 5 H, is the starting material for
Method 9- This method is used to produce additional blood fractions
and, as in Methods 6 and 5 H, consists of a series of centrifugation
steps to separate the desired plasma fractions.
In general, the production process for vaccines is lengthy and in-
volves numerous batch operations. Figure IVA-3 schematically out-
lines a typical vacine production process. The primary unit oper-
ations include mincing, trypsinizing, centrifugation, incubation,
freezing, and drying. Liquid wastes associated with the process con-
sist primarily of spent media broth, waste eggs, glassware and vessel
washings, and bad batches of production seed and/or final product.
Production of material extractions involves the processing of bulk
botanical drugs and herbs. Typical unit operations used to manu-
facture products in this group include milling, grading, grinding,
and solvent extraction. These manufacturing operations are usually
carried out on a small scale, and the quantity of wastewater generated
is small. Most extraction processes practice solvent recovery and
recycle, and therefore the degree of contamination remaining in the
washwater depends on the extent and efficiency of the recovery
operations. The used plant tissues are generally incinerated with
any waste solvents or are landfilled, and therefore these wastes
seldom enter the wastewater stream.
Subcategory C - Chemical Snythesis
Production
The Pharmaceutical industry employs a greater variety of complicated
steps in its manufacturing processes than almost any other chemical
process industry. The complex chemical structure of many medicaments
probably has a relationship to the even greater complexity of the
ailments of the human and animal bodies which the products of the
Pharmaceutical industry are designed to ameliorate. Also, except
for the Nuclear industry in certain cases, as a rule the Pharma-
ceutical industry places greater emphasis upon the purity of its
products than does any other industry.
IV-16
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DRAFT
At first glance, a chemical plant often appears to be a chaotic maze
of equipment, piping, and buildings that is totally unlike any other
facility, even those which manufacture the same product. Nevertheless,
there are certain basic components common to almost all chemical plants:
a process area; storage and handling facilities for raw materials, inter-
mediates, and finished products; electrical, steam, air, and water systems
with associated sewers and effluent treatment facilities; and, in most
cases, a laboratory, an office, control rooms, and service roads.
The storage facilities associated with any chemical plant obviously de-
pend upon the physical state (i.e. solid, liquid, or gas) of the feed-
stocks and products. Storage equipment frequently utilized includes:
cone-roof tanks, with or without "floating" roofs, for storage of
liquid hydrocarbons; cylindrical or spherical gas-holding tanks; under-
ground and above ground storage tanks; and concrete pads or silos for
storage of sol ids.
Wastewater emanating from storage facilities normally results from
storm run-off, tank washing, accidental spills, and aqueous bottoms
periodically drawn from storage tanks. Although the generation rate
is sporadic and the volume small, these wastewaters have in most cases
contacted the chemicals which are present in this area. For this reason,
they are normally sent to a process sewer and given the same effluent
treatment as contact-process wastewaters.
Utility functions, such as steam supply, deionized water, ice water sup-
ply, hot water supply, and cooling water, are generally set up to service
several processes. Boiler feed water is prepared and steam is generated
in a single boiler house. Noncontact steam used for surface heating is
circulated through a closed loop, making varying quantities available
for the specific requirements of the different processes. The condensate
is almost always recycled to the boiler house, where a certain portion
is discharged as blowdown.
The three major uses of steam generated within a chemical plant are:
1. For noncontact process heating. In this application, the steam
is normally generated at pressures of 125 to 650 psig, or low-
pressure steam at pressures of 5 to 50 psig, for heat-sensitive
products.
2. For power generation, such as in steam-driven turbines, compressors,
and pumps associated with the process. In this application, the
steam is normally generated at pressures of 650 to 1500 psig and
requires superheating.
3. For use as a diluent, a stripping medium, or a source of vacuum
through the use of steam jet ejectors. This steam actually con-
tacts the hydrocarbons in the manufacturing processes and is
IV-18
-------
DRAFT
a source of contact process wastewater when condensed. It is
used at a substantially lower pressure than the foregoing and
frequently is exhaust steam from one of the other uses.
Water conditioning or pretreatment systems are normally part of the
utilities department of most plants. From the previous discussions,
it should be obvious that the required treatment may be quite extensive.
Ion-exchange demineralization systems are very widely employed, not
only for conditioning water for high-pressure boilers, but also for
conditioning various process waters. Clarification preceding an ion
exchange operation may be employed. In some cases, a demineralization
system is dedicated to a single processing step with a high demand
for continued water and, therefore, is operated as part of that pro-
duction unit.
Noncontact cooling water also is normally supplied to several pro-
cesses from the utilities area. The system is either a loop which
utilizes one or more evaporative cooling towers, or a once-through
system with direct discharge.
A closed system is normally used when converting from once-through
river cooling of plant processes. In the closed system, a cooling
tower is used for cooling all of the hot water from the processes.
Figure IVA-^ illustrates this method. With the closed system, makeup
water from the river is required to replace evaporation loss (at the
tower), drift, and blowdown. Drift is droplet carry-over in the air
(as opposed to evaporative loss). The cooling tower industry has a
standarized guarantee that drift loss will not exceed 0.2 percent of
the water circulated. Blowdown to a sewer or river is necessary to
avoid a build up of dissolved solids. Although blowdown is usually
taken off the hot water line, it may be removed from the cold water
side to comply with regulations that limit the temperature of cooling
water discharged. Blowdown from a tower system will vary, de-
pending on the dissolved solids concentration in the make-up water
and the cycles of concentration maintained in the system. Generally,
blowdown will be about 0.3 percent per 10°F of cooling, in order to
maintain a dissolved solids concentration in the recirculated water
of three to four times that of the make-up water.
The quantity and quality of the blowdown from boilers and cooling towers
depend on the design of the particular plant utility system. The heat
content of these streams is purely a function of the heat recovery equip-
ment associated with the utility system. The amounts of waste brine and
sludge produced by ion exchange and water treatment systems depend on
both the plant water use function and the intake water source. None
of these utility waste streams can be related directly to specific
process units.
Quantitative limitations on parameters such as dissolved solids, hard-
ness, alkalinity, and temperature, therefore, cannot be allocated on
IV-19
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DRAFT
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DRAFT
a production basis. The limitations on parameters like these, which
are associated with noncontact utility effluents, will be established
in the effluent guidelines for the Steam Supply and Noncontact Cooling
Water industry.
The service area of the plant contains the buildings, shops, and
laboratories in which most of the plant personnel work. The sanitary
wastes from this area obviously depend on the number of persons em-
ployed. It should be noted that most bulk chemical synthesis plants
run continuously and have 3 operating shifts per day. There are also
wastes associated with the operation of the laboratory, machine shops,
laundry, etc. Depending on the size of the , lant, there may be tank
car and/or tank truck cleaning facilities which could add to the pro-
cess wastewater load. The wastes from the service area normally are
combined with the wastes from the process area prior to treatment.
Each chemical synthesis process is itself a series of unit operations
which causes chemical and/or physical changes in the feedstock or
products. Flow sheets illustrating typical chemical synthesis of pro-
cesses are shown in Figures IVA-5 and IVA-6. In the commercial synthesis
of a single product from a single feedstock, there generally are unit
operations associated with the preparation of the feedstock, the
chemical reaction, the separation of reaction products, and the final
purification of the desired product. Each unit operation may have
drastically different water usages associated with it. The type and
quantity of contact wastewater are therefore directly related to the
nature of the various processes. This in turn implies that the types
and quantities of wastewater generated by each plant's total pro-
duction mix are variable.
The production from a given process is obviously related to the design
capacities of the individual unit operations within it. In many cases
the unit operations are arranged as a single train in series. In
other cases, certain unit operations are arranged in parallel, as in
an operation utilizing several small reactors simultaneously.
There are two major types of manufacturing process within the industry:
1. Continuous Processing Operations.
2. Batch Processing Operations.
Manufacturing processes can be classified in this manner by the flow
of material between unit operations within a process, which may be
either a continuous stream or a series of batch transfers. Both
types of processes normally have an associated design capacity which
is expressed in terms of thousands of pounds of product per year.
In large-scale continuous processes, all of the subsections of the
process module are operated with the use of automated controls; in
some cases, complete automation or computer control is utilized. Re-
cording instruments maintain continuous records of process variables
IV-21
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FIGURE IVA6
TYPICAL CHEMICAL SYNTHESIS PROCESS
(ANTIBIOTIC MANUFACTURE!
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IV-23
-------
DRAFT
such as temperature, pressure, flow of fluids, viscosity, pH, liquid
level, and the composition of various process streams. Instrumentation
for the indicating, recording, and control of process variables is an
outstanding characteristic of modern chemical manufacture. The
function of the operators, mechanical technicians, and supervising
engineers in this type of operation is to maintain the process module
in proper running order and to keep process parameters within desirable
ranges. In large continuous operations, equipment is frequently
segregated to the extent that each process module is located in its
own building or plant location. In such operations, there is usually
complete segregation of contact process waters from noncontract cooling
waters.
In the manufacturing of fine chemicals, batch processes are frequently
used for reasons of quality control, economic considerations, low
product demands, FDA requirements, or specific manufacturing require-
ments. Batch operations are more easily controlled when varying reaction
rates and rapid temperature changes are key considerations. This requires
more supervision on the part of operators and engineers, since conditions
and procedures usually change from the start to the finish. Batch oper-
ations with small production and variakle products may also use the same
equipment to make several different chemicals by the same type of chemical
conversion. Hundreds of specific products may be manufactured within
the same building. This type of processing requires the cleanout of
reactors and other equipment after each batch. Purity specifications
may also require extensive purging of the associated piping. Rapid
changes in temperature during the batch sequence may also require the
direct addition of ice or quench water instead of slower non-contact
cooling through a jacket or coils.
Contact process waters from batch and continuous processes include
not only water produced or required by the chemical reactions but
also any water which comes in contact with chemicals within each of
the process modules. Although the flows associated with these sources
are generally smaller than those from non-contact sources, the organic
pollution load carried by these streams may be greater by many orders
of magnitude.
In general, the chemical processing area of a plant is made up of a
number of batch reactors followed by intermediate product storage and
purification steps, such as crystallization, distillation, filtration,
centrifugation, solvent extraction, and other unit operations either
singularly or in combination. Since some equipment may be common to
several product needs, careful equipment cleaning is necessary to avoid
cross-contarni nat ion.
The washings follow the drainage system, and can thus be collected for
subsequent treatment. Where a solvent is necessary in the cleaning
steps for a vessel cleanout, the vessel is closed and cleaned by re-
circulation of the solvent through a pump system. The contaminated
solvent is then discharged to a hold tank for purification by stripp-
ing and subsequent recovery drawoff. The tars or sludges are usually
IV-24
-------
DRAFT
incinerated or hauled to a landfill. In some very small production fa-
cilities, the solvent may be disposed of to an approved disposal firm.
Where solvents are used for cleaning, plant safety becomes a primary
concern. It is extremely important to minimize the discharge of water-
insoluble solvents to plant drains, where a simple spark could create
a major castastrophe. Plant safety is of constant concern, and fire
hazards are to be avoided as much as possible. Consequently, plant
safety measures help eliminate gross discharges of such organics,
although low concentrations remain in dissolved, dispersed, or emulsi-
fied form and require subsequent treatment.
There are several possible major pollution sources in chemical synthesis
production. If the reaction is carried out in a batch kettle or auto-
clave, then the washout solutions will be high in contaminant loadings.
If distillation is done under vacuum, the process vacuum jet water will
be saturated with the lighter components of the reaction mix. If fil-
tration is involved, two possibilities exist. If the filter cake is
unwanted, then there is a solid waste disposal problem. If the fil-
trate is the unwanted material, this portion usually goes to the process
sewer, where it is either treated separately or combined with the main
effluent for subsequent treatment. Since chemical reactions frequently
involve acids or bases, an effluent needing pH adjustment may result,
especially if one reactant is used in excess of stoichiometric pro-
portions. Reactor effluent will sometimes contain emulsions from
which the oil may be separable by pH adjustment.
Where solvents are used, both for process and vessel cleaning, most
plants practice solvent recovery. A few plants also strip weak organic
solutions to reduce contaminant loadings further. The stripping oper-
ation is carried to the point where the organic solution can safely be
combined with other process wastes.
A number of the plants have evaporation and incineration units to aid
in their disposal of specific organic wastes which might be difficult
to treat biologically.
Subcategory D - Mixing/Compounding
or Formulation Production
Pharmaceutical formulation represents all the various operations that
are involved in producing a packaged product suitable for administering
as a finished, usable drug. It would include such things as mixing of
ingredients, drying of granules, tableting, capsulating, coating of
pills and tablets, preparation of sterile products, and finally the
packaging of the finished product. Figure IVA-7 illustrates three
typical pharmaceutical formulation processes.
IV-25
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DRAFT
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-------
DRAFT
In general, the specific unit operations of the formulation procrss
cannot be considered serious water polluters, for the simple reason
that they do not use water in any way that would cause pollution. It
should also be pointed out that most pharmaceutical formulation plants
work on an eight-hour day, five-day per week work schedule, and the
usage of water is limited primarily to that period. As a result of
both the shorter work schedule and the lower water requirements per
unit operation that characterize the plants in this subcategory, the
amount of wastewater generated per pound of product is considerably
lower for the plants in subcategory D than for the plants in the other
categories. This can be seen from the survey results presented in
Table VA-1. In spite of this, however, there are a number of places
where water pollution can be expected. Washup operations are always
a potential pollution source. The application of too much water over
too great an area can flush materials (into a sewer) that are unusual
in terms of both quantity and concentration. Dust and fume scrubbers
used in connection with building ventilation systems or, more directly,
on dust and fume generating equipment, can be a source of water pol-
lution, depending on the nature of the material being removed from the
a i rstream.
Most pharmaceutical manufacturing firms are compounders, special
processors, formulators, and product specialists. Their primary ob-
jective is to convert a desired prescription into tablets, pills,
lozenges, powders, capsules, extracts, emulsions, solutions, syrups,
parenterals, suspensions, tinctures, ointments, aerosols, suppositories,
and other miscellaneous consumable forms. These operations can be clas-
sified as labor intensive and low in waste production.
Manufacturing descriptions for the different forms of pharmaceutical
dosages are discussed in the subsequent paragraphs.
Tablets are formed by compaction of powders, crystals, or granulations.
The various modifications which are possible can be seen in the fol-
lowing list:
Form of Tablet Drug Release Characteristics
Plain compressed Rapid or sustained
Coated Rapid, delayed, sustained,
and repeat action
Molded Rapid
The process of plain compression tableting can be divided into the fol-
lowing three basic approaches: wet granulation, direct compression,
and slugging.
IV-27
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DRAFT
For drugs which are not prone to degradation in the presence of mois-
ture, the wet-granulation step has heretofore been the most widely used.
The process consists of carefully blending the powdered ingredients (ex-
cept for the lubricants and disintegrants) and then wetting the powder
with a solution or dispersion of the binders. The damp mass is screened
to form coarse granules and dried. The classic method of drying has
been to spread the mass on trays and dry the granules in a hot-air oven.
Recent advances in technology have produced a fluidized-bed drying
technique in which the damp mass is placed into a cylindrical container
with a screened bottom. Heated air is forced through the mass, causing
the mass to be suspended in air and dried rapidly. This new method has
reduced drying time to about one-fifth of that required by conventional
methods. The fluidized-bed driers have also been modified so that the
granulating fluid can be introduced into the air stream and can there-
fore granulate the powders and dry them in one operation. The dry
granules are rescreened to about 20 to 40-mesh granules and then
mixed with the lubricants and disintegrants. The granulation at this
point is ready to be compressed into tablets.
The second technique for the preparation of tablets is direct compres-
sion. Much work has been carried out on this process in recent years
because of the obvious advantage of reduced labor time. The process
consists simply of blending the ingredients and compressing it into
tablets.
The "slugging" technique is used only as a last resort in the case of
drugs which cannot be wet-granulated because of instability and cannot
be compressed directly. Slugging, as the title suggests, is the com-
paction of a powder blend into large tablets. They may be 1 or 2
inches in diameter and may weigh up to 30 grams. The large tablets
are collected and ground up and converted into granules and then re-
compressed into final tablet form.
The method for compressing granules into tablets, regardless of the
method of manufacture, is basically identical. The granulation is
fed into a die cavity. The fill is volumetric and consequently the
weight must be controlled by changing the height of the lower punch,
which regulates the volume available for filling. Since volume is
directly measured, the necessity of having a free-flowing and uniform
granulation becomes apparent. Once the cavity is filled, the upper
punch compresses the powder mass into a tablet. After the tablet is
ejected by the lower punch, the cycle is repeated.
Compressing equipment varies from small single-punch machines which
have one upper and lower punch and a die, to large rotary tablet processes
having up to fifty-five sets of punches and dies. The rate of production
can vary from 100 tablets per minute on the single-punch machines to
^4,500 tablets per minute on the larger presses.
IV-28
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DRAFT
In addition to conventional tablets, methodology has been developed
to compress so-called layer tablets. In this method, two different
granulations are fed into the machine. First, a portion of one
granulation is compressed into a rather soft tablet, and then a
measured quantity of the second granulation is layered upon the
partially compressed tablet. The mass is then fully compressed,
resulting in a layer tablet. This approach may be used for two
reasons: 1) separation of incompatible ingredients, and 2) pre-
paration of sustained-action tablets where one layer provides the
immediate-release dose and the second the slow sustaining drug
dose.
Tablets prepared as above can be coated to improve taste, stability,
and appearance or to control the rate and site of drug release. The
coating of tablets can be accomplished by three basic methods: pan
coating, air-suspension coating, and compression coating.
Pan coating is the classical technique in which cores, free from dust
and broken tablets, are tumbled in pear-shaped pans. While the tablets
are in motion, they are wet down with a concentrated syrup containing
a film-forming agent such as gelatin, acacia, or methylcellulose.
When all surfaces have been wet, a dusting or engrossing powder such
as flour or powdered sugar is added and tumbled under a flow of warm
air. This is usually repeated two or three times to coat the tablet
rapidly and to round off the edges. After these coats, the tablets
are usually dried overnight to prevent moisture from penetrating the
core. This portion of the process is generally called subcoating.
The process is continued by repeated applications of the heavy syrup
without dusting powder to smooth out the tablet surface. Color coats
are applied if desired, and then the tablet is polished with carnauba
wax in a canvas- or wax-lined pan. Pan coating is the standard method
of tablet coating, and as a rule the finished coated-tablet weight is
double that of the uncoated core.
As in the case of the compression of tablets, recent advances in the
technology have greatly modified coating procedures. The process of
film coating has achieved great popularity. In this method, tablets
are given a thin coat of a polymeric material, either by repeated ap-
plication by hand or automated by means of a programmed system. Air-
suspension coating, known as the Wurster process, is suited for film
coating. The cores are placed in a cylindrical chamber and "fluidized"
(suspended in a stream of air). The coating solution is atomized into
the air stream. Because of rapid evaporation of the solvent, the coating
material is continuously deposited upon the tablet. The time required
for coating in this method is about one-tenth that for conventional
method.
The coatings discussed so far have all had one common factor, i.e.,
the coating materials were either suspended or dissolved in a solvent.
Another method of coating is compression (or dry) coating. In this
IV-29
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DRAFT
process, a core tablet is prepared and then an outer coating is com-
pressed around the inner tablet. This results in what might be called
a tablet within a tablet.
Molded tablets are prepared by molding a damp mass into the general
shape of tablets.
Most individuals refer to tablets of any type as "pills". Actually,
pills are a definite and distinct class of dosage form and were the
forerunner of today's tablet. Pills combine a drug and an "excipient"
which, when damp, gives the mass a doughlike consistency. The mass is
divided into dose units and then rolled into balls and allowed to dry.
Although pills can be produced mechanically, the inherent problems of
accuracy as compared to tablet production have caused a dramatic decrease
in their use. The basic process is to mix the drug with the excipient
and then dampen this with some agent such as acacia syrup, glycerol,
sugar syrup, or synthetic gums. The plastic mass is rolled into long
pipes of uniform diameter and then cut into pieces equivalent to one
dose of the drug. The divided portions pass between two belts and
are rolled into spherical pills, dusted with a powder to prevent
sticking together and finally dried. The finished pills may be
coated in the same manner as tablets.
Next to tablets, capsules rank second as the most widely used solid
oral dosage form. They have an advantage over tablets in that they
do not require the addition of binders and disintegrants. Capsules
fall into two basic categories, hard and soft. Hard gelatin capsules
are prepared in two sections, one of which slips over the other. They
are prepared empty and filled with powder when needed. The soft gelatin
capsule is made with gelatin and glycerol, and retains its plasticity
even when dry. The soft capsules are not prepared in advance but as
part of the manufacturing process.
The manufacture of hard-gelatin capsules is a rather precise technique,
since the seal of the capsule depends upon the tight fit of the top
over the body of the capsule. The process consists of dipping steel
pins into a solution of gelatin maintained at a precise temperature.
When the pins are removed from the bath, a film of gelatin adheres
to the pins. The temperature is critical, since the viscosity of
the gelatin is affected by temperature, and this determines the thick-
ness of the film adhering to the pins and consequently the wall thick-
ness of the finished capsule.
When the capsule has been dried, trimmed to proper length, and removed
from the pin, the upper and lower portions are joined. The sizes of
the capsules vary greatly from those holding approximately 30 mg to
those holding several grams for veterinary use. The colors of the
capsules can be controlled by added dyes or pigments.
IV-30
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DRAFT
Capsules are filled by various pieces of equipment. All machines
separate the upper and lower portions of the capsules, filling the
powder into the lower half, and then rejoining the capsule components.
Since the fill is volumetric, the ratio of drug to diluent must be
adjusted to obtain the correct dose of drug for a specific capsule
size. After the capsules are filled they are usually cleaned with
air and tumbled with sodium chloride to remove any dust which may
cling to the capsule. They may subsequently be imprinted with a
name or trademark for identification.
Although the majority of soft-gelatin capsules contain nonaqueous
solutions or soft masses containing the drug, powders can be filled
into this type of dosage form. In soft-gelatin capsule manufacture,
two continuous films of gelatin are passed between two rotary die
plates which contain cavities, each corresponding to one-half of
the capsule. As they come together, the mass or liquid is injected
into the partially-sealed capsule. Upon further rotation, the edges
are pressure-sealed and the capsule is cut out of the ribbon. If the
capsules are to be filled with powders, one ribbon is passed under a
hopper containing the powder, which is fed into a cavity created when
the gelatin is molded into the die by vacuum. After filling, the
second ribbon seals the capsules in a manner analogous to that for
the 1iquid capsules.
Although aerosols have been used for over twenty years for dispensing
insecticides and insect repellents, the usefulness of this medium
for the dispensing of drugs has been recognized widely only since
the 1950's.
Aerosols are usually manufactured by the cold-filling method. The
propellants are usually fluorinated hydrocarbons of varying com-
positions having different vapor-pressure and boiling-point charac-
teristics. Generally, the solution or suspension of the propellants
and the drug is chilled to reduce the vapor pressure, and the solution
is filled volumetrically into suitable containers. The valves are
then firmly attached and sealed to the container. Care must be exer-
cised in this operation to exclude moisture, since the propellants
are hydrolyzed by moisture to yield corrosive products. Generally,
the operations are carried out in dehumidified areas. The finished
containers are usually placed in water, and defective units are de-
tected by the appearance of bubbles.
An alternative method of manufacture is to seal the valve to the
empty container and then force the solution through the valve under
pressure. This method is useful for the preparation of small quantities.
Liquids may be simple solutions, syrups, elixirs, or suspensions. These
preparations are usually manufactured in jacketed glass-lined or stainless-
steel vessels similar to chemical reactors. The solutions are filtered
under pressure through plate filters and then pumped into suitable
storage tanks prior to filling. At this stage the bulk product is
usually sampled for analysis and control of physical specifications.
IV-31
-------
DRAFT
The manufacturing processes for suspensions and emulsions are similar
to that for solutions, except that after dispersion by simple mixing
the system Is passed through a homogenizer or colloid mill. These
units may force the dispersion through a small orifice under high
pressure or pass the dispersion between two plates, one stationary
and the other rotating at high speed. The aperture between the
plates is adjustable to vary the shearing action of the mill. Ad-
vances in ultrasonics have made it possible to utilize this form of
energy in production for dispersion of substances. This method has
proved useful for both suspensions and emulsions.
The manufacturing of ointments involves melting a base material and
then blending in the drug. The mass is allowed to cool and is then
passed through roller mills, high-speed coloid mills, or mills of
the rotor and stator type. In the last case, adequate cooling of the
mill is important, since too much heat buildup will cause the ointment
to melt, resulting in a nonhomogeneous product.
Creams are manufactured in a similar manner, except that the products
consist of two phases, and therefore each phase must be heated separately
and the drug incorporated into one of them. The two phases are mixed
with rapid stirring and are stirred continuously until cool.
The manufacturing process for suppositories consist of melting a loose
material, dispersing the drug, and pouring the mixture into pre-chilled
molds. This can be carried out by manual or automatic methods. Sup-
positories can also be made by compression of a powdered base in which
the drug has been dispersed. The latter method is not used in full pro-
duction unless specifically required by the nature of the drug.
Subcategory E - Research (Microbiological,
Biological, C hem i ca1)
A new drug normally takes five to six years to reach the market, result-
ing in an average cost of five million dollars. On the average, 5,000
chemical compounds are investigated before one is found that is thera-
peutical ly useful. Research in the Pharmaceutical industry is a real
team effort. The industry employs pure and applied scientists of
almost all disciplines from mathematicians and physicists to pharma-
cologists, pharmacists, chemists, and medical practitioners. 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 discussed in the following paragraphs are
chemical, microbiological, and biological. The range of wastes generated
from these various research areas range from exotic chemicals to animal
wastes.
IV-32
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DRAFT
The organic chemist synthesizes or isolates from natural sources chemical
entities of potential therapeutic use. The great majority of the syn-
thetic work is directed by intuition, knowledge of other compounds of
natural or synthetic origin, and ideally by cooperation with biochemists
and pharmacologists. The resulting compounds may be screened for a
great variety of activities. It is possible that a compound synthesized
for one therapeutic activity actually finds its way to the market as a
cure for some totally unrelated ailment.
The biochemists can be divided into two major groups, those engaged
in investigations of absorption, excretion, and metabolism of the
drugs in the various tissues and organs, and those involved in more
fundamental research, such as the study of enzyme systems in the body
and of the ways in which various physiological conditions modify such
systems. Work of this kind, it is hoped, will provide indications of
chemical structures of potential therapeutic usage.
The physical chemist is concerned principally with physical measure-
ments such as absorption spectra, nuclear magnetic resonance, optical
rotatory dispersion, and X-ray diffraction, to verify chemical structures
and to check the occurrence of polymorphic crystal forms which may
have widely differing biological activities. The physical chemist
may also be involved in testing the stability of a drug, both as a pure
material and in aqueous solution.
The analytical chemists serve several functions, mainly as a service
group. The organic chemists require routine elemental analyses of
their products and intermediates. When a new drug is found, then
analysts must develop specific assays for the chemical entity, both
in pure form and in the various pharmaceutical formulations proposed.
Thirdly, analysts are involved in the routine physical and chemical
analysis of raw materials and finished products.
Microbiological research in the U.S. Pharmaceutical industry is now
channeled into five areas: 1) discovery, evaluation, and production
of antibiotics; 2) production and evaluation of vaccines and immunizing
bJologicals (including viruses); 3) microbial production of food sup-
plements including amino acids, vitamins, and growth factors; k) trans-
formations of organic compounds of pharmaceutical interest; and 5) the
search for pharmacologically active materials in microorganisms.
All of these programs require not only microbiologists, but often the
cooperation of bacteriologists, geneticists, mycologists, biochemists,
and organic chemists is needed. For example, in a program searching
for new antibiotics, the bacteriologists and biochemists prepare con-
centrates from various fermentations which are evaluated by the bacterio-
logist in infectious diseases in animals and observed by the pharma-
cologist and pathologist. Once "interesting" activity is found, the
chemist is often asked to assist in the isolation of "pure, active ma-
terial." When the pure compound is available, the chemist will deter-
mine the structure and will seek to make useful derivatives and analogs,
IV-33
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DRAFT
while, at the same time, the biochemist will attempt to determine the
mechanism of action. If the chemistry is complex (as is the case with
most antibiotics), a geneticist may be enlisted to prepare new cultures
of the antibiotic-producing microorganisms which produce more of the
desired substance. Thus, it is conceivable that more than forty people
will be involved in laboratory studies and related activities prior to
preclinical pharmacology and clinical trial.
Scientists of various disciplines, including pharmacology, biochemistry,
organic and physical chemistry, zoology and bacteriology, may be involved
in the preclinical testing and evaluation of a new drug. Meaningful
biological tests using laboratory animals such as rats, dogs, and
monkeys are designed to test the pharmacological actions of the
chemical entities. Potential antibacterials, antivirals, and related
drugs must be tested against a broad spectrum of microorganisms. If
these preliminary tests are promising, short- and long-range toxicity
studies must be performed and dose levels suitable from both the pharma-
cological response and toxicity points of view must be determined.
As previously pointed out, laboratory animals are used extensively
by pharmaceutical research facilities. The types of animals used
include dogs, cats, monkeys, rabbits, guinea pigs, rats and mice.
The animal colonies where these test animals are housed can be a
major wastewater source. The animal cages are usually dry cleaned
and the residue washed into the plant sewer system. The collected
feces and any animal carcasses are incinerated or landfilled if the
waste matter is not infected. The exhaust gases from the incinerators
pass through wet scrubbers, and the scrubber blowdown is subsequently
discharged to the plant sewer system.
Basis for Assignment to Subcategories
The categorization assigns pharmaceutical production facilities to
specific subcategories according to the manufacturing processes which
they utilize. The subcategories selected were:
Subcategory Description SIC
A Fermentation Production 2833
B Biological Production 2831
& Natural Extractions 2833
C Chemical Synthesis Production 2833
D Mixing/Compouding or 283^
Formulation Production
E Research
-------
DRAFT
This subcategorIzation was based on the wastewater quantities and qualities
generated by each of these production categories. Table VA-1 indicates
the plant production level**, waMewrtter flow rates, and RWL's which
typify each of the subcategor les. The tharacler Ut Us of tha wdM^-
waters generated by industries falling Into each of the subcategorles
is also discussed in Section V. Subcategory C (Chemical Synthesis) is
further divided according to manufacturing processes. This was neces-
sary due to the signficant variance in raw waste loads with production
levels observed in this category. For this reason, all industries which
produce antibiotics by chemical synthesis fall into subcategory C?, and
all others are grouped into subcategory C1.
For subcategory E, which encompasses research facilities, a different
measure was used for establishing effluent limitations, i.e., total
built-up area. The raw waste loads computed on a total built-up area
basis were comparable. The number of test animals supported by a re-
search facility was also investigated as a basis for calculating RWL
levels for category E; however, this parameter did not prove to be as
consistent as total built-up area.
IV-35
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DRAFT
B. Gum and Wood Chemicals Industry
Discussion of the Rationale
of Categorization
In developing effluent guidelines and standards of performance for the
Gum and Wood Chemicals industry, it was necessary to determine whether
significant differences existed within the industry which could be used
as a basis for subcategorization, to define those areas of the industry
where separate effluent limitations and standards should apply. A
final subcategorization was developed based on product differences:
A. Char and charcoal briquets
B. Gum rosin and turpentine
C. Wood rosin, turpentine and pine oil
D. Tall oil rosin, pitch and fatty acids
E. Essential oils
F. Rosin derivatives
The following factors were considered in determining whether such a
subcategorization would be the most meaningful one for developing ef-
fluent guidelines and standards of performance:
Manufacturing Process
The process steps by which gum, wood, tall oil chemicals and essential
oils are produced are similar in that steam distillation is employed
for mechanically separating the major constituents. Wood chemical pro-
duction processes are somewhat different in that solvent extraction is
employed. The production of charcoal and rosin based derivatives is
different from the other processes because steam distillation is not
employed. Charcoal is a carbonization, or destructive distillation,
product, while rosin derivatives are products of chemical reactions.
Therefore, it is concluded that production processes for charcoal and
rosin derivatives are significantly different from the manufacturing
processes employed in the other industries.
Product
The major products presented above are significantly different. The
essential oils are chemically related to turpentine. However, their
product yield, based on raw materials, is about one percent because there
is no market for the spent wood, while the total product yields for gum
and wood chemicals approach 100 and 25 percent respectively, on a clean
raw-materials basis. Thus, it would not appear justifiable to group
IV-36
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DRAFT
essential oils production with gum or wood chemicals because of differ-
ences in product make up yield.
Raw Materials
The basic raw materials for each of the proposed product subcategories
are as follows:
Product Raw Material Source
Char and Hardwood and softwood
Charcoal Briquets scraps
Gum Rosin and Crude Gum from the
Turpentine sapwood of living trees
Wood Rosin, Wood stumps and other
Turpentine and resinous woods from cut
Pine Oil over forest
Tall Oil Rosin, By-product crude tall oil
Pitch and Fatty from the Kraft process
Acids
Essential Oils Scrap wood fines, twigs,
barks or roots of select
woods
Rosin Derivatives Rosin products from gum,
wood and tall oil chemicals
Variation in raw materials can be expected within each group. For ex-
ample, seasonal changes bring about changes in crude gum composition.
Late in the growing season, crude gum is termed scrape, which general-
ly contains less turpentine and more trash.
However, variations in quality can be expected in the raw material
stocks within any of the groups. Where variations in raw materials re-
quire additional processing to achieve product quality, it is probable
that additional waste will be generated. For purposes of this study
these ancillary refining processes can be classified into groups ac-
cording to the type of waste they generate (i.e., wet or dry). Filtra-
tion and absorption processes, which generate semi-solid waste disposed
of in landfills, are classified as dry. Acid treating and solvent ex-
traction processes generate a liquid waste and therefore are classified
as wet. The solvent, however, is normally recovered for reuse.
IV-37
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DRAF
Dilute acid treatment is commonly employed to remove odor and color
bodies and can be expected to yield higher raw waste loads per unit of
production. The prevalence of acid treating of raw materials, the quan-
tity of specific pollutants generated, and the impact of dry versus wet
refining methods on the final products and resulting RWL's could not be
quantified in this study.
Plant Size
Operations in the Gum and Wood Chemicals industry range in size from
intermittent batch operations, which are operated by a handful of per-
sonnel, to large complexes, which employ hundreds of personnel. Water
use management techniques are affected by economy of scale, as well as
other factors, such as geographical location. On the other hand,
smaller operations may have waste treatment and disposal options, such
as retention, land spreading, and trucking to landfill, that are imprac-
tical for large scale operations.
The impact of plant size was evaluated for essential oil production.
RWL's were calculated before and after a plant modernization which re-
placed a battery of 32 small retorts with 3 larger retorts. The mod-
ernization decreased water usage but increased the total quantity of
oxygen-demanding materials in the wastewater as shown below:
RAW WASTE LOAD SMALL UNITS LARGE UNITS
Flow (gal/M Ibs) 20,200
COD (Ibs/M Ibs) 59.^ 86.9
BOD (Ibs/M Ibs) 2^.0 70.8
TSS (Ibs/M Ibs) jo.1 O.k
This specific information, however, would not be applicable to Gum and
Wood Chemicals industry as a whole.
Plant Age
Plant age cannot be considered as a basis for subcategori zat ion in
itself because the industry has continuously upgraded and modernized
its operations as dictated by the competitive market. Equipment is
modernized as it becomes necessary, so that the actual age of a
production facility could not be determined accurately. Furthermore,
the actual age of the equipment does not necessarily affect wastewater
generation. Operation and maintenance of the equipment are more
important factors.
IV-38
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DRAFT
Plant Location
Table IVB-1 shows that most of the U.S. Gum and Wood Chemical industry
is located in the southern states. According to the 1972 Census of
Manufactures, half of the establishments in gum and wood chemicals
production are located in the southern states, and they produced over
8k percent of the industry output in terms of dollar value added to the
raw material.
Plant location, and specifically local climate, has an impact on the
performance of certain end-of-pipe wastewater treatment system, e.g.,
aerated lagoons and activated sludge.
Air Pollution Control Technology
Air pollution is not a major problem in any of the manufacturing activ-
ities in the six product groupings. Particulate emissions were ob-
served to be a potential problem in pneumatic conveyance systems. How-
ever, these emissions can be controlled with more efficient dry cyclone
separators. This will not have any impact on wastewater generation.
Reaction and refluxing oils from rosin derivatives production are em-
ployed to scrub non-condensable organics which might escape to the
atmosphere via the steam jet ejectors. Two plants that manufactured
rosin derivatives were visited during the field survey. One of the
plants vented the non-condensables to the atmosphere, and no significant
impact on pollutant loading per unit of production was observed. The
total quantity of non-condensable organics vented was probably very
smal1.
A fugitive dust problem was observed at a char and charcoal production
unit. The existing control methods employed a water spray, but quan-
tities were not sufficient to cause contaminated runoff. It is antici-
pated that the ultimate solution of the fugitive dust problem would
involve an improved materials-handling system and the elimination of
dust-wetting techniques.
In conclusion, air pollution is controlled in the Gum and Wood Chemicals
industry by dry mechanical devices and wet-scrubbing units which do not
affect wastewater loading or characteristics. Therefore, air pollution
control technology is not a significant factor in categorization of the
gum and wood chemicals industry.
IV-39
-------
Table IV B-l
Statistics by Geographical Areas
Gum and Wood Chemicals Industry
DRAFT
Geographical Area
Northeast Region
Value added by Manufacturer
$ToEPercent
4.8
North Central Region 13.6
South Region 129.6
West Region 6.1
3.1
8.8
84.1
4.0
Establi shments
Number Percent
22
40
68
5
16.3
29.6
50.4
3.7
154.1
100.0
135
100.0
Source: 1972 Census of Manufacturing
IV-40
-------
DRAFT
Solid Waste Disposal
Significant quantities of solid residue are generated in the manufactur-
ing processes of charcoal, gum, wood and essential oil production.
Spent wood fines are the major fraction of the solids from wood rosin,
turpentine and pine oil production and from production of essential
oils. In both cases these wood fines are fed to boilers, where the
residual BTU value of the fines is used to generate steam. The solids
which are generated in the production of gum rosin and turpentine in-
clude the trash contained in the crude gum material plus filter aid
material which may be employed in the filtration of the melted crude
gum. Filter aid material is also known to be used for the product re-
fining of oil of cedarwood. The use of filtration aids or adsorbent
materials, such as powdered activated carbon, for refining final or
intermediate products is common to all product categories. Such solids
are normally disposed to sanitary landfills.
The handling and final disposal of solid wastes which may be generated
in the Gum and Wood Chemicals industry has not been observed to have
impact on the quantity or characteristics of the wastewater. Therefore,
solid waste generation, handling, or disposal is not a basis for subcat-
egorizat ion.
Wastewater Quantities. Characteristics. Control
and Treatment
Table IVB-2 shows the relative variation in the wastewater quantities
and pollutants per unit of production. In reviewing the Table, some
similarities in the pertinent RWL parameters are apparent; however,
the variations provide added justification for the proposed catego-
rizat ion.
The control and treatment of wastewaters for each of the product cat-
egories is discussed in Section VII of this document. Variations in
the proposed treatment concepts, though not totally dissimilar, will
provide additional justification for the proposed categorization.
Summary of Considerations
For the purpose of establishing effluent limitations guidelines and
standards, the Gum and Wood Chemicals industry should be categorized
by major product grouping. Table IVB-3 provides a summary of the fac-
tors considered for categorization, and indicates those factors consid-
ered for categorization and those factors considered pertinent.
The factors which were significant in developing the basis for cate-
gorization include the following:
IV-M
-------
Table IV B-2
Comparison of Raw Waste Loads
By Product Grouping
Product ion
RWL Characteristics
Flow
BOD
COD
TSS
Oil
Char and
Charcoal
Gum Rosin and
Turpenti ne
Wood Rosin,
Turpenti ne,
P i ne Oil
Tall Oil
Fractionation
Products
Essential Oils
Rosin
Deri vati ve
Zero
N/A
XXX
XXX
XXX
N/A
XXX
XXXX
XXX
N/A
xxxx xxxx
XXX XXX
XX
XX
X
N/A
XX
XX
XXX
X
XX
Legend
Flow
Other RWL's
£100 Gallons/1,000 Ibs. Product
100 to 1,000 Gallons/1,000 Ibs. Product
-'"'"'- 1,000 Gallons/1,000 Ibs. Products
X 40.1 Ib./l ,000 Ibs. Product
XX 0.1 to 1.0 lb./l,000 Ibs. Product
XXX 1.0 to 10.0 Ibs./I,000 Ibs. Product
XXXX >10.0 Ibs./I,000 Ibs. Product
IV-U2
-------
DRAFT
Table IV B-3
Factors Considered for Basis of Gum
and Wood Chemicals Industry
Subcategorization
Proposed Subcategorization
Wood Ros i n,
Gum Rosin. Pitch,
Char, and Rosin, Turpentine and Essen- Rosin,
Charcoal and and Fatty tial Deriva-
Brlquets Turpentine Pine Oi I Acids Oj Is. tiyes
Manufacturing
Process
Product
Raw Material
Plant Size
Plant Location
Air Pollution Control
Technology
Sol id Waste Disposal
Operations
Wastewater Quantities
Characteristics,
Control, and
Treatment
X denotes a contributing factor for categorization
- denotes factor was considered not pertinent for categorization
IV-U3
-------
DRAFT
1. Production Processes
2. Product Types and Yields
3. Raw Material Sources
k. Wastewater Quantities, Characteristics, Control and Treatment
As Table IVB-3 shows, the five other factors also examined did not
justify further subcategorization based on the observations made through-
out this study.
Description of Subcateqories
Subcateqory A - Char and Charcoal Briquets
Plants included under subcategory A are those engaged in the manufac-
ture of char and charcoal briquets, as well as pyroligneous acids and
other by-products. Char and charcoal from hardwood and softwood dis-
tillation are economically the most important products in the Gum and
Wood Chemicals industry. Char and charcoal are produced by the car-
bonization of wood, which is the thermal decomposition of raw wood.
Subcateqory B - Gum Rosin and Turpentine
Plants included under subcategory B are those engaged in the manufac-
ture of gum rosin and turpentine by the distillation of crude gum.
Gum rosin and turpentine products make up 2.3 percent of the total pro-
duct value for the Gum and Wood Chemicals industry, according to the
1972 Census of Manufactures, high labor costs for gum collection and
the development of less costly substitute products have caused a decline
in the value of product shipments in this category. The plants which
were visited during this study operated only on intermittent schedules.
Subcateqory C - Wood Rosin. Turpentine and Pine Oil
Plants included under subcategory C are those engaged in manufacturing
wood rosin, turpentine and pine oil. These industries use solvent ex-
traction and steam distillation as their manufacturing processes, and
their typical raw materials are resinous wood stumps. These products
account for 19 percent of the total product value for the total indus-
try, according to the 1972 Census of Manufactures. The economic life
of this subcategory is limited by a lack of available raw materials
near existing plants and the development of economically competitive
processes within the Gum and Wood Chemicals industry.
-------
DRAFT
Subcategory D - Tall Oil Rosin. Fatty Acids
and Pitch
Plants included under subcategory D are those which manufacture tall
oil rosin, fatty acids and pitch by fractionation of Kraft process crude
tall oil. The growth of the tall oil refining industry has been un-
abated since the inception of modern technology in 19^9. Technology
for the production of high-purity tall oil rosin and fatty acids is
fairly recent. Modern fractionation techniques yield fatty acids and
rosins with very low cross-product contamination.
Subcategory E - Essential Oils
Plants included under subcategory E are those which manufacture the
rosin derivatives: esters, adduct modified esters, and alkyds. These
are produced by chemical reations involving rosins, monohydric or poly-
hydric alcohol, and chemical modifiers. Most of the rosins produced
in the United States are actually rosin-derived products, in which the
rosins are modified to eliminate undesirable properties and to enhance
their application in many manufacturing processes.
Process Descriptions
The following pages in this section contain a profile of the findings
made during field surveys of the Gum and Wood Chemicals industry. The
profiles contain typical process flow schematic diagrams, grouped ac-
cording to the proposed subcategorization of the industry.
Subcategory A - Char and Charcoal Briquets
Char or charcoal is produced by the carbonization of wood, which is the
thermal decomposition of the raw wood. The product yield and purity are
a function of the kiln temperature. Above 270°C, exothermic reactions
set in, and the process can be self-sustaining with the rate of carbon-
ization normally controlled by limiting the air feed to the kiln. Higher-
temperature reactions produce a higher carbon content product but reduce
the product yield. During the decomposition of the wood, distillates
are formed and leave the kiln with the flue gases. The condensable dis-
tillates are collectively referred to as pyroligneous acid, which contains
methanol, acetic acid, acetone, tars, oils, and water. These materials
have steadily declined in economic importance because of cheaper methods
of producting synthetic substitutes; therefore, most plants have dis-
continued recovery of the by-products from the pyroligneous acid.
Instead, the distillate and other flue gases are fed to an afterburner
for thermal destruction before the flue gases are exhausted to the at-
mosphere. The condensable distillates may also be recycled as fuel for
-------
DRAFT
the kiln or recycled in the vapor phase as a fuel supply supplement.
The noncondensable gases contain CO , CO, CH, , H and some higher hy-
drocarbons. The exact composition of the gases depends on the distil-
lation temperature.
A typical flow diagram for char and charcoal briquets manufacturing is
illustrated in Figure IVB-1. During this study, no facilities which
recovered distillation by-products were known to exist in the United
States. The kiln depicted in Figure IVB-1 is loaded with a payloader.
After the kiln is loaded, the wood is set afire and allowed to burn
under controlled conditions for approximately 72 hours. The air for
oxidation is then cut off and water injected in the kiln for quenching.
Approximately 18 hours is required for the material to cool down; after-
wards, it is removed by a payloader. Pine wood char is sold at this
point in the process to fill specialized orders. Hardwood char is
ground, then blended with starch binder and water for feed to the
briqueting operation. The resulting briquets are dried and packaged in
bags for sale.
The off gases from the furnaces presumably contain compounds such as
acetic acid, methanol, acetone, tars, and oils. These materials arc
presently oxidized in the afterburners. The natural gas fuel required
for the afterburners is a significant operating cost. An alternative
emission control is now under consideration, in which off gases from
the furnace would be scrubbed to remove the condensables from the flue
gases. The resulting scrubber liquor would be sent to a separator where
the pyroligneous acid could be recovered. The water and soluble com-
pounds would be reused in the scrubber system. The separated products
could then be recovered for sale or as an auxiliary fuel.
Subcategory B - Gum Rosin and Turpentine
Figure IVB-2 illustrates a process flow schematic for the manufacture
of gum rosin and turpentine. The crude gum raw material is obtained
by gum farmers who collect the gum from scarified longleaf pine and
slash pine trees. The plant receives raw crude gum from the gum farm-
ers in ^35 Ib-barrel shipments. These shipments contain some dirt,
water, leaves, bark, and other miscellaneous trash. Gum is emptied in-
to a vat by inverting the crude gum containers over a high-pressure
steam jet. The melter liquifies the crude gum material , and recycled
turpentine is added to reduce the viscosity. This mixture is filtered
through a pressure filter where trash is periodically removed and haul-
ed to a landfill. The filtered gum is then washed with water. Because
iron and calcium causes gum rosin to discolor at high temperature, a
small amount of oxalic acid may be added to the wash water to precip-
ate the iron and calcium as an insoluble oxalate. The wash water
IV-1*6
-------
\\i-k7
-------
DRAFT
removes soluble acids and oxalate precipitate, and is then discharged
for treatment. The prepared crude gum material is then distilled to
separate the turpentine.
Noncontact shell- and-tube steam heating and sparging steam are used in
the stills. Turpentine and water are distilled overhead and condensed
with shel1-and-tube condensers. The water is separated from the tur-
pentine in the downstream receivers as shown in Figure IVB-2. The tur-
pentine product is dried with a sodium chloride salt dehydrator, and the
gum rosin is removed from the still after each batch distillation in a
fluid state and packaged.
Subcateqory C - Wood Rosin, Turpentine and Pine Oil
The raw material for this process is stumps obtained from the cut-over
pine forests of the southern United States. The stumps are uprooted
by bulldozers and freighted to the extraction plant on railroad flat
cars.
Figure IVB-3 is a flow schematic diagram of the solvent extraction/
steam distillation plant which was surveyed.
The pine stumps from ^0-60 year old long leaf pine trees are brought
into the plant. The stumps are placed on a conveyor and are washed
with 1,000 gpm of water at 9 pressure of 110 psi. The water and dirt
flow to a settling pond where the dirt settles out and the water is re-
cycled back to the washing operation. The accumulated dirt is peri-
odically removed. Wood hogs, chippers and shredders mechanically re-
duced the wood stumps in size in a sequence operation until they become
chips approximately 2" in length and 1/16" diameter. These chips are
placed into intermediate storage. The wood chips are fed to a battery
of retort extractors. The extraction process is accomplished in se-
quential steps as follows:
(1) Water is removed from the chips by an azeotropic distillation
with a select water immiscible solvent which may be ketone or
petroleum fraction such as benzene or naptha.
(2) Extraction of the resinous material from the wood chips with
a select water immiscible solvent.
(3) Steaming to remove the residual solvent from the spent wood
chips.
After the final step, the spent wood chips are removed from the retort
and sent to the boilers as fuel. During steps 1 and 3, the steam-
solvent azeotrope from the retorts proceeds to an entrainment separator.
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l>KAi
Subcateqory D - Tall Oil Rosin. Fatty Acids and Pitch
Technology for the production of high-purity tall oil rosin and
fatty acids is relatively recent compared to the age of the wood and
gum rosin industry. The first commercial fractionation process was
completed in 19^9 by Arizona Chemical. The Arizona plant employed par-
tial vacuum distillation techniques used in the petroleum refining in-
dustry and adapted to protect the integrity of tall oil's heat-sensitive
const i tuents.
Modern fractionation techniques yield fatty acids which contain less
than 2 percent rosin and rosins which contain less than 3 percent fatty
acids. Distillation techniques employed prior to fractionation tech-
nology employed steam distillation which produced rosin and fatty acid
products with relatively high cross-product contamination.
The plant which was surveyed during this study employed modern fraction-
ation distillation techniques. A schematic process flow diagram of
this crude tall oil (CTO) fractionation process is presented in Figure
\\IB-k.
The plant fractionates CTO to produce approximately 20 percent pitch,
49 percent fatty acids, and 31 percent rosin. In addition, part of the
plant's pitch and rosin production is used captively for the production
of paper sizes; however, no wastewater discharges were observed coming
from this unit during the survey period.
The CTO is treated with dilute sulfuric acid to remove some residual
lignins plus mercaptans, disulfides and color materials. The CTO then
proceeds to the fractionation process. In the first fractionation
column, the pitch is removed from the bottoms and is either sold, sa-
ponified for production of size, or burned in boilers to recover its
fuel value. The remaining fraction of the tall oil (rosin and fatty
acid) then proceeds to the pale plant, where the quality of the raw
material is improved through the removal of unwanted materials such as
color bodies. The second column in Figure IVB-^t separates low-boiling-
point fatty acid material while the third column completes the separ-
ation of fatty and rosin acids.
Barometric contact condensers are employed to condense vacuum jet steam.
The recirculated barometric contact water is cooled by a holding reser-
voir, while light separable organics are removed by means of an induced-
draft cooling tower. This contact condenser water recirculation system
produces little, if any, discharge of wastewater, and therefore is con-
sidered exemplary technology. Once-through cooling water is used in
noncontact column reflux heat exchangers and product heat exchangers.
IV-51
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DRAFT
Any entrained wood fines coming from the retorts are removed in the en- •
trainment separator and are used in the furnace as fuel. The vapors
from the entrainment separator are condensed and proceed to one or more
separators where the solvent-water mixture separates. The solvent is
recycled for use in the retorts.
The extract liquor leaving the retorts during step 2 is placed into
intermediate storage tanks prior to further processing. The contents
of these tanks are sent to a distillation column to separate the solvent
from the products. The column is operated under vacuum conditions main-
tained by a steam ejector. The overhead from the column is condensed
and enters a separator where condensed solvent is removed and recycled
to the retorts. The vapor phase from the separator, along with the
steam from the ejector, is condensed in a shel1-and-tube exchanger and
enters a separator. Here the separation is made between the remaining
solvent and the condensed steam from the ejector. The solvent is sent
to recycle and the water to treatment.
The bottoms stream from the first distillation column enters a second
distillation column, also operated under vacuum, as shown in Figure IVB-3,
Steam is introduced into the bottom of the tower to strip off the vol-
atile compounds. This overhead stream enters a condenser and separator.
A portion of the condensed liquor phase is refluxed back to the distil-
lation column, while most of it is stored as Crude Terpene for further
processing. The steam from the vacuum ejector and the vapor phase from
the separator are condensed in a shel1-and-tube exchanger and then sent
to a separator. The nonaqueous phase from the separator is stored as
Crude Terpene while the aqueous phase is removed as wastewater. The
bottom stream from this second distillation column is the finished
wood Rosin product.
The crude terpene, which has been removed in the second distillation
column, is stored until a sufficient quantity has been accumulated,
when this material is processed in a batch distillation column. The
distillation column is charged with the crude terpene material, the
overhead vapors are condensed in a shel1-and-tube exchanger, and the
condensed material enters a separator. The turpentine and pine oil
products are removed from this separator while the vapors and the steam
from the steam ejector enter a second shel1-and-tube exchanger and pro-
ceed to a separator. The nonaqueous phase from the separator is re-
cycled to the extract liquor storage while the aqueous phase is sent
to wastewater treatment. The bottoms from this batch distillation
column is a residue containing high-boiling materials, best described
as pitch. This residue is used for fuel.
IV-53
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DRAFT
metal salts. The rosin derivative manufacturing industry has modified
the various rosins to eliminate these undesirable properties and to
enhance their application in the foregoing production and their many
others.
During this study, two facilities which manufactured rosin derivatives
were surveyed. Plant No. 1 was producing wood rosin ester and a
phenolic modified tall oil ester during the survey. Plant No. 2
produces tall oil and gum rosin based esters, maleic anhydride,
fumaric acid, substituted phenolic, and other modified rosin based
esters, as well as glycerol phthalate alkyd. Historical data on the
manufacture were used, along with survey data, to determine RWL's.
It should be noted that there are many rosin-derivative manufacturing
processes which were not included in the study. Those processes which
were not surveyed include: isomerization, oxidation, hydrogenation,
dehydrogenation, polymerization, salt formation, and decarboxylation.
Figure IVB-6 illustrates the process at Plant No. 2. The processes at
Plant No. 1 are similar, except that the vacuum jet steam is exhausted
to the atmosphere and the process wastewater is discharged from the
receiver without separation.
Process operating conditions in the reaction kettle are dependent on
many variables, such as product specification and raw materials. For
example, at Plant No. 1 a simple ester is produced from stump wood
rosin (WW GRADE) and U.S.P. glycerin. The esterification reaction takes
place under high-temperature vacuum conditions. During the process, a
steam sparge (lasting approximately 2-3 hours) is used to remove excess
water of esterification, which allows completion of the reaction and
removes fatty acid impurities for compliance with product specifications,
The condensable impurities are condensed in a noncontact condenser on
the vacuum leg and stored in a receiver. Noncondensables escape to the
atmosphere through the reflux vent and steam vacuum jets. Plant No. 1
also produces phenol and maleic anhydride-modified tall oil rosin esters,
The process operation is very similar to simple rosin ester production
except that steam sparging is seldom if ever used, and other polyhydric
alcohols may be used in the product formulation.
Plant No. 2 produces rosin-based esters, maleic anhydride, fumaric acid,
substituted phenolic, and other modified rosin based esters, as well
as a glycerol phthalate alkyd. Kettle cook times and pressure condi-
tions vary with type of product. No contact sparge steam is used except
for the production of resins to be used in hot-melt adhesives and
chewing gum products, wherein steam sparge is used at the end of the
cook to remove lights and odors. Unwanted materials, such as fatty
acids, water of esterification, and sparge steam, are pulled from the
kettle by means of the vacuum leg. Condensable materials are condensed
IV-55
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IV-56
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DKAI I
in a noncontact condenser and separated from the noncondensables in the
receiver. Separable materials, such as fatty acids and reaction and
reflux oils, are separated from the processes wastewaters in the
separator. Vacuum jet steam and most noncondensable materials are
removed in a scrubber which uses a recirculated oil stream from the
separator. The oils are recovered for secondary market.
IV-57
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DRAFT
C• Pesticides and Agricultural.. .Chciii.lrc..o.l>.Jiiduv.l)'y
Rationale of Categorization
Industry subcategories were established so as to define those sectors
of the Pesticides and Agricultural Chemicals industry where separate
effluent limitations and standards should apply. The underlined
distinctions between the various groupings have been based on the
wastewater generated, its quantity, chemical characteristics, treat-
ability, and the applicability of control and treatment technologies.
The following factors were considered in determining whether such
subcategorizations are justified:
Manufacturing Processes
Pesticide plants which manufacture active ingredient products use
many diverse manufacturing processes. Rarely does a plant employ
all of the processes found in the industry, but most plants use
several in series. The principal processes utilized include chemi-
cal synthesis, separation, recovery, purification, and product
finishing, such as drying.
Chemical synthesis can include chlorination, alkylation, nitration,
and many other substitutive reactions. Separation processes include
filtration, decantation, and centrifuging. Recovery and purification
are utilized to reclaim solvents or excess reactants as well as to
purify intermediates and final products. Evaporation, distillation,
and extraction are common processes in the Pesticides and Agricul-
tural Chemicals industry. Product finishing can include blending,
dilution, pelletizing, packaging, and canning.
It is concluded that because of manufacturing differences, the formu-
lating/packaging industry requires separate categorization to the
active ingredient manufacturing sectors. Since diverse processes
are used by all sectors of the active ingredient industry, as dis-
cussed above, manufacturing process alone is not a comprehensive
basis for categorization.
Product
Four fundamental pesticide subcategories are evident based on the
generic class of the product and the process chemistry employed:
A. Halogenated Organic
B. Phosphorus-Containing
C. Nitrogen-Containing
D. Metallo-Organic
IV-58
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DRAFT
In addition to the above generic classes, formulation and packaging
of ingredient pesticides generate wastewaters with qualities and
volumes different from the four basic categories. This is because
the starting material is generally a pesticide active ingredient
and the principal wastewaters result from equipment cleanout oper-
ations. The manufacturing processes are usually relatively simple
in nature with few chemical synthesis processes. Accordingly, a
fifth industry subcategory is required for the formulation and
packaging product class:
E. Formulators and Packagers
Raw Materials
Since it can be assumed that the raw materials used in the Pesticides
and Agricultural Chemicals industry are basic feedstocks specific to
the product being manufactured and with narrow ranges of quality and
purity, the choice of raw material does not have a significant im-
pact on the nature or quantities of waste products generated, and,
accordingly, wastewater volumes and qualities are not affected by
choice of raw materials. Thus, the selection of raw materials is
not a significant factor on which to base subcategorization.
Plant Size
There are nearly 100 plants in the United States engaged in the pro-
duction of pesticidal active ingredients, and possibly as many as
500 facilities formulating the active ingredients into final products,
such as liquids, dusts, and packaged aerosols. The sizes of process
units, production complexes, and individual companies in the Pesti-
cides and Agricultural Chemicals industry sector are not published and
they were not available for the purposes of this study. Based on
information obtained during plant visits, it is obvious that plant
size can vary appreciably. Plant size will not affect the appli-
cability or performance of control and treatment technologies, but
potentially will impact markedly on the cost of treatment. Ac-
cordingly, plant size is not considered as a subject for subcategori-
zation of the Pesticides and Agricultural Chemicals industry.
Plant Age
Pesticide plants currently in operation are relatively new, commis-
sioned predominantly in the post-World War II period, and the general
processing technologies have not changed appreciably. Different
processing modes, such as batch, semi-continuous and continuous, are
utilized based on product type, inherent process requirements, and
economies of scale, and not because the technology on equipment has
changed significantly over the years. Therefore, it is concluded
that plant age is not a significant factor for subcategorization.
IV-59
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DRAFT
Plant Location
Pesticide plants are distributed throughout the United States (refer
to Figure IIIC-1). Based on analysis of existing data presented in
recent studies and the results of plant visits to the South, Midwest,
and North geographical areas of the country, plant location has little
effect on the quality or quantity of the wastewater generated. Geo-
graphic location, however, can influence the performance of aerated
and stabilization lagoons, but low performance problems can be over-
come by adequate sizing or selection of alternative processes, such
as activated sludge.
Since most pesticide plants are relatively new, they tend to be
located in rural areas. Those plants that are located in urban
areas, however, tend to occupy and own less land, with the result
that land costs for treatment facilities are higher.
Taking the above points into account, it can be said that, other than
costs associated with land availability, plant location is not a sig-
nificant factor for further subcategorization of the Pesticides and
Agricultural Chemicals industry.
Housekeepi nq
Housekeeping practices vary within the industry; however, they are
influenced more by philosophy of the company and personnel involved
than by the manufacturing process or product mix. In many cases,
plants with comprehensive treatment facilities or a history of
good treatment exhibit good housekeeping techniques. This phenomenon
is founded on necessity and experience that dictate that good treat-
ment requires good housekeeping.
In view of these findings it can be concluded that housekeeping alone
is not a reasonable factor for industry subcategorization.
Air Pollution Control Equipment
No sector of the Pesticides and Agricultural Chemicals industry has
an exclusive need for air pollution control equipment. Vapors and
toxic gas fumes are frequently incinerated. Particulates can be
removed by either baghouse or wet scrubbing devices. In all cases,
the wastes produced by air control devices are treatable and do not
serve as a basis for subcategorization.
Nature of the Wastes Generated
The type and characteristics of the wastes generated by the various
sectors of the Pesticides and Agricultural Chemicals industry are
IV-60
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DRAFT
discussed fully in Section V. In brief, the nature of the generated
wastes is a reasonable basis for subcategorizating the Industry. The:
rationale behind such a subcategorization is adequately covered in
the process descriptions subsections.
Treatability of Wastewaters
The treatability of the wastewater generated by the various sectors
of the industry exhibit different characteristics and specific treat-
abilities. The waste types and treatab!1 I ties are related to the
industry sector, its products and processes, and no qenernlI/c
-------
DRAFT
Pesticides,
Subcategory B includes those pesticide products listed under phosphorus-
containing in Table IIIC-4. The subcategory covers phosphates, phos-
phonates, phosphorothi vates , phosphorothiovates, and phosphorus-nitrogen
pesticide types.
Subcateqory C - Orqano-Ni troqen
Pesticides
Plants included under Subcategory C manufacture those products listed
in Table I I I C-4 under Nitrogen-Containing. This subcategory has more
family groups and is the most diverse of all the pesticide subcategor ies.
Subcateqory D - Metal lo-Orqanic
Pesticides
The metal lo-organic pesticide subcategory could be considered a part of
the inorganic and metal lo-organic sector of the industry. However, since
most inorganic pesticides are essentially simple inorganic chemicals, they
are not covered in this document. The metal lo-organic pesticides in-
cluded in Subcategory D are listed in Table IIIC-4.
Subcateqory E - Formulators
and Packagers
Subcategory E includes all types of pesticide formulating, blending,
packaging, canning, etc. It should be emphasized that the manufacture
or production of active ingredients material is excluded from this
subcategory. This subcategory can be further subcategor i zed, based
on the nature of the production operations and the wastes generated,
into water-based products (Subcategory E^) and solvent-based dry
products (Subcategory
Process Descriptions
Halogenated Organic Pesticides
Four major halogenated organic pesticide groups merit process de-
scriptions and process flow diagrams. These groups are:
DDT and its relatives
Chlorinated phenols and aryloxyal kanoic acids
Aldrin toxaphene
Halogenated aliphated compounds
Although halogenated organic pesticides can involve other halogens,
chlorinated compounds are more common and, in most cases, are il-
lustrative of the processes and wastes associated with the other
halogenated organic pesticides.
IV-62
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DRAFT
DDT and its relatives
Although present DDT production is on the decline, its manufacture
is well documented in the literature and serves as a good example
of the production and associated wastewaters for the DDT family of
pesticides. Analogs of DDT can generally be prepared by simply
changing the aldehyde to be reacted with the chloroben?ene in the
presence of a dehydrating agent, usually concentrated sulfuric acid.
Figure IVC-1 is a simplified process flow diagram for DDT production
and illustrates the type of wastewater generated. The process
description that follows is an example of how the process(es) may be
carried out commercially, although considerable variations exist in
process equipment design, reactant concentrations, amount of recycle
acid, and methods of purification.
An aldehyde, chlorobenzene, and concentrated (95~99 percent) sulfuric
acid or oleum are'charged to a steel reactor. Generally, the aldehyde
and chlorobenzene are mixed together with part of the concentrated
sulfuric acid. External cooling, or cooling by means of internal
coils, is generally necessary to maintain the desired reaction temp-
erature. The batch reaction can take several hours, or it may also
be run continuously by using a number of reactors in series.
At the end of the reaction, the crude product goes to separators,
where the spent acid separates. This acid contains small amounts of
sulfonated chlorobenzene and aldehyde. The recovered acid is purified
and concentrated for re-use. The product liquor from the top of the
separator goes to a liquid-phase scrubber, where water is used to
remove mechanically entrained sulfuric acid. The liquor is then
washed with dilute caustic or sodium carbonate solution in a second
scrubber and finally washed with water. The separator and scrubber
are maintained at sufficiently high temperature to prevent product
crystal 1i zation.
The neutralized product.containing chlorobenzene can be run to a
column, where it is vacuum-distilled. The chlorobenzene distillate
is passed through a separator and condenser and is finally pumped
to storage for recycling. The molten product containing a small
percent of chlorobenzene can be pumped to a still, where additional
chlorobenzene is removed by continuous atmospheric distillation.
The melt is maintained at a temperature to prevent crystallization.
The chlorobenzene-free product melt is generally run to a flaker
(consisting of a chilled drum rotating through a steam heated feed
trough), where it is chilled to flakes. The flaked product is then
pulverized to the proper mesh size and either packaged in concen-
trated form or blended with inert extenders.
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It is becoming standard practice to recycle as much spent acid as
possible and to raise the acid concentration to the desired level
by the addition of oleum.
In the purification and finishing of the product, the most common
solvents used are petroleum fractions and excess chlorobenzene. In
order to pulverize the product adequately, entrained solvent must
be reduced to as low a concentration as possible. Some manufacturers
develop friability by aging the product, others by grinding in the
presence of dry ice.
In summary, the process wastewaters associated with the production
of DDT and its analogs are:
Waste acid from acid recovery unit.
Scrub water from liquid phase scrubber.
Dilute caustic wastewater from caustic
soda scrubber.
Production area clean-up wastes.
Scrubber water from vent gas water scrubbers.
Chlorinated Phenols and Aryloxyalkanoic Acids
Chlorobenzenes are used as a starting material in the manufacture of
chlorinated phenols and in the manufacture of chlorinated aryloxy-
alkanoic acid pesticides. Figures IVC-2 and IVC-3 are simplified
process flow diagrams for the manufacture of the chlorinated phenols
and aryloxyalkanoic acids. Potential wastewater sources are shown.
Chlorobenzene can be converted to a phenol by reacting with dilute
caustic soda or water and a catalyst in a reactor. Pentachloro-
phenol (PCP) is prepared by chlorinating the phenol in the presence
of a catalyst (see Figure IVC-2). Excess hydrogen chloride and
chlorine can be scrubbed with phenol and recycled to the reactor.
The free hydrogen chloride is recycled to the chlorine plant. The
crude PCP is distilled to remove tars which are finally incinerated.
Molten PCP can then be prilled or reacted with NaOH to form the
sodium salt.
Halogenated aryloxyalkanoic acids can be prepared by charging equi-
molecular quantities of a chlorophenol and a monochloroalkyl acid
to a steam-heated closed kettle in the presence of dilute caustic.
The method of synthesis for 2,i4--dichlorophenoxyacetic acid (2,^-D)
is generally applicable to the majority of the class. The reaction
Is carried on for several hours under reflux conditions, after which
time the reaction mass is acidified (to approximately pH = 1.0) with
dilute hydrochloric acid. The acidified liquor is sent to a crystal-
lizer followed by a centrifuge. The reaction is carried out under
optimum conditions of time, temperature, and rate of addition of
IV-65
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DRAFT
roactants to prevent hydrolysis of unconvrrtnd chloronlkyl nchl.
In one process variation, unreactcd dlchlorophrnol Is removed by
distillation prior to acidification. In still another variation,
the reaction is carried out in anhydrous monochlorobenzene (as a
solvent) at the boiling point of the solvent; water is removed
azeotropically. The Insoluble product is separated from solvent
by filtration.
Esters and amine salts are prepared by reacting the phenoxy alkyl
acid with an alcohol or amine, respectively. These products have
better formulation and application properties.
Briefly, wastewaters generated from the production of this group
of pesticides are:
Excess prill tower dust scrubber water
Centrate from liquid/solid separation step
Vent gas scrubber waters
Reactor and processing unit cleanout wastewaters
Processing area washdown wastes
Aldrin-Toxaphene Group
The insecticides of this group, except for Toxaphene and Strobane
which are discussed below, are polychlorinated cyclic hydrocarbons
with endomethylene-bridged structures, prepared by the Diels-Alder
diene reaction. The development of these materials resulted from
the 19^5 discovery of chlordane, the chlorinated product of hexa-
chlorocyclopentadiene and cyclopentadiene. Figure \\IC-k, a simplified
process flow diagram for this type of pesticide, illustrates the
potential sources of wastewater in this process.
Cyclopentadiene, produced by cracking naphtha, is chlorinated to
yield hexachlorocyclopentadiene (CPD), the raw material basic to
the chemistry of this group of pesticides. Cyclopentadiene and
various vinyl organic compounds can be combined with CPD in the
Diels-Alder reactor.
Certain pesticides in this group can be epoxidized with hydrogen
peroxide or peracids to produce a second generation of pesticide
compounds.
Toxaphene and Strobane are members of a group of incompletely chai—
acterized broad-spectrum insecticidal compounds produced by the
chlorination of naturally occurring terpenes. They are insoluble
in water and generally have long residual effects. These compounds,
however, are unstable in the presence of alkali, upon prolonged
exposure to sunlight, and at temperatures above 155°C, liberating
hydrogen chloride.
IV-68
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Wastewater generated In the production of this family of pesticides
are:
Vent gas scrubber water from caustic
soda scrubber
Aqueous phase from the epoxidation step
Wastewater from the water wash and product
purification units
Periodic equipment cleaning Wastewater
General housekeeping
Tars and off-specification products require incineration.
Halogenated Aliphatic Hydrocarbons
This group Includes chlorinated aliphatic acids and their salts
(e.g., TCA, Dalapon, and Senac) herbicides, halogenated hydro-
carbons fumigants (e.g., methyl bromide, carbon tetrachloride,
DDT DBCP and EDB\ and tne insecticide Llndane. Figures IVC-5
and IVC-6 represent simplified process flow diagrams for the pro-
duction of halogenated aliphatics and halogenated aliphatic acid
pesticides. Potential Wastewater sources are illustrated.
Chlorinated aliphatic acids can be prepared by nitric acid oxidation
of chloral (TCA), or by direct chlorlnation of the acid. The acids
can be sold as mono- or di-chloro acids, or neutralized to an aqueous
solution with caustic soda. The neutralized solution is generally
fed to a dryer from which the powdered product is packaged.
Wastewaters potentially produced during the manufacture of pesticides
In this group are:
Condensate from steam jets
Acidic wastewater from fractionation units
Cooler blowdown water
Excess mother liquor from centrifuges
Vent gas scrubber water from caustic
soda scrubber
Aqueous phase from decanter units
Scrubber water from dryer units
Wash water from equipment cleanout
Process area clean up wastes
Phosphorus-Conta? ning Pesticides
The commercial organo-phosphorus pesticides, composed of phosphates,
phosphonates, phosphorothioates, phosphorodithioates, and phosphorus-
nitrogen compounds, account for about 95 percent of the phosphorus-
containing pesticides produced today.
IV-70
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Seven of the 10 most popular organo-phosphates start with the prepar-
ation of a phosphite trlester (P(OR)j) which can be readily oxidized
to the respective phosphates, but are more commonly reacted with
a ketone or aldehyde having an alpha-carbon hallde. The product thus
formed Is a phosphate with an unsaturated aliphatic grouping. These
compounds can then be halogenated across the double bond to form
yet another compound with pestlcldal properties.
Phosphates and Phosphonates
Figure IV-7 Is a simplified process flow diagram of phosphite triester
production showing potential wastewater sources.
In the manufacture of the phosphite triester, an alcohol and phosphorus
trichloride is fed to a reactor using a base (for example, sodium
carbonate) to produce the crude product, with hydrogen chloride as a
by-product. The phosphite triester is then reacted with a chloro-
ketone or chloraldehyde in a reactor/stripper vessel. Light-ends are
continuously removed under vacuum. The condensible fraction contain-
ing the by-product alkyl halide can be recovered but is generally
wasted. Noncondensibles captured in the steam condensate go to
treatment.
The technical-grade intermediate dissolved in an inert solvent is
then halogenated. After halogenation in a batch reactor/stripper,
the vented gas Is scrubbed with a solution of caustic soda. This
wastewater goes to treatment. Then under reduced pressure, the
solvent Is removed, condensed and recycled back to the reactor.
Condensate from the steam jet system is collected for treatment.
Generally, the ketone or aldehyde is manufactured on-site, and these
wastes usually become part of the "pesticide" process wastes.
Phosphorothioates and Phosphonothioates
This family of pesticides include the parathions, malathion, ronnel,
diazinon, Guthion, Dasanlt, disulfoton, dimethoate, chlopyrifos,
ethion, Folex, and carbophenothion, each of which is produced in
greater than one million pounds quantity annually.
Figure IVC-8 is a generalized process and waste flow diagram for
this group of compounds. In the first step, phosphorus pentasulfide
(P2Sr) is reacted with an alcohol (generally In a solvent) to form
the dialkyl phosphorodlthioic acid (dithio acid). This is an an-
hydrous reaction.
The dithio acid can then be: (1) converted to a dithio salt, (2)
chlorinated to the dialkyl phosphorochloridothionate (DAPCT), or
(3) reacted, as the dithio acid with an aldehyde or an alkene to
form a desired intermediate or product.
IV-73
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Using the production of the dlthlo salt as an example, caustic soda
Is added to the dlthlo acid In a separate reactor to produce the
dlthlo salt. The dlthlo salt In the aqueous phase Is separated to
be used In the next reaction step. The organic phase serves to re-
move residuals, namely unreacted trlester. Solvent Is recovered and
returned to the dlthlo acid unit. Wastes from the solvent recovery
step are sent to treatment.
The dithlo acid can also be chlorinated to produce a phosphorchlori-
dothionate (PCT) which can combine with the dithio salt in a con-
densation step. The crude PCT can be purified by distillation. Dis-
tillation residues are hydrolyzed, yielding sulfur and phosphoric
acid as by-products. Organic wastes require treatment.
The dithio acid can be further reacted with an aldehyde or alkene
under slightly acidic conditions in a batch process. Caustic soda
is added to maintain the correct pH. In a recovery system, product
is recovered, water washed, and then air dried. The recovery step
wastes include distillation wastes and solids (filter cake). Acid
wastewater from the wash step is combined with scrubber water from
the overhead drier. These wastewaters constitute the major portion
of the process waste stream.
Process wastewater can be detoxified (alkaline hydrolysis at elevated
temperatures) before combining with other plant waste streams.
In summary, the following wastewaters are generated during the pro-
duction of organo-phosphorus compounds.:
Hydrolyzer wastewater
Aqueous phase from product reactors
Wash water from product purification steps
Aqueous phase from solvent extractor
Wastewater from overhead collectors and
caustic soda vent gas scrubbers
Reactor and process equipment cleanout wastes
Area washdowns
Orqano-Nitrogen Processes
The nitrogenous pesticides include the greatest number of chemical types,
broadest raw material base, as well as the most diverse process schemes.
Product and process types to be described are the aryl- and alkylcar-
bamates, thiocarbamates, amides and amines, ureas and uracils, tri-
azines, and the nitroaromatics.
Aryl and Alkyl Carbamates and
Related Compounds
The carbamates in this grouping include carbaryl, carbofuran, chloro-
propham, BUX, aldtcarb and propoxur. A generalized production flow
IV-76
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DRAFT
diagram Is shown In Figure IVC-9 together with the principal waste-
water sources.
In general, carbamates are synthesized In a combination of batch and
continuous processes. Wastes include liquid streams, vents and some
heavy residues. Potentially toxic wastewaters require detoxification
(via alkaline hydrolysis) before being sent to the general plant
treatment system. Vents are flared, or pass through a caustic scrubber.
Heavy residue requires incineration.
Wastewaters associated with the production of these compounds are:
Brine process wastewater from reactors
Wastewater from the caustic soda scrubbers
Aqueous phase wasted following the isocyanate
reaction
Reactor cleanout washwater
Area washdowns
Thiocarbamates
This family of pesticides include Eptam, butylate, vernolate, pebulate
and EPTC. In a series of semi-continuous and batch operations, as
shown in Figure IVC-10, phosgene is reacted with an amine to give a
carbamoyl chloride. Reaction of the carbamoyl chloride with a mer-
captan gives the corresponding thiocarbamate.
Alternately, the amine can be reacted with an alkyl chlorothiolformate
to yield the thiocarbamate. Thiocarbamates are generally volatile
compounds. Therefore, these products can be distilled.
Acidic process wastewater from the first reactor are combined with
the brine wastes from the second reactor along with vent gas scrubber
water before treatment. Still bottoms are generally incincerated.
Liquid wastes are biodegradable, especially following acid or alka-
line hydrolysis at elevated temperatures.
In summary, the production of thiocarbamates will generate the follow-
ing wastewaters:
Acid wastewater from the initial
reaction step
Brine from the second reaction step
Wastewater from caustic soda scrubbers
Kettle clean-out wash waters
Area washdowns
IV-77
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Amides and Amines
(without sulfur)
Compounds in this group include Deet, naptalam, CDAA, propachlor,
alachlor, propanil and diphenamid, each of which has been produced
at greater than one million pounds per year. Typically, these
herbicides include two major groups: herbicides based on substi-
tuted anilide structures and chloroacetamide derivatives.
A generalized process flow diagram, indicating wastewater sources,
is presented in Figure IVC-11. Briefly, the process is based on
the reaction of an acid chloride with a suitable amine. Generally,
the amine is prepared within the same plant. Wastewater from the
preparation of amine can be included in the raw waste load for the
production of these pesticides. Such wastewaters are generated
from the intermediate product separation and purification steps.
If the acid chloride is also prepared on-site, then acidic process
wastewater from the purification step vent gas scrubbers should be
considered part of the overall pesticide raw waste loas.
In summary, wastewaters resulting from the production of the amide
and amine group of pesticides are:
Aqueous fractions from reactors
Wastewater from purification steps
Vacuum jet condensate
Wastewater removed in purification step
Water from washing steps
Kettle cleanout wastes
Area washdown
Ureas and Uraci1s
Pesticides in this group include diuron, fluometuron, linuron and norea
urea compounds and the herbicide bromacil, each of which has a pro-
duction level in excess of one million pounds per year.
the production of monuron is typical of the general process used to
manufacture this family of pesticides. Figure IVC-12 shows the
generalized process flow diagram and wastewater sources associated
with the production process. Reaction of para-chloroani1ine in
dioxane or another inert solvent with anhydrous hydrogen chloride
and phosgene generates para-chlorophenyl isocyanate, which then can
be reacted with dimethylamine to yield monuron. Another commercial
process involves the reaction of an aniline and urea in alcohol or
phenol solevent to generate the phenyl isocyanate, which is further
reacted with an appropriate amine. The ureas are generally insoluble
in the inert solvent and precipitate out. The inert solvent can be
flash-distilled and recycled to the reactor. Aqueous hydrochloric
acid is added to the crude product to remove insoluble components.
The product is then water washed in a precipitator to yield the final
product.
IV-80
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DRAFT
Uracils are a relatively new class of herbicides whose group is
growing. The process Illustrated In Figure IVC-12 Is as follows:
An alkylamlne, phosgene, and ammonia are reacted to yield an
alkyl urea. Following a caustic wash purification step, the
alkyl urea Is then reacted with an alkyl acetoacetate, caustic
washed and neutralized with sulfuric acid. The uracil can then
be halogenated (commonly with bromine), filtered, dried and
fInally packaged.
No solid wastes are generated and no significant quantities of
chemicals are recycled. Liquid wastes from the purification,
neutralization and filtration steps require treatment via either
biological oxidation or incineration technologies.
In summary, wastewaters generated in the manufacture of urea and
uracil pesticides can be as follows:
Aqueous wastes from preclpltator (Urea)
Scrubber waters (Urea and Uracil)
Brine from purification steps (Uracil)
Aqueous sodium sulphate from neutraliz-
ation and Intermediate product
separations (Uracil)
Brine from fiItration
Reactor wash water (Urea and Uracil)
Production area washdowns (Urea and Uracil)
s-Triazines
The herbicidal value of derivatives of s-triazine has been a recent
discovery. Atrazine leads all other herbicides in the U. S. in volume
of usage. It has an unusually large margin of selectivity for corn,
this country's leading field crop.
The starting material for the production of the s-triazines is cyanuric
chloride. It is obtained industrially by trimerization of cyanogen
chloride. A generalized process flow diagram showing potential waste-
water sources is presented in Figure IVC-13. One chlorine atom is
replaced by an amine, phenol, alcohol, mercaptan, thiophenol or a
related compound under controlled reaction conditions. Hydrogen
chloride and hydrogen cyanide gases are evolved and are vented.
The gases pass through a caustic soda scrubber, and the resulting
scrubber wastewater requires treatment.
Amination of the cyanuric chloride, as depicted in Figure IVC-13
requires one to three steps in a continuous process. Solvent can
be recovered and recycled to the process. The liquid wastes are
combined with the caustic scrubber waters prior to combined treat-
ment.
W-83
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DRAFT
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IV-84
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DRAFT
Dust generated in formulation and packaging is collected in a baghouse
and then returned to process. Vapors are caustic scrubbed and combined
with other process waste streams.
In summary, wastewaters generated In the production of trlazlne herbi-
cides generally come from the following sources:
Caustic soda scrubbing and filtration of
vented HC1 and HCN gases
Aqueous wastes from the solvent recovery
unit
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control equipment used in formulation
areas
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Reactor clean-out wash waters
Ni tro Compounds
This family of organo-nitrogen pesticides include the nitro phenols
(and their salts), for example, dinoseb, and the substituted dinitro-
anilines, trifluralln and nitralin, each of which amounts to more
than one million pounds annually of active ingredients.
An example of a typical commercial process for the production of a
dinitroaniline herbicide is illustrated in Figure IVC-T+. In this
example, a chloroaromatlc is charged to a nitrator with cycle acid
and fuming nitric acid. The crude product is then cooled to settle
out spent acid, which can be recovered and recycled. Oxides of
nitrogen are vented and caustic scrubbed. The mono-nitrated product
is then charged continuously to another nitrater containing 100
percent sulfuric acid and fuming nitric acid at an elevated tempera-
ture.
The dinitro product is then cooled, filtered (the spent acid liquor
is recoverable), the cake is washed with water, and the resulting
wash water is sent to waste.
The dinitro compound is then dissolved in an appropriate solvent and
then added to the amination reactor with water and soda ash. An
amine is then reacted with the dinitro compound. The crude product
is passed through a filter press and decanter and finally vacuum dis-
tilled. The salt-water layer from the decanter is discharged for
treatment. The solvent fraction can be recycled to the reactor.
Vacuum exhausts are caustic scrubbed. Still bottoms are generally
i ncinerated.
In summary, wastewaters generated during the production of the nitro
family of pesticides are:
IV-85
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DRAFT
Aqueous wastes from the filter and de-
canting system
Distillation vacuum exhaust scrubber wastes
Caustic scrubber wastewaters
Periodic kettle cleanout wastes
Production area washdowns
Metallo-Organic Pesticides
The metallo-organic group of pesticides includes principally the
organic arsenicals and the dithiocarbamate metal complexes. A
discussion of their manufacture and wastewater sources is applic-
able to the production of other compounds in this group.
MSMA is the most widely produced of the group of organo-arsenic
herbicides (estimated production in 1972 was 24 million pounds),
that also includes the octyl- and docecyl-ammonium salts, the
disodium salt (DSMA), and cacodylic acid (dimethyl arsenic acid).
The DSMA can apparently serve as an intermediate in the manufacture
of all the others.
The process is described by the production and waste schematic flow
diagram presented in Figure IVC-15.
The first step of the process is performed in a separate, dedicated
building. The drums of arsenic tri-oxide are opened in an air-
evacuated chamber and automatically dumped into 50 percent caustic
soda. A dust collection system is employed. The drums are care-
fully washed with water; the wash water is added to the reaction
mixture; the drums are crushed and sold as scrap metal. The inter-
mediate sodium arsenite is obtained as a 25 percent solution and
is stored in large tanks prior to further reaction. In the next
step, the 25 percent sodium arsenite is treated with methyl chloride
to give the disodium salt, DSMA. DSMA can be sold as a herbicide;
however, it is more generally converted to the monosodium arsenate,
MSMA, which has more favorable application properties.
In order to obtain MSMA, the solution is partially acidified with
sulfuric acid and the resulting solution concentrated by evaporation.
As the aqueous solution is being concentrated, a mixture of sodium
sulfate and sodium chloride precipitates out, about 0.5 pound per
TOO pounds of active ingredient. These salts, a troublesome dis-
posal problem because they are contaminated with arsenic, are re-
moved by centrifugation, washed in a multi-stage, countei—current
washing cycle, and then disposed of in a State-approved landfill.
Methanol, a side product of methyl chloride hydrolysis, can be re-
covered. In addition, recovered water is recycled.
IV-87
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DRAFT
The, products are formulated on nlte as solutions (for example MB
percent (6 Ib A. I./gal) and 58 percent (8 Ib A. I. /gal)) am! M
In 1 to 30-gallon containers.
Figure IVC-16 fs a typical process and waste generation schematic
flow diagram for the production of ethylene bisdlthlocarbamate metal
complexes. Raw materials include carbon disulfide, ethylene diamine
and sodium hydroxide (50 percent). These materials are first re-
acted in stainless steel, cooled vessel. The exothermic reaction
is controlled by the feed rate. Excess carbon disulfide is distilled
out, collected and eventually recycled to the reactor. The sodium
hydroxide addition controls pH. The resulting concentrated nabam
intermediate solution is reacted (within 2k hours) with a sulfate,
and the desired metal organic complex is precipitated. The slurry
is water washed to remove sodium sulfate and then dried to less
than 1 percent water content. Process by-products include sodium
sulfate and small amounts of carbon disulfide and sodium hydroxide.
Air emissions are controlled by cyclone collectors, bag filters, and
scrubbers. The small amount of hydrogen sulfide from process vents
is caustic scrubbed before release to the atmosphere. A cyclone
collector, bag filter and scrubber are used to remove particulates
from air. The liquid waste streams contain primary salt.
In summary, wastewaters generated in the preparation of metallo-
organlcs are from the following areas:
Spillage from drum washing operations
Washwater from product purification steps
Scrub water from vent gas scrubber unit
Process wastewater
Area washdowns
Equipment cleanout wastes
Formulators and Packagers
Pesticide formulations can be classified as liquids, granules, dusts
and poweders. There are 92 major formulation plants according to this
class!fication.
The scale on which pesticides are produced covers quite a range. Un-
doubtedly, many of the small firms having only one product registration
produce only a few hundred pounds of formulated pesticides each year.
At least one plant that operated in the range of 100,000,000 pound of
formulated product per year has been Identified. The bulk of pesti-
cide formulations, however, is apparently produced by independent
formulators operating In the 20,000,000 to ^0,000,000 pounds per
year range (C-4).
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DRAFT
Formulation Processes
Most pestlcfdes are formulated In mixing equipment that Is used only
to produce pesticide formulations. The most Important unit opera-
tions Involved are dry mixing and grinding of noIMn, rllinol vlrcj
solids, and blending. Formulation systrms arc? virtually nil botch
mixing operations. Formulation units may be completely enclosed
within a building, or may be out In tha open, depending primarily
on the geographical location of the plant.
Individual formulation units are normally not highly sophisticated
systems. Rather, they are comparatively uncomplicated batch-blending
systems that are designed to meet the requirements of a given company,
location, rate of production, and available equipment. Production
units representative of the liquid and solid formulation equipment
in use are described in the following subsections.
Liquid Formulation Units: A typical liquid unit is depicted
in Figure IVC-17. Technical pesticide is usually stored in its
original shipping container in the warehouse section of the plant
until it is needed. When technical material is received in bulk,
however, it is transferred to holding tanks for storage.
Batch-mixing tanks are frequently open-top vessels with a standard
agitator. The mix tank may or may not be equipped with a heating/
cooling system. When solid technical material is to be used, a
melt tank is required before this material is added to the mix
tank. Solvents are normally stored in bulk tanks. The necessary
quantity of an appropriate solvent is either metered into the
mix tank, or determined by measuring the tank level. Necessary
blending agents (emulsifiers, synergists, etc) are added directly
from their original container to the mix tank. From the mix tank,
the formulated material is frequently pumped to a hold tank before
being put into containers for shipment. Before being packaged,
many liquid formulations must be filtered by conventional cartridge
filters or equivalent polishing filters.
Air pollution control equipment used on liquid formulation units
typically involves an exhaust system at all potential sources of
emission. Storage and holding tanks, mix tanks, and container-
filling lines are normally provided with an exhaust connection or
hood to remove any vapors. The exhaust from the system normally
discharges to a scrubber system or to the atmosphere.
Dusts and Wettable Powders: Dusts and powders are manufactured
by mixing the technical material with the appropriate inert carrier,
and grinding this mixture to obtain the correct particle size. Mix-
ing can be affected by a number of rotary or ribbon blender type
mixers.
IV-91
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DRAFT
IV-92
-------
DRAFT
Air pollution control In dust formulation units Is accomplished
primarily by baghouse systems. In some plants, however, wet
scrubbers are used. Discharges from these systems are usually
low because the scrubbing water can be largely reelrculated.
Granules: Granules are formulated in systems similar to the
mixing sections of dust plants. The active ingredient is absorbed
onto a sized, granular carrier such as clay or a botanical material
This is accomplished in various capacity mixers that generally
resemble cement mixers.
If the technical material is a liquid, it can be sprayed directly
onto the granules. Solid technical material is usually melted
or dissolved in a solvent in order to provide adequate dispersion
on the granules. The last step in the formulation process, prior
to intermediate storage before packaging, is screening to remove
fi nes.
Packaging and Storage: The last operation conducted at the
formulation plant is packaging the finished pesticide into a market-
able container. This is usually done in conventional filling and
packaging units. Frequently, the same liquid filling line is used
to fill products from several formulation units; the filling and
packaging line is simply moved from one formulation unit to another,
Packages of almost every size and type are used, including 1-, 2-,
and 5-gallon cans, 30- and 55~gal1on drums, glass bottles, bags,
cartons, and plastic jugs.
On-site storage, as a general rule, is minimized. The storage
facility is very often a building completely separate from the
actual formulation and filling operation. In almost all cases,
the storage area is at least located in a part of the building
separate from the formulation units In order to avoid contamin-
ation and other problems. Technical material, except for bulk
shipments, Is usually stored in a special section of the product
storage area.
In formulation and packaging plants, wastewaters can be potentially
generated at several sources. These sources and operations are
discussed in the following subsection.
Miscellaneous Plant Operations
For housekeeping purposes, most formulators clean out the build-
ings housing formulation units on a routine basis. Prior to wash-
down, as much dust, dirt, etc., as possible is swept and vacuumed
up. The wastewater from the building washdown is normally con-
tained within the building, and is disposed of in whatever manner
is used for other contaminated wastewater. At least one plant
had raised curbs around all floor drains and across all doorways
to keep spills within the area. Absorbent compounds and vacuum
sweepers are then used to remove the contaminants.
1V-93
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DRAFT
W.a^r-scrubblng devices are often used to control emissions to the
oh". Most of thestf devices qenerate a wastewater stream that Is
potentially contaminated with p^tlclilal materials, Although the
quantity of water In the system U high, almut ?U yalhwti |M»i
1,000 cfm, water consumption Is kept low by a recycle-sl utlqp rp-
moval system. Effluent from air pollution control equipment
should be disposed of with other contaminated wastewater. One
type of widely used air scrubber Is the toro-clone separator, In
which air Is cleaned by centrifugal force.
A few formulation plants process used pesticide drums so that they
can be sold to a drum recondltloner or reused by the formulator for
appropriate products, or simply to decontaminate the drums before
they are disposed of. Drum-washing procedures range from a single
rinse with a small volume of caustic solution or water to complete
decontamination and reconditioning processes. Wastewaters from
drum-washing operations are contained within the processing area
and treated with other processing wastewater.
Most of the larger formulation plants have some type of control
laboratory on the plant site. Wastewater from the control labora-
tories relative to the production operations, therefore, can range
from an insignificantly small, slightly contaminated stream to a
rather concentrated source of contamination. In many cases, this
stream can be discharged into the sanitary waste or municipal
treatment system. Larger, more highly contaminated streams, how-
ever, must be treated along with other contaminated wastewaters.
The major source of contaminated wastewater from pesticide formu-
lation plants is equipment cleanup. Formulation lines, including
filling equipment, must be cleaned out periodically to prevent
cross-contamination of one product with another. Occasionally,
equipment must also be cleaned out so that needed maintenance may
be performed. When possible, equipment is washed with formula
solvent. The collected solvent can be used in the next formulation
of the same product.
Liquid formulation lines are cleaned out most frequently and gener-
ally require the most water. All parts of the system that potentially
contain pesticidal ingredients must be cleaned. More than one rinsing
of process vessels and lines is required to get the system clean. As
a general rule, the smaller the capacity of the line, the more critical
cleanup becomes, in order to avoid cross contamination. Thus, large
volumes of washwater are required, relative to production quantity,
for smaller units.
Granule, as well as dust and powder lines, also require cleanup.
Liquid washouts are generally required, however, only in that portion
of the units where liquids are normally present, i.e., the active
ingredient pumping system, scales, and lines. The remainder of these
production units can normally be cleaned out by "dry washing" with
an Inert material, such as clay.
-------
DRAFT
Spills of technical material or material in process are normally
absorbed on sand or clay, and are disposed of with other potentially
toxic solid wastes in a Class-1 landfill. If the spill area is
washed down, the resultant wastewater should be disposed of with
the other contaminated wastewaters.
Natural runoff at formulating and packaging plants, If not properly
handled, can become a major factor In the operation of wastewater
systems simply because the relatively high flow and the fact that
normal plant wastewater volumes are generally extremely low. Iso-
lation of runoff from any contaminated process areas or wastewaters,
however, eliminates Its potential for becoming significantly con-
taminated with pesticides. Uncontamlnated runoff Is usually allowed
to drain naturally from the plant site.
In some plants, formulation units, filling lines, and storage areas
are located in the open. The runoff from these potentially con-
taminated areas, as a rule, cannot be assumed to be free of pol-
lutants and should not be allowed to discharge directly from the
plant site.
In summary, wastewater generated at formulator and packaging plants
are:
Formulation equipment cleanup
Spill washdown
Drum washing
Air pollution control devices
Area runoff
Basis for Assignment to Subcategories
The assignment of subcategories to pesticide plants manufacturing
active ingredient products (that is, Subcategories A through D) can
best be described by Table IIIC-^, where most pesticides are listed
by common name and basic chemical structure. Pesticides not listed
in Table IMC-^ because they are small production-volume commodities,
or because they were first manufactured after preparation of this
document, can be assigned based on their chemical structure or nature
of the active component (halogen, phosphorus, etc.) Additionally,
subcategory assignment can be made based on the production process
similarities with other pesticides in the same chemical family or
homolog group.
Plants not producing active ingredient commodities, but using the
premanufactured active ingredient for formulated or package product,
obviously fall into Subcategory E. Formulations or packaged products
in the form of water solutions or suspensions belong in Subcategory
E]. Solvent-based and dry products should be assigned to Subcategory
E2. "Dry" products, which contain small quantities of water as an
impurity or binding agent, do not qualify as water-based products.
IV-95
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DRAFT
D. Adhesive anu Sealants Industry
Discussion of the Rationale
of Categorization
In the development of effluent guidelines and standards of performance
for the Adhesive and Sealants Industry, it was necessary to determine
whether significant differences exist which could form a basis for
categorization of the industry. The following factors were considered
in determining the meaningful subcategorization:
Production Processes
The manufacturing processes for all subcategories within the industry
are basically the same. From one-man garage-type operations to large
industrial complexes, the manufacturing process consist of mixing or
compounding the various components in batch mix tanks or kettles.
Both water base and organic solvent base adhesives are produced by
mixing the raw materials in mixing tanks under ambient temperatures
or heating the tank contents with steam. The non-solvent base ad-
hevsives (thermoplastic and dry-blend adhesives) are produced in
mixing tanks also. Thermoplastic adhesives require heat while dry-
blends do not. All production processes descriked akove are batch
processes. The one exception is animal glude production, which in-
volves hot water applications for the extraction of glue from the
raw materials.
Product Types and Yields
There are hundreds of adhesive preparations on the market today, sup-
plemented by hundreds of available formulations, which are capable of
holding materials together by surface attachment. Although the basic
components of the products are generally obtainable, their specific
formulas are not always known to the public. Many adhesive compositions
are protected by patents. Adhesives can be classified in several dif-
ferent ways: by the chemical composition of their main components, by
their use in bonding various types of materials, or according to the
adherends with which they are commonly used, for example.
Solvents are needed in most adhesives to disperse the binder to a
spreadakle liquid form. In most wood- and paper-bonding adhesives
the solvent is water. In many adhesives based on synthetic resins,
rubbers, and even natural gums, a variety of organic solvents are
required to achieve the necessary solubility and to provide some
minimum percentage of base solids. However, thermoplastic adhesives
and dry blended adhesive materials are composed completely of
solids and contain neither water nor solvent-based materials.
Polymeric, thermoplastic solids are converted to mobile fluids
when subjected to sufficient amounts of heat.
-------
DRAFT
Raw Materials
In addition to the base, binder, or chief ingredient, adhesives contain
different types of chemicals, each having a specific function in the
formulation. Other ingredients used in adhesives are solvents, thinners
or diluents, catalysts, hardeners, fillers, extenders, preservatives,
fortifiers, and carriers. These ingredients involve a wide variety
of chemical commodities. The basic raw materials listed in Table IVD-1
are the major ones used for production of the four types of adhesives.
Plant Size
Operations in the Adhesive and Sealants industry range in sizes from
one-man garage-type processes to large industrial complexes producing
many kinds of adhesives. Wastewater quantities and characteristics
can vary from similar production processes in different plants due to
water use management, in-house practices, and pollution abatement
measures. However, the same pollution abatement measures can be ap-
plied to similar production processes in different sized plants.
Plant Age
In some segments of the Adhesive industry, notably animal glue, the
age of the plants and equipment is one of the most important aspects
of reducing loads of waterborne pollutants. These plants were de-
signed and built in an era when there was little concern about the
emission of water pollutants. Process, equipment and plant layout
designs did not provide a way to incorporate techniques for reducing
water flows, and segregating and preventing pollutants from entering
the water streams. The process conditions and engineering applicability
of techniques such as countercurrent washing, segregation of non-
process water streams from process waste water streams, water usage
in housekeeping, and so on, are well known; however, incorporation
of these procedures into old plants is a question of economics rather
than a question of applying methods of water conservation and reduction
in pollutant loads.
Plant Location
Plant location, and specifically local climate, will impact on perfor-
mance of certain end-of-pipe wastewater treatment systems, e.g. aerated
lagoons and activated sludge. Adhesive and sealants plants are scat-
tered all over the United States, with the major concentrations being
in the northeastern areas. According to the Adhesive Red Book, a large
number of plants are also located in California and Illinois especially
around the Chicago area (D-1).
Air Pollution Control Technology
Air pollution is not a major problem in any of the manufacturing acti-
vities in any subcategory. Odor problems are possible in the animal
glue manufacturing process and might have to be controlled. A dust
IV-97
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Table IVD-1
Principal Raw Materials Used in
Adhesive and Sealants Manufacturlnq
1. Water based solutions containing natural and synthetic materials.
Starches Polyvinyl acetate - homo-polymers,
Oextrins co-polymers
Sugars Acrylic Polymers and Co-polymers
Syrups Synthetic and natural elastomeric
Animal & Fish Glue lattices
Gelatins Polyvinyl chloride
Caseins Polyvinyl alcohol
Cellulosic Rosin and rosin derivatives
Marine Colloids Bituminous
Lignin Hydrocarbon resins
Phenolic resins
2. Solvent solution adhesives and cements (Non-water based solutions).
Synthetic and natural Solvents
elastomers Aliphatic hydrocarbons
Synthetic and natural Ketones and mixed ketones
resins Aromatic hydrocarbons
Synthetic and natural Nitrated Halogenated hydrocarbons
rosins, and modified Alcohols
rosins Esters
Plasticizers Ethers
Anti-oxidants Amines
Peptizing Agents
3. Solid and Semi-Solid and Thermoplastic Thermosetting Compounds
Synthetic polymers and Synthetics and natural waxes
copolymers Synthetics and natural oils
Synthetic natural resins Plasticizers
Synthetic natural rosins
and modified rosins
k. Dry-Blended Adhesive Materials
Silicas Assorted Cements
Clays Fillers
Plaster
IV-98
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DRAFT
Table IVD-1
(conti nued)
5. The following materials can be found, as additives, in the preceeding
groups.
A. Fillers B. Solvents and Plasticizers
Clays Aliphatic hydrocarbons
Calcium carbonates Ketones and mixed ketones
Calcium sulphates Aromatic hydrocarbons
Talcs Nitrated Halogenated hydrocarbons
Pigments, dyes, oxides Alcohols
Asbestos Esters
Sand Ethers
Fly Ash, etc. Amines
C. Surface Active Agents D. Preservatives
Surfactants Fungicides
Soaps MiIdewicides
Defoamers Bactericides
Penetrating Agents
E. Miscellaneous Components
Organic Salts
Inorganic Salts
Acids
Bases
Humectants
Metals
Thickeners - Polymeric or
cellulosic, etc.
Anti-oxidants
IV-99
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DRAFT
problem is possible In the dry-blending operations. Careful operation
involving Improved materials-handling techniques «md nwt Intoitancn tit
equipment could reduce this problem substantially. Therefore, air
pollution control technology Is not a significant factor In sub-
categorization of the Adhesive and Sealants Industry.
Sol id Waste Disposal
Quantities of solid residue generated from adhesive production are
minimal. Significant quantities of tankage are generated from
animal glue manufacturing, but this tankage Is recycled for the
production of fertilizer. The handling and final disposal of solid
waste which may be generated in the Adhesive and Sealants industry
would not impact the quantity or characteristics of the wastewater;
therefore, solid waste generation, handling, and disposal are not a
basis for subcategorization.
Wastewater Quantities, Characteristics,
Control and Treatment
The general adhesive manufacturing process has been examined for the
type of contact process water usage associated with it. Contact pro-
cess water is defined to be all water which comes in contact with
chemicals within the process and includes:
1. Water required or produced (in stoichiometric quantities) in the
chemical reation.
2. Water used as a solvent or as an aqueous medium for the reactions.
3. Water which enters the process with any of the reactants or which
is used as a diluent (including steam).
*4. Water associated with mechanical devices such as vacuum pumps or
steam-jet ejectors for drawing a vacuum on the process.
5. Water used as a quench or direct-contact coolant such as in a
barometric condenser.
6. Water used to wash, rinse, or flush adhesive mix tanks or kettles
and pipelines.
Noncontact flows not included in the raw waste load data include the
following:
1. Sanitary wastewaters.
2. Boiler and cooling tower blowdowns or once-through cooling water.
IV-100
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DRAFT
3. Chemical regenerants from boiler feed water preparation.
^4. Storm water runoff from nonprocess plant areas, e.g., tank
farms.
The manufacturing process has also been examined according to the raw
waste loads associated with the manufacture of specific adhesive formu-
lations. The water-base and solvent-base groups of adhesives have each
been subdivided into two subcategories because of differences in the
types and characteristics of wastewaters generated. The wastewater
characteristics generated for each of the subcategories do not reflect
total raw waste loads because of in-plant pollution abatement measures
practiced by the industries in all subcategories.
Summary of Considerations
The diverse range of adhesive products to be covered suggested that
separate effluent limitations guidelines need to be designated for
different segments of the industry. Therefore, a subcategorization
of the Adhesive and Sealant industry was developed. The factors
which significantly impacted on the basis for subcategorization in-
clude the following:
1. Production
2. Product Types
3. Raw Material Sources
k. Wastewater Quantities and Characteristics
For the purpose of establishing effluent limitations guidelines and
standards, the Adhesive and Sealants industry has been subca tegorized,
as shown below:
A. Water-Based Animal Glues and Gelatins
B. Other Water-Based Adhesive Solutions
C. Solvent-Based Adhesives Generating Contaminated Wastewaters
D. Solvent-Based Adhesives Generating Noncontact Cooling Waters Only
E. Thermoplastic Adhesives
F. Dry-blended Adhesives
Adhesives in each of the subcategories are manufactured by batch pro-
cesses; however, the adhesives in Subcategory A are produced by dif-
ferent processes than the adhesives in other subcategories.
Description of Subcategories
The following pages in this section contain a profile of the findings
made during field surveys of the Adhesive and Sealants industry. The
profiles contain typical process flow schematic diagrams and are grouped
according to the proposed categorization of the industry.
IV-101
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DRAFT
Subcategory A - Water Based
Animal Glues and Gelatins
The processes for the manufacture of glue and gelatin are similar, the
difference being in the highly selective raw material used for gelatin
and in the degree of hydrolysis. Following an initial washing, the raw
material is placed in vats to soak in 5~15 percent lime slurry for a
period of a month or more. After this soaking period, the limed stock
is washed, neutralized with dilute sulfuric acid and given a final wash.
The washed stock is cooked, which involves repeated hot water applica-
tions for the extraction of the glue/gelatin fractions. The initial
raw material washings, spent lime slurry from the soaking vats, acid
from the neutralization of residual lime and the associated washings,
and the cooker wastes comprise wastewater volumes from this manufacturing
process. Large volumes of wastewater with high concentrations of BOD,
COD, TOC, and suspended solids are generated during the manufacturing
process. In-plant pollution abatement measures to reduce raw waste
loads include grease recovery and recirculation of large solids in the
waste stream. Tankage is also reclaimed as a by-product for the manu-
facture of fertilizer.
Subcategory B - Water-Based Adhesive Solutions
Containing Synthetic and Natural Materials
Next to animal glue, the water-based adhesives consume the largest amounts
of water (i.e. water in product) and have the most frequent discharges of
high-strength wastes. These batch processes are carried out in jacketed
reaction kettles which are equipped with agitators and usually have pro-
visions for injecting steam directly into the materials being mixed or
circulating steam or cooling water in the jacket around the mixer.
Most water-based adhesives produced are hot blends. Raw ingredients and
water are added to process vessels, and steam is injected directly into
the materials being blended to raise their temperature. After cooking is
complete, the adhesive temperature is lowered by passing cooling water
through the jacketed process vessel. The reactants and products are
transferred from one piece of equipment to another by gravity flow or
pumping. Much of the material handling is manual, with some use of
automatic process control.
Other types of water-based adhesive preparations include jacket cooks
and cold blends. In the jacket cook preparation, steam circulating in
the process vessel jacket allows the product to be jelled and provides
the close temperature control required for the manufacture of certain
adhesives. The procedure for cold blend production entails the mixing
of raw materials and water at ambient temperature until the desired
viscosity is obtained.
IV-102
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DRAFT
In at I ol thesp proe«>*&(!"», the cooling water U usually circulated
once through the Jacket and thr*n discharged. Cleaning of the nun
continuous production equipment constitutes a major source of wa^lp
water. Depending upon the succession of products manufactured In
the process vessels, one of three principal washing procedures may
be employed. These include:
1. a hot water wash at the end of the day;
2. a hot water wash following each product mixing; and
3. a hot, dilute caustic solution wash followed by a hot water rinse
following the preparation of one or more batches of special types
of products.
In addition to above cleaning procedures, process vessels may be filled
with holding water after each working day to prevent encrustation of
adhesive residue in the vessels.
Subcategory C - Solvent Solution Adhesives
and Cements Generating Contaminated Wastewaters
There are many types of sol vent-based adhesives and variations of each
type of adhesive. Distinct types of solvent-based adhesives, each with
varying properties, may be produced by using different solvents or by
adding of other ingredients. These adhesives are produced in jacketed
reaction mixing vessels as described in Subcategory B. Raw materials
are mixed, steam heated, and cooled by noncontact cooling water. The
mixture is cooked until the proper solids concentration has been at-
tained by removing distillate from the process vessel during the cooking
process. The distillate is removed by means of a vacuum pump or steam-
jet ejector. This contaminated distillate constitutes the major source
of liquid process wastewater generated. Another source of wastewater is
caustic washwater used at some plants in the cleaning of the process
vessels. Noncontact cooling water from the process vessels is the
major water discharge from adhesives plants in this subcategory. Other
wastewaters discharged are noncontact cooling water from rubber milling
machinery and waste from boiler blowdown and from quality control lab-
oratories.
Subcategory D - Solvent Solution Adhesives
and Cements Generating Noncontact
Cool ing Water Only
Like subcategories B and C, heating and cooling in Subcategory D are
done indirectly in jacketed reaction vessels. However, water is not
required as a reactant or diluent and is not formed as a reaction pro-
duct. Process raw waste loads should approach zero, with variations
caused by spills or process upsets. Washwater loads can be eliminated
by washing with a controlled amount of solvent which can be recycled
back into the product.
IV-103
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DRAFT
Some adhesives plants in this subcategory have the capacity to manu-
facture their own solvents, such as formaldehyde which they use in ad-
hesive production. These may be continuous processes, like the Reich-
hold formaldehyde manufacturing process. Water discharges from this
process include noncontact cooling water and water from demineralizatlon
units. Contaminated wastewater and process cleaning water can be re-
cycled back into the product.
Subcategory E - Solid and Semi-Solid Hot
Melt Thermoplastic Adhesives
Thermoplastic adhesives are produced from solids which are converted to
mobile fluids when subjected to sufficient amounts of heat. These are
totally solids and contain neither water nor solvent based materials.
Because thermoplastics adhesives contain no water, hot oil circulated
through the process vessel jackets is used to provide the heat energy
needed for the manufacturing process. The hot oils are continually
heated and circulated and therefore are not a source of waste. Be-
cause water is incompatible with thermoplastic adhesives, it is normally
not used for any purpose during the manufacture and packaging of these
adhesives products. The hot-melt adhesives may be packaged while hot
to take the shape of their containers, or they may be cooled by cryogenic
nitrogen cooling systems. In some plants, thermoplastic adhesives may
be cooled by water chilling units. The chilling unit recirculates the
cooling water and has intermittent discharges. The process raw waste
loads should approach zero for this particular subcategory of the ad-
hesives industry.
Subcategory F - Dry-Blended Adhesive Materials
The dry-blending formulation process consists of a mixing tank where
raw materials are added by bulk and manual addition, and mixed to the
proper consistency. The principal product is a grout mix or under-
layment, which is a patching compound. The finished products are
usually bagged in paper sacks and hauled from the plant by truck.
There is no water use associated with this simple mixing process,
and thus, there is no wastewater discharge from the dry-blending
operation. The process raw waste loads should be zero for this sub-
category.
Process Descriptions
Animal Glue and Gelatin
Animal glue and gelatin are proteins derived from the simple hydrolysis
of collagen, which is a principal protein constituent of animal hide,
connective tissue, and bones. The formula for this reaction is only
-------
DRAFT
an indication of the complex changes that take place, proceeding from
quite variable raw materials to almost as variable products.
C102H11*9°38N31 + H2° '•« C102H151°39N31
which gives an approximate chemical composition for glue or gelatin
of:
Percent
Carbon 51.29
Hydrogen 6.39
Oxygen 24.13
Nitrogen 18.19
100.00
The formula has been confirmed within close tolerances by many investi-
gators (D-2). As a protein, animal glue is essentially composed of
polyamides of certain alph-amino acids.
The animal glue manufacturing process may be divided into three areas,
as shown in Figure IVD-1: the mill house, where stock is made amenable
to glue extraction by washing and milling; the cook house, where the
stock is cooked and the light liquor is extracted; and the drying rooms,
where the light liquor is condensed and dried to the final product.
The bulk of water-borne wastes come from the mill house and includes
lime from soaking, acids, wash water, dirt, hair, and miscellaneous
solids brought in with the stock. Three types of hide stock (raw ma-
terial) are used - green fleshings, hide stock, and chromesplit stock -
and processing is somewhat different for each. Fleshings, the substance
which joins animal skins to the carcass, are the most perishable raw
material. They are washed for approximately 12 hours, acidulated, and
then soaked before being brought to the cook house. Hides are first
desalted and cleaned by milling, then limed and soaked for 80 to 90
days in large vats. After this soaking period, they are washed free
of lime, acidulated, and sent to the cook house. Chrome splits are
first chopped up mechanically and limed. The lime is washed out,
sulfuric acid is added, and the washing begins. After the acid has
been washed out, the stock soaks in dilute acid for approximately
8 hours before neutralization is provided. After a final period of
soaking the stock is sent to the cook house.
Cook-house operations consist of loading the prepared stock into
large kettles and cooking it with steam. After about 6 hours, the
light liquor is drained off. The process is repeated three more
times, each cook yielding a lower grade of glue. The material left
IV-105
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HIDE
PREPARATION
(MILL-AND
VAT-HOUSE)
FIGURE IVD-1
ANIMAL GLUE MANUFACTURING BATCH
PROCESS FLOW CHART
CHROME STOCK
WASH
LIMING AND
VATTING
LIME OR GREEN
FLESHINGS
WASHING FREE
OF LIME
DRAFT
HIDE STOCK
WASH
I
LIMING AND
VATTING
GLUE
PRODUCTION
(COOKHOUSE OR
KETTLEHOUSE)
DRYING ROOM
CHEMICALS
WASHING
i
ACIDULATION
REWASHING j
ALKALIZATION
TO GLUE EXTRACTION
LIGHT ACID
WASH
TO GLUE EXTRACTION
WASHING
ACIDULATION
TO REMOVE
LIME AND
IMPURITIES
REWASHING
TO REMOVE
ACIDS
TO GLUE EXTRACTION
SOLIDS
DRAINING AND CONCENTRATING
BY EVAPORATION
COOK KETTLE
RESIDUAL SOLIDS
INEDIBLE ANIMAL
GREASE
[ REFINING
DRIED COMMERCIAL
TANKAGE
1ST EFFECT: VACUUM
CHEMICALS
, 2ND EFFECT: VACUUM
AIR-DRYING
IV-106
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DRAFT
after the final cook cycle is called tankage. This is further treated
to yield products such as grease, hair, and fertilizer.
Animal glue and gelatin may also be produced by using bones as the raw
materials. The procedures include grinding bones, degreasing the ma-
terial by percolating a grease solvent through it, liming and plumping,
washing, making several extractions by hot water, filtering liquors,
evaporating chilling, and drying the jelly slabs in a tunnel drier.
When dry, the slabs of glue are flaked or ground, blended, graded,
and barreled or bagged for shipment. Figure IVD-2 shows some of the
products from this process.
Variations of this process which do away with the tunnel drying and
considerable hand labor have been developed. These consist of forcing
the evaporated chilled extraction liquors containing 50 percent glue
through a wire grill or colander instead of placing slabs in a tunne!
dryer. The glue, when forced through the wire grill, is cut off into
small pellets by knifelike blades. The pellets are dried in a three-
stage drying system, using bins and rakes to stir them. in some pro-
cesses, the pellets are dropped from the co'iander or gril! into a
chilling bath, such as benzene, where they solidify. The adhering
benzene evaporates, and the pellets are dried. This pel let form of
glue is known as pearl glue. However, more than three-fourths of
the glue produced in the United States is sold in the ground form,
and the remaining fourth is sold mostly in flake form. Pellet or
pearl glue makes up only a small portion of the total glue production.
Water and Solvent Base
Adhesives Manufacture
Water-based and solvent-based adhesives are both produced by batch pro-
cesses in jacketed or non-jacketed process vessels, as shown in
Figures IVD-3 and IVD-*». The jacketed process vessels or mix tanks
have provisions for injecting steam directly into the materials being
mixed or circulating steam or cooling water in the jackets around the
mixers. Hot blends are produced by adding the raw materials and water
to process vessels, and by injecting steam directly into the materials
being blended to raise the temperature. Raw materials are added man-
ually or metered into the process vessels, depending on the quantities
required. After cooking is complete, the adhesive temperature is
lowered by passing cooling water through the jacKeted vessels. The
cooled product is then either drained to 55~gallon drums or smaller
containers for storage or shipment, or is pumped to a larger storage
vessel for eventual transfer to a tanker truck. In the jacket-cook
preparation, steam circulating in the process vessel jacket allows
the product to be jelled or provides the close temperature control
usually required for the manufacture of protein base products (animal
or casein glues). In the cold-blend preparation, neither steam nor
cooling water is required, and therefore, non-jacketed process vessels
IV-107
-------
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IV-108
-------
FIGURE IVD-3
BATCH ADHESIVE MANUFACTURING PROCESS FLOW CHART
RAW MATERIAL STORAGE TANKS
J
STEAM-
JACKETED
PROCESS
VESSEL
PACKAGING
OR
FILTERING
AND
PACKAGING
FINISHED PRODUCT
STORAGE TANKS
IV-109
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DRAFT
FIGURE IVD-4
FORMALDEHYDE-RESIN BATCH
MANUFACTURING PROCESS FLOW CHART
RAW
MATERIAL
STORAGE
TANK
WEIGH
TANK.
RAW MATERIAL
STORAGE TANKS
1
STEAM-
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PROCESS
VESSEL
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COOLING
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DISTILATE
HOLDING
TANK
DISCHARGE
FINISHED
PRODUCT
STORAGE
TANKS
IV-110
-------
DRAFT
may be used. Non-jacketed vessels can be used for cold-blend prep-
arations only, while jacketed vessels may be used for all three types
of adhesive preparations. The procedure for cold-blend production
entaPs the mixing of raw materials and water at ambient temperatures
until the desired viscosity is obtained. Again, the products are
drained or pumped to containers or large storage vessels for storage
or shipment.
Some plants have the capability to manufacture their own organic solvents
like formaldehyde, which they can use in the production of adhesives. For-
maldehyde results from the oxidation of methano], as described in the EPA
Development Document for the Organic Chemicals industry (D-3)•
Thermoplastic Adhesives Manufacture
Hot-melt thermoplastic adhesives, like other adhesives, may be prepared
in jacketed or non-jacketed process vessels. Heated oil may be circulated
through the process vessel jackets to provide the heat energy needed for
the manufacturing process. Because water is incompatible with thermo-
plastic adhesives, it is not used for an/ purpose during the manufacture
of these adhesives. Since these adhesives are totally solids ami contain
neither water nor solvent, they cannot be cooled in the process vessels.
Hot-melt adhesives may be packaged while hot and allowed to cool in the
shape of the container, or they may be cooled by cyrogenic nitrogen
cooling systems or water chilling units. Hot melt thermoplastic ad-
hesives are available in bulk, block, billet, candle, cake, chunk,
pillow, or pellet forms.
Dry-Blended Adhesive Materials Manufacture
Dry-blended adhesive production requires only a non-jacketed tank or
compartment with some type of mixing apparatus. A screw type mixer
is normally employed for this process. Water is incompatible with
the dry-blended powdered materials, and therefore, it is not used for
any purpose during the manufacture or packaging of these materials.
These materials are also completely solids, and they are packaged in
paper sacks for shipment.
Basis for Assignment to Subcategories
The subcategorization of the Adhesive and Sealants industry assigns
specific products to specific subcategories by the type of product
produced and the quantities and qualities of wastewaters generated.
The subcategories form four main groups: water-based adhesives,
solvent-based adhesives, hot-melt or thermoplastic adhesives, and
dry-blended adhesive materials. All adhesive products are produced
by batch processes. Water-based adhesives are split into two sub-
categories because of differences in batch manufacturing processes
and quantities and qualities of wastewater produced. Solvent-based
IV-111
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DRAFT
adhesives are also divided into two subcategories because of differences
in the types of wastewaters generated. In the manufacture of solvent-
based adhesives, the reaction vessel, is basically the same for both pro-
cesses, but one method produces contaminated wastewater as distillate
from the cooking process, while the other manufacturing process discharges
noncontact cooling water only. The production of thermoplastic adhesives
should have no discharge of process wastewater pollutants, and the dry-
blending formulation process is a zero discharge process.
IV-112
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DRAFT
E. Explosives Industry
Discussion of the Rationale of Categorization
In the development of effluent guidelines and standards of performance
for the Explosives industry, it was necessary to determine whether
significant differences exist which could form a basis for categori-
zation of the industry. The following factors were considered in
developing a categorization of the industry.
Raw Material, Production Processes and Product Type
The general production process for the manufacturing of explosives
involves the nitration of an organic molecule. Raw materials used
in this process are nitric acid, acting as the nitrate source, and
sulfuric or acetic acid, acting as a dehydrating agent. Examples of
the organic molecules used are glycerin, toluene, resorsinol,
hexamine and cellulose. After nitration, these organic molecules
produce the following products; nitroglycerin and dinitroglycerin;
trinitrotoluene and dinitrotoluene; trinitroresorscinol; nitromanite;
and nitrocellulose, respectively. Additional production processes
involve the formation of highly sensitive initiators with nitrogen
salts as a nitrogen source. An example of this product would be
lead azide.
A categorization based on product or process is possible. For ex-
ample, the Explosives industry could be broken down into three areas;
explosives, propellants and initiators. Explosives and propellants
are manufactured in bulk, while initiators (highly sensitive compounds
used to ignite the explosive or propellant) are manufactured in small
quantities. The differences between explosives and propellants are
only theoretical. Explosives oxidize at an extremely fast rate, giving
off large volumes of gas. Propellants burn layer after layer at a
much slower rate than explosives. These facts make products a basis
for subcategorization.
Plant Size
Plant sizes ranged from a few hundred to several thousand acres. Ex-
plosive plants are generally spread out (each area isolated from the
other) so that, if a serious accident occurs, a chain reaction will
be minimized. Plant size had no bearing on waste characteristics.
Plant Age
Most plants visited were old plants, ranging from 20 - 50 years in
age. Waste characteristics could not be correlated to age. Plant age
could affect the water segregation practices in the industry. Most
plants do not separate uncontaminated cooling waters, and load and
pack operations use large amounts of water for corrosion control.
IV-113
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DRAFT
Plant Location
Most explosives plants are evenly distributed in the eastern portions
of the United States, away from large population centers (See Map
IVE-1). They are generally located in rural areas or areas that were
rural when the plant began operations. Local climate could have an im-
pact upon treatment plant performance or design. For example, aerated
lagoon could be more cost-effective than activated sludge in warmer
climates.
Air Pollution Technology
Air pollution can be a major problem in the Explosives industry,
since the imperfect explosives are collected and burned. Air pol-
lution controls were almost non-existant at the plants visited, but
most plants had plans for controlling emissions. Wet-scrubbers are
used in three areas, demilitarization, sulfate liquor incineration
and sludge incineration.
Sol Id Waste
Solid waste, other than the imperfect explosives, is not a major
problem. The imperfect explosives are collected and in general,
burned in the open air. However, at least one plant incinerates
its waste in a starred oxygen incinerator. Disposal of the ash can
be done by landfill ing.
Military vs. Commercial Explosives
Two major sectors of the Explosives industry are the military and
the commercial sectors. Military plants can be separated into two
areas: plants manufacturing of explosives and propellents and
load and pack plants. Common military explosives are trinitrotoluene
(TNT), RDX, HMX and Composition B. These are less sensitive explo-
sives and are manufactured in bulk. In addition, the military manu-
factures sensitive explosives commonly called initiators. Examples
of such initiators are mercury fulminate, tetryl, and lead styphnate.
The commercial sector of the Explosives industry can also be divided
into plants manufacturing explosives and propellants and load and
pack plants. Examples of explosives manufactured commercially are
nitroglycerin (NG), ammonium nitrate, dynamites and gelatin dynamites.
Load and pack plants typically buy the raw materials and blend ex-
plosives on site in a recipe operation.
Since both sectors of the Explosives industry are basically involved
with the same production processes, the waste loads on a production
basis were similar. Hence, the military and commercial sectors of
the industry were considered as one in this study.
iv-m
-------
DRAFT
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-------
DRAFT
Nature of Wastes Generated
Wastewater characteristics in the Explosives industry have extreme
variability. Characteristics are presented for the industry by sub-
category in Section V. For this reason, subcategorization of the
industry was based on wastewater characterization. The industry has
been divided into three initial subcategories:
A. Manufacturing Plants
B. Load and Pack Plants
C. Specialty Plants (Manufacture of Initiators)
Description of Subcategories
Subcategory A - Manufacturing Plants
Manufacturing plants are those plants that formulate explosives from
raw materials by a specific industrial process. Such plants are
generally large, complex facilities. Products can be generally
classified as explosives or propellants. On the basis of this product
difference, the manufacturing plant category was further subdivided
into two areas: manufacture of explosives and manufacture of pro-
pel lants.
Although there is no sharp boundary between the two areas, there are
basic differences between them, including effluent characteristics.
Explosives are compounds or mixtures of compounds which, when ignited,
decompose rapidly, releasing large volumes of gases and heat. Pro-
pel lants differ in their mode of decomposition in that they only burn.
Burning in a propellant does not proceed through the material as in
an explosive but in layers parallel to the surface. Examples of ex-
plosives are nitroglycerin, dynamite, ammonium nitrate and ammonium-
nitrate-based explosives, RDX, HMX, and TNT. Propellents are generally
all nitrocellulose-based. Single, double and triple based propellants,
ball powder, high energy propellant and solventless propellants are
all examples of propellants.
The wastes associated with the manufacture of explosives are of
moderate strength, while wastes emanating from the manufacture of
propellants are in some cases orders of magnitude higher. For ex-
ample, the Ib COD/ton production for the manufacture of propellant
was 22.6 times larger than that for the manufacture of explosives.
Constantly higher values for other water quality parameters for pro-
pel lant manufacture necessitated the division of explosives manufac-
turing into these two areas. Note that, within each subcategory, the
deviation from the average value is not excessive. For example, the
average COD raw waste load for propellant manufacture was 17^.8 Ib
COD/ton production and ranged from 70.7-271; for explosive manufacture,
it was 7-73 and ranged from 1.1-20.6.
1V-116
-------
DRAFT
Subcategory B - Load and Pack Plants
Load and pack plants are those that typically buy all the necessary
ingredients from an outside supplier then mix and pack them as a
final product. Examples of this type of industry would be plants
involved in the filling of shells, plants which load and pack
ammonium nitrate and fuel oil (ANFO), nitrocarbo-nitrate (NCN) ,
and blasting caps, and water slurry plants. In the military area
munitions are filled with blends of TNT and other ingredients.
The process of filling is proceeded by melting in a kettle. These
kettles are cleaned after use along with other equipment.
Small rocket motors can be loaded with preshaped propellants that
fit snugly into the casing. Pollutant loads from this operation
generally come from the preshaping area. The wastes generated
from this subcategory are small, coming from sloppy handling, ac-
cidental spills and wash downs of floors and equipment.
The Load and Pack operation in this definition exclude demilitariza-
tion. That is the process by which the military disposes of obso-
lete and detective munitions by scouring out the shells.
Subcategory C - Specialty Plants
Specialty plants are those manufacturing "sensitive" explosives.
Examples of these explosives would be Pentaerythritol Tetranitrate
(PETN) , lead azide, lead mononitroresorcinate (LMR) , lead styphonite,
tetrl, nitromannite (HNM) and isosorbidedinitrate. The waste volume
generated from this third category is generally small but highly con-
centrated .
Process Descriptions
Subcategory A1 - Manufacture of Explosives
Ni troglycerin
Nitroglycerin (NG) is synthesized in a batch rractor by a controlled
reaction between a concentrated sulfuric acid (dehydrating agent), a
concentrated nitric acid solution (nitrate source), and a mixture of
ethylene glycol and glycerin. Figure IVE-1 shows a typical schematic
diagram for the manufacture of nitroglycerin. The reactor contains
cooling coils through which circulate a cooled brine solution. The
reactor is initially charged with the nitrating acid mixture. The
glycerin-glycol solution is then added, at a rate that maintains a
1V-117
-------
FIGURE IVE-1
TYPICAL NITROGLYCERIN PRODUCTION SCHEMATIC
DRAFT
NITRATOR
NG-ACID
MIXTURE
GRAVITY
SEPARATOR
NG
SPENT ACIDS
TO RECOVERY
OR
NEUTRALIZER
WASTE WATER.
GLYCERIN PLUS
ETHYLENE GLYCOL
NITRIC PLUS
SULFURIC ACIDS
WASH
TANK
(WATER)
NG
WATER
NEUTRALIZER
TANK
SODIUM
CARBONATE
SOLUTION
NG'
1
CATCH
TRAP
SODIUM
CARBONATE
NG
I
NEUTRALIZER
TANK
H20
FINAL
WASH
NG
IV-118
-------
DRAFT
constant temperature in the reactor. The reacted product (a mixture
of NG, ethylene glycol dinitrate, water and spent sulfuric and nitric
acid) passes into a gravity separator tank where the spent acid is
drawn from the bottom of the mixture and either discharged or sent
on for recovery of nitric and sulfuric acid. The nitroglycerin is
then dropped into a prewash tank and mixed with water. The resulting
"sour water" is removed from the top and goes to a catch tank. The
NG is drained from the catch tank and sent to neutralizer tanks. In
the neutralizer tanks the NG is emulsified with a soda (Na2C03) water
solution. After a final wash with water the NG is taken to the dyna-
mite formulation building. Ethyl acetate, a desensitizing-carrier
solvent, is sometimes mixed with the NG when it is to be stored for
a period of time.
Ammonium Nitrate
Ammonium nitrate is used primarily in granular or "prill" form in
explosives. Anhydrous ammonia and weak nitric acid are reacted to
yield concentrated (99%) ammonia nitrate. This solution is then
crystalized by steel bowls or belts. The crystals are ground or
crushed and screened. Various additives, including wax to coat the
prill, and fullers' earth for moisture control are also blended, as
show in Figure IVE-2.
Dynami tes
There are many different formulations of dynamite, although the
basic ingredients are nitroglycerin and ammonium nitrate. Ammonium
nitrate is first mixed in batches with various minor ingredients.
The most common of these are listed in Table IVE-1. This mixture
forms a "dope", to which the nitroglycerin is added. The proportions
of nitroglycerin and ammonium nitrate, and the specific minor in-
gredients and their proportions, determine the particular properties
of the dynamite. Many dynamites are formulated to customer specifi-
cation. After formulation, the dynamite is transported to a
cartridging house for packaging into waxed cardboard or plastic
tubes, and then shipped or stored in magazines.
Trinitrotoluene (TNT)
TNT is the most Important military high explosive. It exceeds all
other explosives by far, in tonnage produced per year. In its finished
form it is a lightly yellow crystal. Figure IVE-3 presents an over-
all schematic of the TNT manufacturing process, which can be divided
into two integrated sub-processes, nitration and purification.
IV-119
-------
DRAFT
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IV-120
-------
DRAFT
Table IVE-1
Common Ingredients of Dynamites
Ni troglycerin
Ammonium Ni trate
Sodium Nitrate
Sodium Chloride
Sulfur
Ni trocellulose
Phenolic Resin Beads
Bagasse
Sawdust and Wood Flour
Coal
Corrt Meal and Corn Starch
Trace Inorganic Salts
Grain and Seed Hulls and Flours
IV-121
-------
FIGURE IVE-3
TYPICAL TNT PRODUCTION SCHEMATIC
TOLUENF
ACIDS
NITRATION PROCESS
NITRATOR
3 steps
PURIFICATION,, PROCESS
SPENT
"ACID"
SPENT
ACID
RECOVERY
WATER
AND
SODA ASH WASH
SELLITEWASH
FINISHING
CRUDE TNT
PROCESS
DRYING
FLAKING
! YELLOW,
WATER
OFTEN
RECYCLED IN
NITRATION PROCESS
J _?!?_
1 WATER
HOLDING
TANK
TO
SULFURIC
ACID CONCENTRATOR
PACKAGING
FINISHED TNT
IV-122
-------
DRAFT
In the nitration process, acids (sulfuric and nitric) and toluene
are combined in the nitrator to form raw TNT in three steps. The
TNT is then sent to the purification process. In the purification
process, the crude TNT is first subjected to water and soda ash
washes which neutralize the excess acid and then to a sellite wash
which reacts preferentially with the unsymmetrical (asymmetrical)
isomers of TNT to remove them. The crude TNT is then sent to the
finishing process.
Three important pollution problems associated with the manufacture of
TNT are "red water", "Yellow water" and "Pink water" shown on Figure
IVE-3. TNT in its purification is first washed with water. TNT is
soluble in water up to 100 mg/L at ambient conditions. The exposure
to sunlight or ultraviolet light cause the formation of highly colored,
complex, substances similar to dyes. They Impact a pink or yellow
color to the water. Pink water can also occur in the LAP area by
washing down kettles and other machinery. The product stream after
the water wash is a mixture of TNT and unwanted isomers (about ^.5
percent). Removal of these isomers is through extraction by a sodium
sulfite wash (sellite). The waste effluent producted is brick red or
almost black color and is commonly called "Red Water". Currently none
of the "Red Water" in any of the military plants is being discharged.
It is either being sold for its sulfate content to paper mills or
incinerated.
Cyclotrimethylenetrinitramine (RDX) and
Cyclotetramethylene Tetran?tramine (HMX)
Two of the most powerful explosives, RDX and HMX, are manufactured
exclusively by the military sector of the industry. The processes
for manufacturing RDX and HMX are essentially identical, except for
the relative amounts of raw materials which are reacted. This can
be seen in Figure \\IE-k. In fact, some HMX is present in commercial
grade RDX and vice versa. Acetic acid, hexamine acetic acid, ammonium
nitrate, nitric acid, and acetic anhydride are reacted to form crude
RDX or HMX. The crude material is then washed, recrystal1ized to the
proper crystal size, filtered, blended with other explosives and dried.
It is then packaged for shipment. Special ingredients like lacguers
and waxes are sometimes blended and added.
Subcategory A2 - Manufacture of Propellants
The term "propellants" refers to a broad range of compounds. Pro-
pellants are classified as solvents or solventless, according to
the use of solvent ingredients in the mixing operation. Solvent
propellants are either single-base, double-base, triple-base or
high energy. All solventless propellants are referred to as rolled
powders.
IV-123
-------
FIGURE IVE-4
TYPICAL SCHEMATIC FOR RDX HMX PRODUCTION
ACETIC ACID
HEXAMINE
I
ACIDIC
ANHYDRIDE
AMMONIUM
NITRATE
I
REACTOR
NITRIC ACID
CRUDE HMX OR RDX
RECRYSTAIZATION
LOAD & PACK
I^BM „ M_J n n i F n
BLENDING
OF OTHER
EXPLOSIVES
-------
DRAFT
Differences in each kind of solvent propellant can be found in the
specific chemicals and explosive ingredients added during the mixing
operation. Most propellants use nitrocellulose as a base.
Nitrocellulose Powder
This powder (sometimes called smokeless powder), in its finished form,
is the basic material for all types of propellants.
Figure IVE-5 presents an overall schematic of the finished NC manu-
facturing process. This process is divided into two integrated sub-
processes, nitration and purification. Supplemental operations in-
clude kier boiling and bleaching and drying of cellulose fibers
prior to ni tration.
In the nitration process, acids (sulfuric and nitric) and cellulose
(in the form of loosening fibers) are combined in the nitrator to
form raw nitrocellulose (NC). The NC is dewatered and sent to the
purification process. Purification is accomplished by boiling,
beating and poaching the nitrocotton fibers in acidic and basic
aqueous solutions.
Solvent Propellants
Figure IVE-6 shows a schematic diagram for the manufacture of solvent
propellants. In the manufacture of single-base propellant, finished
NC is sent to a mix house where it is mixed with solvents (alcohol
and ether) and various other chemical ingredients. The raw pro-
pel lant is then sent to a blocker house where it is screened and
pressed into blocks. From the blocker house it is taken to the press
and cutting house where it is pressed into strands and then cut to
specified lengths. From here it proceeds to solvent recovery and
drying and finishing steps.
In the manufacture of double- and triple-base propellants, finished
NG is combined with finished NC in a pre-mix process and then sent
to the "DEHY" process for mixing with solvents and other chemicals.
In the mix house, nitroguanidine is combined with the NG-NC mixture,
solvents and other chemicals to form triple-base propellants. High
energy propellants require a separate blending process for the ad-
dition of ammonium perchlorate. Solvents used in multi-base and high-
energy propellants include acetone and alcohol.
Solventless Propellants
The manufacture process of solventless propel lants (rolled powder) is
similar to the process for solvent propellants, but without the
IV-125
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DRAFT
addition of solvents in the mix house. Propellants, after the addi-
tion of NG, air drying and temporary storage, are processed through
a blender. From the blender, the powder Is transported to a pre-
roll process and then to a final roll process. The sheets produced
from the rolling operations are cut and made into "carpet rolls" or
otherwise shaped as desired. These products then undergo final proces
sing preparation.
Subcategory B - Load and Pack Plants
Water Gels and Slurries
Water gel manufacture is a batch process involving mixing of ammonium
nitrate, sodium nitrate and other ingredients listed in Table IVE-2
to form a semisolid product. Certain water gel formulations include
proprietary supplemental components as explosive boosters. Guar gum
is added to provide binding. The product is then bagged or shipped
in bulk by truck for on-site injection. A gelling catalyst such as
chromate is injected when water gel is used in bulk on-site. Bagged
products do not incorporate the catalyst. The only wastewater sources
from the manufacture of water gel are clean-up of spills, mixing
equipment and bulk transport trucks.
Ammonium Nitrate - Fuel Oil (ANFO) Mixtures
ANFO is a mixture of ammonium nitrate prills and fuel oil, to which
a variety of other minor ingredients (listed in Table IVE-3) may be
added. ANFO is formulated by either a batch or continuous dry mixing
operation, and the only wastewater source is the clean-up of spills
and equipment. Occasionally the fuel oil (#2) is dyed before it is
mixed with ammonium nitrate to identify specific formulations. The
product is bagged in paper, plastic or burlap, depending upon its
intended use.
Nitrocarbonitrates (NCN)
These explosive products are similar in composition and manufacture
to ANFO. In addition to or in place of fuel oil, the product may
also contain mineral oil. Carbonaceous material, aluminum powder
and dinitrotoluene (DNT) are also common ingredients. The formula-
tion is a dry batch mix, with wastewater restricted to clean-up of
spills and equipment.
Additional Load and Pack Processes
Additional load and pack processes involve filling blasting caps or
shells with highly sensitive explosives. In addition, primers use
large amounts of water since they are loaded wet.
IV-128
-------
DRAFT
Table IVE-2
Ingredients of Water Gels and Slurries
Typical Ingredients Optional Ingredients
Ammonium Nitrate Fuel Oil
Sodium Nitrate Aluminum Powder
Guar Gum Smokeless Powder
Water Nitroglycerin
Gel 1 ing Agents Trinitrotoluene
Fumaric Acid Proprietary Agents
EthyJene Glycol Carbon Fuel
Ammonium Sulfamate
Table IVE-3
Ingredients of ANFO Explosives
Ammonium Nitrate Fuel Oil
Ferrophosphate Aluminum
Calcium Silicate Coal
Atticote Mineral OiIs
IV-129
-------
DRAFT
Subcategory C - Specialty Plants
Pentaerythritol Tetran it rate (PETN)
Figure IVE-7 provides a schematic of PETN production. The penta-
erythritol is nitrated with concentrated nitric acid, and PETN
separated in a centrifuge, after which the spent acid is recovered.
The PETN cake is mixed with water, and the slurry is filtered to
removal residual acid. The crystalline PETN is then dissolved in
acetone, with sodium carbonate added to further neutralize residual
acidity. After graining with water, the slurry is again filtered,
and the granular PETN taken to storage. The acetone-water filtrate
is digested with sodium hydroxide at pH 10 to destroy residual PETN,
and the acetone recovered by distillation. Still bottoms are dis-
charged as wastes.
Lead Azide
Figure IVE-8 provides a schematic of lead azide production. Sodium
aztde is mixed with water and dextrinate to form a precipitate of
lead azide, which is then separated from the wastewater. Frequently,
dissolved lead azide in the wastewater will lead to an additional
step where nitric acid, sodium nitrite and soda water are added to
precipitate any additional lead previously in solution.
Nitromannite (HNM) and Isosorbide Dinitrate
Figure IVE-9 provides a schematic of HNM or isosorbide dinitrate
production. Mannitol, a powdered solid, is fed into an agitated
mixture of sulfuric and nitric acids in a nitrator. After the
nitration phase is completed, the liquid mixture, composed essen-
tially of suspended nitromannite and spent acids, is drawn down
into a drowning vessel which contains water.
From here the suspension is drawn into and washed into a centrifuge.
The solid material is retained on a cloth filter and is washed acid
free. The spent acid and wash waters pass through a catch tank and
are neutralized.
The solid nitromannite from the centrifuge is dissolved in acetone.
A small amount of chalk is added to neutralize the solution. It is
allowed to separate into layers. The water layer is drawn off through
the same catch tank described above. The acetone layer is diluted
with water in a continuous precipitator to form a slurry which is
filtered and then washed. The acetone water mixture and the filtrate
wash waters are collected for processing through a still for acetone
recovery. Solid material collected at the catch tank is period-
ically collected and burned.
IV-130
-------
FIGURE IVE-7
TYPICAL PETN PRODUCTION AND ACETONE RECOVERY SCHEMATIC
CONC. HN03
•*•
PEIMTA-
ERYTHRITOL
CONTINUOUS
NITRATOR
ACETONE
STORAGE
STILL
STEAM
CENTRIFUGE
SLURRY
HN03 TO
RECOVERY
ACETONE
SODIUM
CARBONATE
CAUSTIC
I
PETN
DIGESTOR
FILTER
I
H2O
PETN
DISSOLVER
H20
GRAINER
FILTER
ACETONE/WATER
I
PETN
STILL
BOTTOMS
IV-131
-------
DRAFT
FIGURE IVE-8
TYPICAL LEAD AZIDE PRODUCTION SCHEMATIC
LEAD
AZIDE
PbN
6
NITRIC ACID
NaNO2
Na2CO3
WATER
PREC1PITATOR
KILL TANK
DISCHARGE
WATER
Pb (N0)
[or Pb (C
PPT LEAD CARBONATE
IV-132
-------
DRAFT
Primer Explosives
Several less freqeuntly used types of explosives form the raw materials
for primer explosives and are used primarily in small arms ammunitions.
Examples of these explosives are lead styphnite and tetracene. They
are combined, along with other chemicals, to form the primer explosives.
Tetryl (Trinitrophenylmethylnitramine) is chiefly used as a base
charge in blasting caps, as the booster explosive in high explosive
shells and as an ingredient of binary explosives. Nitric acid,
sulfuric acid, and DMA (dimethylani1ine) are the raw materials in
its manufacture. The major steps in production are nitration of DMA
to tetryl, refining the product, drying and packaging.
Basis of Assignment of Subcategories
The subcategories chosen are intended to encompass the entire
Explosive industry. They include both military and commercial ex-
plosives and propellants. Although there are some differences, both
in volume and product, between the military and commercial industries,
their waste loads are equivalent. For example, the load and pack
subcategory in the commercial explosives averaged .973 lb COD/ton
explosives handled, while the military explosives averaged .253 lb
COD/ton explosives handled, with a range of .727 to .003.
Explosive plants sometimes manufacture additional products besides
explosives. Fertilizer or raw materials for the manufacture of
explosives (such as sulfuric and nitric acid) have been excluded
from this subcategorization, since it is anticipated that they will
be covered under other effluent limitation guidelines. Considerable
effort was spent in segregating these sections to produce an unam-
biguous set of effluent limitation guidelines for the Explosives in-
dustry without contradicting any other industrial guidelines.
It is anticipated that no single plant will fall under only one of
the subcategorizations developed. Plants that fall into more than
one subcategory will have to conform to effluent guidelines for each
category. If a plant chooses to combine its wastes from two subcate-
gory areas in a treatment center, then total plant effluent limitation
guidelines should be calculated according to the method presented in
Section IX.
IV-133
-------
FIGURE IVE-9
TYPICAL NITROMAIMITE OR ISOSORBIDE DINITRATE PRODUCTION SCHEMATIC
MIXED
ACID
WASTE
WASTE
NITRATOR
DROWNING
TANKS
CENTRIFUGE
MANITOL
(ISOSORBIDE)
DISSOLVING
TANKS
CHALK
• ACETONE
SEPARATION
TANK
PRECIPITATION
TANK
r
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RECOVERY
WASTE
FILTER
HNM WASH
HNM OR
ISOSORBIDE
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-------
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IV-135
-------
DRAFT
F. Carbon Black Industry
Discussion of the Rationale of Categorization
Industry subcategories were established so as to define those sectors
of the Carbon Black industry where separate effluent limitations and
standards should apply. The distinctions between the subcategories
have been based on the wastewater generated, its quantity, character-
istics, and applicability of control and treatment. The following
factors were considered in determining whether such subcategorizations
are justified:
Manufacturing Process
The manufacturing processes used to manufacture carbon black consist
of the furnace, thermal, channel, and lamp black processes. The final
product from each of these processes is carbon black, differing only
in particle size and structure.
Furnace black is produced by the incomplete combustion of hydrocarbons.
This process is a net user of water and generally has no process contact
wastewaters.
Thermal blacks are produced by cracking of natural gas to form carbon
and hydrogen gas. The major wastewater source from this process is the
blowdown from a recirculating dehumidifier system.
Channel black is produced by impingement of under-ventilated natural
gas flames on moving, continuously scraped channels.
Lamp blacks are manufactured by the burning of petroleum or coal tar
residues in open shallow pans.
Product
The Carbon Black industry manufactures a single product. Therefore,
subcategorization by product basis was not considered.
Raw Materials
The raw materials consumed in the manufacture of carbon black consist
of hydrocarbons. Liquid hydrocarbons are used in the furnace process.
The most desirable feed stock oil for the furnace process comes from
near the bottom of the refinery barrel and is similar in many respects
to residual fuel oil. It is low in sulfur and high in aromatics and
olefins.
IV-136
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DRAFT
The raw material used In the manufacture of thermal blat.k I
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DRAFT
Air Pollution Control Equipment
In the past, air pollution control equipment had a significant Impact
upon wastewater quantities and characteristics. Cyclones and wet scrub-
bers were used to remove the carbon black from the process stream. How-
ever at present, the industry universally uses bag filters for this pur-
pose. Therefore, air pollution control equipment no longer has an
impact.
Nature of Wastes Generated
The furnace black and thermal black processes have been examined for
type of contact process water usage associated with each. Contact pro-
cess water is defined to be all water which comes in contact with chem-
icals within the process and includes:
1. Water required or produced (in stoichiometric quantities) in
a chemical reaction.
2. Water used as a solvent or as an aqueous medium for reactions.
3. Water which enters the process with any reactants or which is
used as a diluent (including steam).
k. Water used as an absorbent or as a scrubbing medium for sepa-
rating certain chemicals from the reaction mixture.
5. Water introduced as steam to strip certain chemicals from the
react ion mixture.
6. Water used to wash, remove, or separate chemicals from the
reaction mixture.
7. Water associated with mechanical devices, such as stream-jet
ejectors for drawing a vacuum on the process.
8. Water used as a quench or direct contact coolant such as in a
barometric condenser.
9. Water used to clean or purge equipment used in batch type
operations.
Noncontact flows which were not considered include:
IV-138
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DRAFT
1. Sanitary wastewoters
2. Boiler and cooling tower blowdowns or once through cooling Writer,
3. Chemical regenerants from boiler feed water preparation.
k. Stormwater runoff from non-process plant areas, e.g., tank farms.
An evaluation of the furnace process showed that the process wastewater
source is the quench water used to cool the process stream. However,
all of this water is vaporized and vented to the atmosphere as steam.
The thermal black process also uses quench water to cool the product.
However, in this process, this water is condensed through further water
sprays in the dehumidifier and is usually recycled.
Based on these considerations, the nature of the wastes generated could
form a basis for subcategorization.
Treatability of Wastewaters
The treatment technology applied throughout the Carbon Black industry
is gravity settling. Settling ponds are the primary form of gravity
settling demonstrated. However, some structural gravity settling de-
vices were found.
Summary of Considerations
For the purpose of establishing effluent limitations, guidelines and
standards the Carbon Black industry should be divided into two subcate-
gories. This subcategorization was based on distinct differences in
manufacturing processes and the nature of the wastewater generated by
each process. The two selected subcategories are:
Subcategory A - Furnace Black
Subcategory B - Thermal Black
As discussed in Section III, these two manufacturing processes are, in
fact, the only ones of significance in the United States.
Description of Subcateqories
Sub-Category A - Furnace Black Process
This subcategory consists of carbon black manufacture by the furnace
process. The process is a net user of water; water is not required as
a reactant and is not formed as a reaction product. Process raw waste
loads should approach zero, with variations caused only by intermittent
equipment washdown.
IV-139
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DRAFT
Sub-Category B - Thermal Black Process
This subcategory consists of carbon black manufacture by the thermal
process. Process water In the thermal process consists of direct
contact quench water. It appears feasible to reduce process waste
loads to nearly zero through increased recycle of contact quench water
in this subcategory.
Process Descriptions
Sub-Category A - Furnace Black Process
The furnace black process produces carbon black from the Incomplete
combustion of hydrocarbons, usually oil.
Oil is supplied to the process oil storage. The oil is usually pre-
heated in a heat exchanger prior to firing the reactors to recover
some of the waste heat from the reactor. Also, preheated air may be
supplied to the reactor for partial burning of the fuel. The particle
size of the carbon black is controlled by the air supply.
Carbon black particles are formed in refractory-1ined reactor units
designed for the incomplete burning of the fuel oil. The carbon black
particle is formed in this unit. The reactor temperature is approximat-
ely 3200 F. (Reactor design configurations are generally the major
area of difference between manufacturers and production processes.)
The combustion products (gases and carbon black) pass through the air
preheater (at approximately 1100 F.) and an oil preheater (at approxi-
mately 800 F.). In-line water sprays cool the gas carbon black stream.
The combustion products then pass through a quench tower where water
sprays further cool the stream to approximately *+00°F. All quench water
is vaporized and vented to the atmosphere.
The carbon black particles are filtered from the "quenched" gas stream
by passing through baghouses. The captured carbon black is collected
in hoppers below the baghouse and passed through a micro-pulverizer to
a pelletizer. Water is added to the "fluff" and it is agitated and
mixed to form pellets with a higher density. The "fluff" has a density
of approximately 2 pounds per cu. ft., whereas the pellets have a den-
sity of approximately 20 pounds per cu. ft.
The wet pellets are then dried in a rotary external fired direct/indirect
dryer. The indirect exhaust gases from this drier are vented to the
IV-1/tO
-------
DRAFT
atmosphere and the direct (contact) gases are exhausted to a bag
filter. The dried carbon black pellets are then conveyed to storage
and or bulk loaded. A simplified process flow diagram is shown in
Figure IVF-1. No contact process waste streams are generated by Ihi's
process. Good housekeeping and/or roofing over the process areas will
minimize stormwater runoff contamination.
Sub-Category B - Thermal Black Process
The thermal black process produces carbon black by the ':cracki ng!' oi hy-
drocarbons (i.e., separation of the carbon from the hydro-joni. The-
feed stock is generally natural gas. Thermal furnaces are built in
checkerboard brickwork patterns.
Each thermal black unit consists of two reactors. To make the operation
continuous, one reactor is automatically switched to a heating cycle
while the other is producing carbon black. The reactor refractory is
heated by separating the carbon black froir the hyorogen gas in a bag
filter and returning and burning the hydrogen gas in the reactor that
is in the "heat" cycle.
Each reactor consists of a firing zone and a cracking zone. The crack-
ing zone contains refractory brick which stores the heat required to
crack the natural gas into carbon and hydrogen. Natural gas is in-
jected into the top of the unit. The energy supplied by the heated
refractory brick cracks the natural gas to thermal b!ack and hydrogen
gas. This mixture leaves the reactor at a relatively high temperature
and at an increased standard volume and enters the quench section of
the reactor, where the temperature of the reaction products is de-
creased by adding water. Because the temperature at this point is
still much higher than the boiling point of water, the quench water is
converted into steam.
The cooled reaction products flow through a vertical cooler where ad-
ditional quench water is added for further cooling. The temperature
at this point is still excess of the boiling point of water, and there-
fore the quench water is converted to steam.
From the vertical cooler, the reaction products fnter the bag filter, where
the thermal black is separated from the hydrogen fps. The filtered
thermal black falls into a conveyor beneath the hag filter. The filtered
hydrogen gas and water vapor pass through ^ water seai (to prevent ex-
plosions) into a dehumidifier. Water sprays in the dehumidifier cool
the reformed gases below the boiling point of water, removing most of
the moisture. Water collected in the dehumidifier flows to the. hot
well where it is cooled and transferred to the cold wei "I . it is then
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DRAFT
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used to supply the sprays in the dehumidifier. The gases leaving the
dehumidifier are in excess of the amount required to heat the reactor
and the excess is vented.
The loose thermal black is collected under the bag filter in a closed
screw conveyor and conveyed to a micro-pulverizer. The micro-pulver-
izer breaks up large agglomerations of thermal black and small pieces
of refractory which may be present. The loose black from the micro-
pulverizer is pelletized to make it more suitable for handling. The
pelletized black is directly conveyed to a hopper car for shipment or
conveyed to bulk storage. The black can be loaded into hopper cars or
bagged from bulk storage.
Figure IVF-2 is a simplified flow diagram illustrating the thermal
black product. The flow diagram shows a single unit with its two re-
actors .
The major RWL's for this process are summarized below:
Waste Stream Flow TSS
kg/kkg
Dehumidifier Cooling Tower Slowdown 721 0.089
The dehumidifier cooling tower (cooling pond) blowdown is the only de-
finable wastewater discharge from the thermal process. The ways in
which the recirculated dehumidifier is handled may vary depending upon
company practice, plot location, etc. Cooling ponds are sometimes em-
ployed rather than cooling towers, depending on the same considerations.
Good housekeeping and/or a roof over the process areas will minimize
the stormwater runoff contamination.
Basis for Assignment to Subcategories
This subcategorization assigns carbon black products to a subcategory by
the manufacturing process by which they are produced. It should be
noted that only two carbon black manufacturing processes were sub-
categorized. Other processes exist, but either on a very limited scale
or not at all, in the United States.
Field sampling was not performed at the plants visited because of the
nature of the processes subcategorized. They either had no discharge,
or the discharge was intermittent,consist ing of occasional equipment
washdowns or other incidental flows.
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G. Photographic Processing Industry
Discussion of the Rationale
of Categorization
The Photographic Processing Industry serves the photographic trade
and general public in the developing of films and in photoprint ing
and enlarging. The following factors were considered to determine
whether a subcategorization of the industry and the establishment of
separate effluent limitation guidelines for different segments of the
industry were justified.
Plant Type
Photographic processing laboratories differ in the services they pro-
vide. Among the estimated 12,500 processing plants in the United
States, approximately 3,000 are amateur operations, 3,000 are "captive"
laboratories in business and industrial firms, 650 are major labs
specializing in work for professional and industrial photographers,
and the remaining plants are portrait and commercial studios (G-2).
Plant Size
Photoprocessing laboratories range in size from the small amateur oper-
ation to the major professional laboratory which may produce as much as
25,000 square feet of film and paper daily.
Plant Location
Plants are located mostly in urbanized areas throughout the country.
The three plants visited were located in Michigan, Massachusetts and
Texas.
Products
The products produced by the industry are finished color and black and
white films and prints. Most large plants process both color and black
and white materials; however, one plant visited produced only color
products.
Plant Processes
There are a wide variety of photoprocessing machines used to finish a
specific film or paper. These may be either the continuous or "rack
and tank" or "dip and dunk" operations.
IV-145
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DRAFT
Wastewater Characteristics
Because of the high production of both color and black and white
products, large volumes of wastewater are discharged during the
process. These process wastewaters include both photoprocessing
solution overflows and washwaters; together, these spent waters
are high in BOD, COD, TOC, TDS, silver and complexion cyanide.
Generally, the pollutants of significance are the same for both
color and black and white photofinishing operations with the ex-
ception of ferrocyanide which is generated during the bleaching
step in color development. Sufficient data is not available to
establish the variability in treatability of the wastewaters.
Summary of Considerations
Data was collected on both color and black and white processes
at three different plants identified as Plants 32, 33 and 3^.
These plants varied in size by production, flow rate, and geo-
graphic location, as shown in the following tabulation:
32
33
Average Daily
Production
sq ft
19,300
22,AOO
13,300
Average
Flow Rate
gpd
62,600
67,900
3^,900
Locat ion
Michigan
Massachusetts
Texas
Based on the total quantity of production, measured in square feet
of product, pollutant loadings from the color and black and white
processes compare well in order-of-magnitude. The raw waste loads
are fairly uniform throughout the industry in color and black and
white operations because of the standardization of processes within
the industry. Because of this uniformity, subcategorization of the
industry for the development of effluent limitation guidelines could
not be justified. The Photographic Processing industry is treated
as a whole for the purposes of this document, and any analyses and
regulations which are developed will be applicable to the whole
industry. Separate discussions of process types have, however,
been presented for a more thorough understanding of the industry.
Process Descriptions
Most commercial photoprocessors handle many square feet of film and
paper with automatic processing machines. The basic machines are
called the "dip and dunk" or "rack and tank" types, which consist of
a series of tanks with each tank containing photoprocessing solutions,
These solutions impart the desired effect on the film or paper in
each progressive step of development. Continuous length processors
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DRAFT
are used by most large firms, and roller transports are used
graphic arts and for hospital X-ray films.
in
During photoprocessing, many changes occur within the processing
solutions. Because of these changes, the chemicals used in photo-
processing need to be replaced, strengthened or replenished. Develop-
ing agents become oxidized and exhausted; developer activators and
preservatives wear out; anti-foggants become used up; bromides or
other halides resulting from the reduction of the silver by the
developer become more concentrated; acid short stops become neutra-
lized; and the removal of silver from the emulsion causes increased
concentrations of silver in the fixers or hypo baths. Chemicals are
added to maintain the correct chemical strength and photographic pro-
perties. When replenisher is added, its volume must be sufficient, to
cause enough overflow of the unwanted by-products. Overflows from
the processing tanks caused by the addition of replenishers and wash
water overflows are the two sources of effluent from photoprocessing.
Black and White Film
General
Black and white film consists of a foundation layer, which is coated
with a light-sensitive emulsion and an outer protective layer. Silver
halide salts, made up of positively charged silver ions and negatively
charged bromide ions are among the chemicals contained in the emulsion.
When radiant energy from light strikes the crystal, a dislodged electron
from the bromide ion is captured by a silver ion to form metallic silver.
The metallic silver clusters together on the film surface and a latent
image is formed. This image is made visible by a step in photoprocess-
ing called development. Two development processes are used in industry:
the two-step negative-positive process and the one-step reversal process.
Negative-Positive Process
The silver bromide crystals in the gelatin emulsion are bathed in a
chemical solution called a developer, which causes the visible image
to form. The developer solution contains developing agents, acti-
vators, preservatives, restrainers, anti-foggants, and water con-
ditioners. In general, the developing agents for black and white
photography are aromatic compounds ( for example, hydroquinone).
After the photographic material has been developed to the desired
amount, the developing process must be stopped. This is normally
done by treatment in an acidic solution called a short stop, which
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DRAFT
neutralizes the basic activators of the developer and conditions the
emulsion for future processing steps. Sometimes plain water is suf-
ficient for a stop bath. After stopping the action of the developer,
the unexposed and undeveloped silver must be removed from the emulsion.
This is done not only to make the image more visible and the film more
transparent, but to prevent the remaining unused silver from eventually
being reduced to metallic silver by the action of light. There are a
number of solvent fixers, including sodium thiosulfate, ammonium thio-
sulfate, and sodium thiocyanate. Following fixation, photographic ma-
terials are washed and dried. The process flow diagram for black and
white film is shown in Figure IVG-1.
FIGURE IVG-1
BLACK AND WHITE FILM PROCESSING
FILM
DEVELOPERS
DEVELOPMENT
SHORT STOP
INGREDIENTS
cunoT cTf\o
orUJrl 1 o I Or
FIXERS
FIX
WATER
WASH
DRY
WASTE
WASTE
WASTE
WASTE
WASTE
The quality of effluent wastewaters from black and white film develop-
ment are relatively uniform throughout the industry and are characterized
by high concentrations of hydroquinone in the developer waste; sulfates
and sulfites in the stop bath waste; and acetates, sulfites and silver
thiosulfate complex in the fixer waste. The major pollutants which
contribute to BOD are acetates, sulfites, and thiosulfate. Other
wastes are generated during the processing; these pollutants, however,
vary in type and concentration depending upon which photoprocessing
operation is employed.
Once the black and white negative has been fully processed and is al-
lowed to dry, the negative is converted to a positive paper print by
the black and white paper process. The process begins by directing
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DRAFT
a controlled exposure of light onto the negative, thereby creating a
positive image on the paper, which has an emulsion layer similar to
black and white film. The latent image formed is then developed, using
different chemicals from those used in the film development process.
However, effluent wastes from the paper process are similar in type
to the wastes in the film development process, although the concentra-
tions are usually higher.
Reversal Development
This is a method for obtaining a positive image on the same film used
for the original exposure. The exposed film is first fully developed
to a negative. The film is then washed and the silver image removed
by bathing in an acidic permanganate or dischromate bleach bath. A
clearing bath (for example, bisulfite) is used to remove the bleaching
agent and reaction products; the film is then given a uniform controlled
exposure of light, and is developed a second time. As an alternative to
the second exposure, a highly fogging developer or nonselective reducer
may be used for the second development. The process continues as in
other black and white processes with a wash, fix, final wash and dry.
Reversal development is often used in processing amateur and 16-mm
motion-picture film. Effluent wastes in reversal processing are
similar to other black and white film processing wastes, except that
acetate and bromide are generated during negative removal by the ad-
dition of dichromate bleach. The process flow diagram for black and
white reversal film is shown in Figure IVG-2.
FIGURE IVG-2
BLACK AND WHITE FILM PROCESSING
FILM
PRE-
HARDENING
BATH
NEUTRALI-
ZING BATH
NEGATIVE
REMOVAL
EXPOSURE
TO LIGHT
OR CHEMICAL
FOGGING
AGENT
WASH
1
WASTE
WASTE
WASTE
WASTE
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DRAFT
Color Film
General
In black and white photographic materials, the emulsion is sensitive
to wavelenghts of light up to visible blue light. However, certain
organic compounds can be included in the emulsion to extend the wave-
length sensitivity of the silver grains. The silver grains then be-
come latent images when exposed to green or red light. Color film
has three separate light-sensitive layers which record an image of
the blue light components on one layer, the green light components
on another and the red light components on a third layer.
Negative-Positive Development
Color developer agents are generally N, N-d!alkyl-p-phenlyene-diamines
whose reaction products react with a group of organic molecules called
couplers to form dyes. The oxidized components of this special category
of developers form colored dyes in the film emulsion layers with the in-
corporated color couplers. Frequently a stop bath follows the color
developer step. As in black and white film processing, metallic silver
is formed in color film upon exposure to light. However, in color film
processing the silver image which is formed with the dye is converted
back to silver halide by reactions with one of several complex iron
compounds and a halide. Either ferricyanide with sodium bromide or
ferric ammonium ethylenediamine tetracetic acid (ferric EDTA) with
ammonium bromide is commonly used. Continuing the procedure of re-
moving the unwanted silver image after the bleaching step, the film
is treated in a fixer or hypobath. The film is then washed to remove
residual processing chemicals and dried. Films of this type include
Kodacolor and Agfa CMS. The process flow diagram for color film
development is shown in Figure IVG-3-
FIGURE IVG-3
COLOR FILM PROCESSING
COLOR STOP
DEVELOPERS AGENTS
BLEACHING
AGENTS
FIXERS
WATER
FILM-
I
COLOR
DEVELOPMENT
SHORT
STOP
BLEACHING
FIX
WASH
DRY
WASTE
WASTE
WASTE
WASTE
WASTE
IV-150
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DRAFT
Effluent wastewaters from color film development are also relatively
uniform in quality and are characterized by high concentrations of
benzyl alcohol, developing agents, sulfates, sulfites, borate and
phosphate in the developer wastes; acetates, sulfates diethylene
glycol and phosphate in the short stop bath waste; ferrocyanide
or ferric EDTA in the bleach waste and acetates, sulfites and
silver thiosulfate complex in the fixing bath waste. The major
pollutants which contribute to BOD are benzyl alcohol, sulfites,
acetates, and thiosulfate. Other wastes are generated during the pro-
cessing; these pollutants, however, vary in type and concentration de-
pending upon which photoprocessing operation is employed.
Many variations of this basic process exist. Some color processes com-
bine the bleach and fixing steps to give a monobath which performs both
operations simultaneously.
After the film is dried, positive paper prints are made by exposing
light through the film onto a color photographic paper with three
color sensitive layers containing couplers. Processing of the print
is similar to that used in the negative development.
Color Reversal Development
There are two different types of color reversal films and their proces-
sing is slightly different. In one, the compounds which form the
color image are incorporated into the emulsion layers at the time of
manufacture. Most color reversal films are of this type. The second
type of color reversal film has three black and white color sensitive
layers. In this type of film the color couplers are included in the
color developer solutions.
In processing the first kind of color reversal film, after the negative
image is formed, the emulsion is washed and may be treated in a harden-
ing bath. The silver not used to form the negative image in the three
layers is made developable either by light or chemical action, and a
positive silver image is formed by the action of a color developer.
The oxidized developer combines with the couplers in the three layers
to form the three dye images. This part of the process is very similar
to the processing of color negative material, except that the image on
the film is positive. The remaining steps are much the same. Films
of this type include Ektachrome, Ansochrome, Agfachrome and Fugichrome.
The process flow diagram for color reversal development with incor-
porated couplers is shown in Figure \\IG-k.
IV-151
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DRAFT
FIGURE IVG-4
COLOR REVERSAL PROCESSING (INCORPORATED COUPLERS)
FILM-
DEVELOPMENT
-».
WASH
HARDENING
.EXPOSURE TO
LIGHT OR
CHEMICAL
FOGGING
PROCEED
WITH NORMAL
COLOR
PROCESSING
WASTE
WASTE
WASTE
The effluent wastes in the reversal process are similar to the color
process wastes except for the addition of sulfamic acid and sulfate
from the reversal bleach process and acetate and sulfate from the
hardening bath.
Color reversal film without the incorporated couplers are processed
in a manner similar to those just described up to the formation of
the negative image in all three layers. After this, all three layers
in the emulsion are treated separately. First, the red-sensitive layer
is made developable by exposure to red light through the base of the
film. The other two layers, which are not sensitive to red light, are
unaffected. The film is then treated with a color developer that con-
tains, among many other ingredients, a soluble cyan dye coupler. As
the color developer agent reduces the silver and forms an image, the
oxidized color developer in the vicinity of the developed silver grains
forms a positive cyan dye (red) image.
After washing, the film is exposed from the top with blue light, forming
a latent image in the top blue-sensitive layer. A yellow filter layer
protects the middle green-sensitive layer. A second color developer,
containing a soluble yellow coupler, produces both a silver and yellow
positive dye image in the top layer.
1V-15*
-------
DRAFT
After a wash the film is either exposed to white light or chemically
fogged and a third color developer, containing a magenta coupler,
forms the final positive silver and magenta colored dye image (green).
In the film or paper, there are three negative silver images, three
positive silver images and three colored dye images. The silver images
are removed as in the negative color process by bleaching and fixing,
washing and drying. Films of this type include Kodachrome and GAF
Moviechrome. The process flow diagram for color reversal development
with couplers in the developer is shown in Figure IVG-5-
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H. Hospitals
Discussion of the Rationale of Categorization
Prior to attempting development of effluent limitation guidelines
for the Hospitals category, the potential of need for establishing
subcategories was investigated to determine whether there were areas
of the Hospitals category where separate effluent limitations and
standards should apply. The following factors were considered in
determining whether subcategorization was justified.
Hospital Size
From inspection of historical and survey data, it was determined
that hospital size, measured in terms of number of occupied beds
served, apparently has no significant effect on the pounds of pollu-
tant per occupied bed generated by a hospital. It was also observed
that there was no apparent relationship between the volume of waste-
water generated, measured as gallons per 1,000 occupied beds, and
the sfze of the hospital in terms of number of occupied beds.
Hospital size, measured In terms of number of occupied h«Hs sf-rvnd,
was used as the basis for computing raw waste loads for hospitals.
This proved to be a more consistent yardstick for hospitals than
floor area.
Hospital Age
During the survey, both old and new hospitals were studied. Follow-
ing analysis of the survey and historical data, it was concluded
that hospital age is not a significant factor in determining the
characteristics of a hospital's wastewater.
Hospital Location
The states surveyed during the study include Pennsylvania, New York,
West Virginia, California, New Jersey, Maine, Wyoming, and Georgia.
Analysis of data from hospitals in these various geographical areas
of the United States indicated that location has no effect on the
quality or quantity of the wastewaters generated by a hospital
faci lity.
Hospital Type
Hospitals specializing in different types of services were studied
during the project. These services included general medical and
surgical, psychiatric, tuberculosis, cancer, orthopedic,and research.
It was concluded that the type of service provided by a hospital did
not form a basis for subcategorization.
IV-155
-------
DRAFT
Nature of Wastes Generated
Hospital wastewater samples were collected and analyzed during the
project, and additional data compiled by the Veterans Administration
were also obtained. Analysis of this data indicated that the waste-
water characteristics exhibited by all the hospitals studied were
fairly uniform. Therefore, it was concluded that the nature of the
wastewaters generated by hospitals is similar, and this factor does
not form a basis for subcategorization.
Treatability of Wastewaters
Although most hospitals discharge their wastewaters to municipal
sewer systems, biological on-site treatment systems are employed
in some cases. The predominating type of on-site treatment utilized
by hospitals is trickling filters, although some activated sludge
and aerated lagoon systems were also observed. The contaminant
concentrations and pollutant loadings recorded by the hospitals
studied were very similar. It was concluded that hospital waste-
waters are amenable to biological treatment and therefore wastewater
treatability characteristics did not warrant subcategorization.
Summary of Considerations
It was concluded that the wastewater characteristics of the hospitals
studied were very similar and independent of all of the above factors.
Therefore, for the purpose of establishing effluent guidelines and
standards for hospitals, additional subcategorization of this category
was not required.
Category Description
The three major areas in a hospital which generate wastewaters are
patient rooms, laundries, and cafeterias. Sanitary flows are the
primary wastes from hospital patient rooms and, obviously, the more
beds a hospital has, the more significant this flow will be. Cafe-
terias are another large contributer to the wastewaters generated
by hospitals. The cleaning of foodstuffs, preparation of meals,
washing of dishes, and floor and equipment cleaning are all activi-
ties which generate wastewaters from a cafeteria. These wastes
usually contain organic matter, in dissolved and colloidal state,
and oils and greases in varying degrees of concentration. The third
major contributor of wastewaters in a hospital is laundries. Laundry
wastes^originate from the use of soap, soda, and detergents in re-
moving grease, dirt, blood, and starch from soiled clothing and linens.
Clothes and linens are usually placed in a double cylinder with water,
soap, and other washing agents (bleaches, softeners, etc.). Rotation
of the inner perforated cylinder (the outer cylinder is stationary)
IV-156
-------
DRAFT
produces the agitation necessary to free or dissolve the impurities
from the fabrics. Following the washing cycle, the dirty wash water
is discharged to the sewer. Laundry wastes generally have a high
turbidity, alkalinity, and BOD content.
Three other areas in a hospital which discharge smaller quantities
of wastewaters are surgical rooms, laboratories, and X-ray depart-
ments. Surgical room wastewaters are primarily washwaters from
cleaning activities. Laboratory wastes generally consist of solvents,
glassware washwater, and various reagents used in the laboratory.
Research hospitals may also have animal cage washings in their laboratory
wastes. X-ray departments are an additional source of wastewaters.
These wastes consist of spent solutions of developer and fixer,
containing thiosulfates and compounds of silver. The solutions are
usually alkaline and contain various organic reducing agents. Most
hospitals recover the silver from spent X-ray film developing solutions.
All pathological wastes from surgical suites are collected and dis-
posed of in hospital pathological incinerators.
Some hospitals generate radioactive wastes from diagnostic and
therapeutic uses. lodine-131 and phosphorus-32 are the radioisotopes
which predominate in hospital radioactive wastes. Fortunately, these
possess short half-lives, and simple detention tanks can render them
inactive. The handling of radioactive waste is closely monitored by
AEC, and these wastes are not discharged to the hospital sewer system.
IV-157
-------
SECTION V
WAST': CHARACTERIZATION
Genera I
This section is intended to describe and identify the water usage and
wastewater flows in individual processes in each industry. Each industry
is presented separate!/. After developing an understanding of the funda-
mental production processes and their inter-relationships in each industry,
determination of the best method of characterizing each industry's dis-
charges will enhance the interpretation of the industry water pollution
profile, if unit raw waste loads could be developed for each production
process within an industry, then the current effluent wastewater profile
could be obtained by simply adding the components, and future profiles
by projecting the types and sizes of the Industry. However, the dctaih-d
information required For such approach is not available from any of the
industries included in the Miscellaneous Chemicals.
A common approach for discussion of waste characteristics of the various
Miscellaneous Chemicals industries could not be taken because of the basic
differences in the manufacturing processes and practices of various indus-
tries. Each industry's waste characteristics are therefore discussed
separately in the following text.
V-l
-------
DRAFT
A . Pharmaceutical Industry
Plunls in the Phjrmdi <-u t 1 ca 1 industry operate continuously throughout
the year. Their processes an: characterized largely by batch operations,
which have significant variations in pollutions! characteristics during
any typical operating period. However, some continuous-unit operations
are used in the Fermentation and Chemical Synthesis subcategor ies .
Batch operations refer to those processes that utilize reactors on a
f i 1 1 - ind-draw basis. The reactor is charged with a batch of raw materials,
and at the conclusion of the reaction, the vessel is emptied, cleaned,
and charged again with row materials. In a batch operation, the flow
of raw material into a reactor and the flow of product from the reactor
are intermittent. In a continuous operation, the flow of raw materials
into a reactor and the flow of product from the reactor are continuous.
The major sources of process wastewater in the Pharmaceutical industry
include product washings, product purification and separation, fermenta-
tion processes, concentration and drying procedures, equipment washdowns,
barometric condensers, and pump-seal waters. Wastewaters from this
industry can be characterized as having high concentrations of BOD^.
COD, TSS, and volatile organics. Wastewaters from some wet chemical
syntheses may contain heavy metals (Fe, Cu, Ni , Ag) or cyanide, and may
have ant i -bacterial constituents which can exert a toxic effect on
biological waste treatment processes. Considerations significant to
the design of joint treatment works are the highly variable BOD^ loadings
high chlorine demand, presence of surface-active agents, and trie possi-
bility of nutrient deficiency.
Subcategory A - Fermentative Product
Manufacturers
Fermentation is an important production process in the Pharmaceutical
industry. Liquid wastes from a fermentation plant can be classified
as (1) strong fermentation beers, (2) inorganic solids, such as
diatomaceous earth, which are utilized as a product or an aid to the
filtration process, (3) floor and equipment wash waters, (k) chemical
wastes such as solvent solutions used in extraction processes, and
(5) barometric condenser water resulting from solids and volatile gases
being mixed with condenser water.
The most troublesome waste of the fermentation process is spent beer.
The beer is the fermented broth from which the valuable fraction,
antibiotic or steroid, has been extracted, usually through the use
of a solvent. Spent beer contains the residual food materials such
as sugars, starches, and vegetable oils not consumed in the fermenta-
tion process. Spent beer contains a large amount of organic material,
protein, and other nutrients. Although spent beer frequently contains
high amounts of nitrogen, phosphate, and other growth factors, it is
also likely to contain salts like sodium chloride and sodium sulfate
as the result of extraction processes.
V-2
-------
r
Mi'-vhoe,, ' ,-t t r "3 \ i c-i'j i hi: iiqui I i e ' men tot i on waste ere qenerally hio-
loq'c.t'. i1- 'Miui1 . /',', i in .:,• ii, i'-i iiontation wn'.tes, even in .1 hiqhly
_ o'!..c • • ' or., , ;., ; saH ;'no^ori1v ideated by b i ol O'ii' <> I '-y, I cms ,
. t i« .' 'i 'ic' .er . pie !»•• •, i ! k e i y to up>-ei the system il these wasles
- re i i >'SL di iiit<-!; ro '-.or,1 ee > <;nis .
Or-; -, i. c n > econ lie ided i it-.. ' . K' ' c; to combine f e rnvr.tat i on wastes with
i • r |C oijirp.::s of " ''1 c-ry c' f I Licnt s . No ^urther nitrocjen, pho^pliorus
"r i r-i. (- cUMT'cnts ore qenorri' i v needed to rjrry out ,1 sati .ffic'orv
:;'t io:\_ ! i. ,' jc • • : ^i: "n 1,-3'ni na.i1 s i ti t-'T? combined w" e. 1..-•">.
i-V" -.>•-• on ;as ..-.s ...,
Tne tu'i, iiiojot' product '< on processes > ^i !i :* ., re iiMnm ,:ctur e i>'< o] i>.( i c blood ir>'Ci i or," I i on ari<1 \ -r,i. ,"• " , r'oduct i .':,"!. i he nri:n,ir\'
sources of wastewatc'' in o '! oc-d ' "ract 5 ona t i c,n pi cce ses arc spe'»t
solvents, wast' plasna ;'roc t: on , and equipment ('c.ictoi') .vcici' \vntet ;.
Genera M\ , tie spe::t solvents are recovered or incinerated with I h<
vj^jte pldsjna fraction. The [jritun1'" sources of vvasLev»ater qen • t o
c!u:"'.';tj v.icc'n*. product;.1!") a re spent rnecia hroth, spent eqr:->, «| lassv-/,". i">-
n .d ye:, sel washinos, arn bad batches ni product ; <3ii sect) and/or i " na '
l-r-cdijc . The spent media brovn and spent «. q^ wastes are iiji.cslfv
i-e : legatee], v.hiie the vjashwa ter v-jastes are sewereu. Na'.'irai t. ••. t -"act i OP
P'"odL';., i or, Includes the processing oc rulk botanical druqs and he.-bs.
", v. ir-'ma y wastewater sources include floor washinqs., resioue,1;, equip-
ment nn(j vessel vj-ash waters, and SJ.H" 1? , Wlienevc i possible, baci hatches
a •"; rec\.clee, if this is noi feasible, the had batches arc- di soho r,cd
oj i"i:o plan.: process sev/er sysr.-jrn,. Solid wastes, 3u<:h as -'pent plant tis
ar" usually lanc'Hlied or i rrai nera ted. The Caster-.'at- ", from thes"
product'on processes are characterised by low BODrr. ad COD coric.cn1 ra L i ons
a,:J p'rl ya lues between b and 8.
:2 'i' l£^ e'J3'->rV C ~ Chemical bynthesis_ _Pj_odu_c _t_i o_n
The effluent f r-Qni the chemual synthesis seqment of the Pha rmacc'ut i'~a 1
industry prol>ably is the most difficult to treat compared with the
orhcrs, because oc the many batch type operations and chenica! re>ctions,
• nc ijdinq nitrmion, ami nation, ha 1 oqena t i cri . suli'onat'on, <. ik^ c-tion.
'_• c. The processina may uenerate wastes containinq hioh COD, acids.
eases, cyanioes, refractory orqanics, suspended and dissolved solids,
ar,<' many other specific contaminants. In some instances, process
solutions and vessel washwaier may also contain residual organic ^nl-
venl's. Thus, it ii.ay be necessary to equal i/e or chemically treat a
p;~~)cess wastewater before it is acceptable for discharge to a r:in;cipal
or on-site conventional bioioqical treatment facility.
V-3
-------
DRAFT
Wastewaters from the production of fine chemicals are characterized
by hiqh BODr arid suspended solids concentrations and pH variations
from 1 to 11. Major wastewater sources from these chemical plants
include process wastes (filtrates, centiates, spent solvents, etc.),
floor and equipment wash waters, ejector condensate, spills, wet
scrubber spent waters, and pump seal water. Some wastewaters from
chemical manufacturing plants are net always compatible with biological
waste treatment, and although it is sometimes possible to acclimate
bacteria to various chemicals, there may be instances where certain
chemical wastes .5 re too concentrated or too toxic to make this feasible.
Subcategory D - Mixing/Compounding or
Formulation Production
Pharmaceutical manufacturing represents all the various operations
that are involved in producing a packaged product suitable for adminis-
tering as a finished, usable drug. The majority of pharmaceutical
.manufacturing firms are compounders, special processors, formulators
and product specialists. Their primary objective is to convert the
desired prescription to tablets, pills, lozenges, powders, capsules,
extracts, emulsions, solutions, syrups, parenterals, suspensions,
tinctures, ointments, aerosols, suppositories, and other miscellaneous
consumable forms. These operations can be described as labor intensive
and low in waste production. In rjoneral, none of thf unit operations
utilized in manufacturing a drug (i.e., mixing, drying, Iab1rtln
-------
DRAFT
2. Buik-chenvca 1 preparation areas involving aqueous solutions are
generally curbed and guttered so that spills and washdowns can
be directed to the proper treatment system.
3. Generally, pharmaceutical operations are under-roof; thus,
;.tor,i water contarnl <~;a: ' on does not present a problem.
k. Generally, pharmaceutical operations utilize scrubbing systems
on any vacuum or vent air control systems. Thus, seal and
scrubber water can be discharged to the proper drain system
for appropriate treatment.
Pharmaceutical plants generate wastewater effluents largely sanitnry
in nature and readily treatable in a biological treatment system. The
wastewaters from a pharmaceutical inanufacturlnq plant are ficn^r,i 1 ]y
characterized by low BOD and COD concentrations iint.1 by u pH from 6 to H.
Subcategory E - Research
Generally, quantities of materials being discharged by research oper-
ations are relatively small when compared with the volumes generated
by production facilities. However, the problem cannot be measured
entirely by volume of material going to the sewer. Research operations
are frequently erratic as to Quantity, quality, and time schedule when
wastewater discharging occurs. The most common problem is that of
flammable solvents, especially low-boiling-point solvents like ethyl
ether, that can cause explosions and fires. The major wastewater
sources are vessel and equipment washings, animal cage wash water,
and laboratory-seale production units. The wastewaters are generally
characterized by BODr and COD concentrations similar to domestic sewage
and by pH values between 6 and 8.
Factor;.. Affecting Wastewater Characteristics
The characteristics of the wastewater generated by a plant in the
Pharmaceutical industry depend a great deal on various in-plant pro-
duction procedures. Specifications and standards in "The Good Manu-
factur'ng Practices Regulations" place severe restrictions on the
ability to reuse and recycle process effluents because of cross-product
contamination considerations. However, some of the industrial in-plant
pollution abatement techniques which are used and can significantly
influence a plant's wastewater characteristics are discussed below:
1. Solvent recovery and recycle are normally practiced in both the
chemical synthesis and fermentation production segments of the
industry. Certain products require a high-purity solvent in
order to achieve the required extraction efficiency. This in-
creases the incentive for making the recovery process highly effi-
cient. Ammonia recovery and reuse are also employed in some cases.
V/-5
-------
DRAFT
7. Incineration is a common unit operation in the Pharmaceutical
industry. f!.">n,e solvent streams which cannot be recovered
economically nrc incinerated, incineration is also used to
dispose jt buch items as "sl.il) bottom*." from solvent, recoveiy
units, research animals, sludges, and waste materials from
biological products manufacturing.
3. Dry-vacuum-c'eaning units are used extensively in pharmaceutical
manufacturing plants. In this practice, a potential source of
significant wastewater flows is removed, in exchange for a
solids-handling problem which has significantly less adverse
environmental impact.
kt Chemical synthesis plants also employ various pretreatment opera-
tions for cyanide destruction and the removal of heavy metals
from the wastewaters generated by certain unit operations. This
practice improves the biological treatability of the plant's
wastewater and reduces the potential problem of metals
or cyanide in the plant's wastewater treatment plant final
eff1uent.
The wastewater characteristics generated for each of the five sub-
categories do not reflect total raw waste loads due to the various
in-plant pollution abatement measures practiced by the Pharmaceutical
industry. Although the study survey teams did observe some of these
in-plant measures, information provided by the individual plants con-
cerning their operation was minimal and sampling around these units
was not allowed. For these reasons, it was not possible to evaluate
the efficiencies of such units and determine their effectiveness to
reduce raw waste loads.
Raw waste loads (RWL) were computed for each of the plants visited
during the study survey period. Only contact process wastewaters
were used in calculating these loading values. The noncontact streams
which were segregated from the contact process wastewater flows and
were not included in the raw waste load figures include the following:
1. Sanitary wastewaters.
2. Boiler and cooling tower blowdowns or once-through cooling water.
V-6
-------
DRAFT
3. Chemical regenerants from boiler and process feed water preparation.
k. Storm wc'ler runoff from nonpi ocess plant areas, e.g., tank farms.
Five major parameters were c on-, i oe r<~:l:
1, BOOr Raw Waste Loading (expressed as ibs SODr/1,000 Ibs of
product)
2. COO Raw Waste Lodding (expressed as Ibs COD/1,000 Ibs of
product)
3, TSS Raw Waste Loading (expressed as Ibs TSS/1,000 Ibs of
product)
k. TOC Raw Waste Loading (expressed as Ibs TOC/1,000 Ibs of
product)
5. Contact Process Wastewater Flow Loading (expressed as gals/1,000 Ibs
of product)
The RWL figures for subcategory E are expressed as gallons or pounds
per 1,000 square feet of floor area.
Development of the Raw Waste Loads (RWL) Was accomplished
in stepwise fashion from the data obtained in the field. The RWL
data relating to individual manufacturing processes were grouped
according to the subcategory in which the processes were assigned.
The RWL figures computed for the plants surveyed are shown by sub-
i,ategory in Table VA-1. An attempt was then made to determine if
a relationship existed between the production levels of the plants
in the various subcategories and the pollutant raw waste loads
generated by these same plants. Only in subcategory A was a clear
cut relationship observed, as shown in Figures VA-1 through VA-^
For this subcategory, pollutant raw waste loads decreased as produc-
tion levels increased. Equations defining these plots were then
formulated and serve as the basis for computing average RWL values
for subcategory.
A. The equations developed are as follows:
Flow:
BODc:
COD:
TOC:
Where:
Log y = 5.9 -1.6 Log x
Log y = k.2k - 1.3 Log x
Log y = k.5"\ - 1 .2 Log x
Log y = ^.08 - 1.3 Log x
y = plant pollutant RWL (lb/1,000 Ib production)
x = plant production (1,000 Ib/day)
V-7
-------
Table VA-1
"harrcareut I ca 1 industry
Raw Waste Loads
DRAFT
r
Subcateaory
Plant
k
1
19
20
2
09
Raw Waste Load
6 - Biological and Natural
Production
kkg/day
(1000 Ib/day'l
2,21
(4 87)
3.0
(6.7)
2,4
(5.3)
3.3
(7.2)
1.43
(3.15)
0 64
(1.4)
kkL/day
(rag*)
1.02
(0.^7)
0,30
( 0 . 08 )
1,62
(0.43)
0.94
0). 25)
2.01
(0.53)
1.82
(0.48)
f low
L 'kkq product Raw
(gai/1000 !b
46", 000
(56,300)
V: . 000
(11,400)
''7?, 000
(80,700)
289,000
(34,700)
1 ,400,000
(168,000)
2,860,000
(343,000)
p rod ) BOOi;
'050
1'50
2800
1060
6160
8090
Fig. VA-2
Waste Load
COO
3310
3110
6230
4060
10,900
16.300
(kg/kkg
TSS
788
1180
1400
1940
1840
1900
Fig. VA-3
Prod)1
TOC
993
961
2110
1430
4870
4440
Fig. VA-4
Extraction Products
Subcateaory
Subcateuory
(Antibiotics
Subcateqory
Subcateaorv
12
08
17
Raw Waste Load
Cl - Chem. Synthetic Products
It
10
It
19
15
Raw Waste Load
C2 - Chem. Synthetic Products
only)
1
Raw Waste Load
0.15
(0.34)
0.06
(0.14)
1.94
(4.28)
32.9
(72.5)
31.6
(69.6)
8.8
(19.5)
11.3
(25.0)
11.1
(2U.U)
0.74
(1.64)
0.08
(0.02)
0.08
(0.02)
0.80
(0.20)
4.17
(1.10)
5.68
(1.50)
3.33
(0.88)
1.21
(0.3?)
0.11
(0.03)
0.08
(0.02)
287,000
(34,400)
992,000
(119,000)
397.000
(47,600)
126,000
(15,100)
180,000
(21,600)
374,000
(44,900)
108,000
(13.000)
10,200
(1,230)
100,000
(12,000)
131
79.1
221
144
71
261
859
180
142
302
5200
5200
211
247
350
269
284
603
1390
3/4
708
572
5540
5540
1.2
19.3
7.5
--
98
31
108
61
3.8
--
58.2
—
21.6
25.5
57
34.7
124
204
760
94
107
258
2800
2800
0 - Mlxlnq & Compounding Products
5
17
18
32
Raw Waste Load
E - Research
5
17
14
8.99
(19.80
24.8
(54.7)
5.1
(11.2)
30.4
(67.0)
Floor Area
9,200 m*
(99,000 ft2
37,500 m2
(404,000 ft2
7.900 m2
(85,000 ft2
0.08
(0.02)
0.23
(0.06)
0.04
(0.01)
1.51
(0.40)
0.08
(0.02)
0.53
(0.14)
1.10
(0.29)
8500
(1,020)
6420
(770)
5360
(643)
38,200
(4,580)
7,030
(172)
13,900
(340)
13,900
(340)
Raw Waste Load
8.0
8.2
'7.4
8.74
8.1
Raw Waste
2.15
(0.44)
1.51
(0.3D
1.61
(0.33)
1.76
(0.36)
11.4
12.5
14.0
21.0
14.7
1.14
0
2.4
2.2
--
3.9
5.10
—
6.4
5.1
Load- kg/ 1 000m2 (Ib/ 1000 sa ft)
4.00
(0.82)
3.42
(0.70)
3.46
(0.71)
3.63
(0.74)
0.15
(0.03)
0.049
(0.01)
4.88
(1.0)
__
--
0.78
(0.16)
0.58
(0.12)
1 95
(0.40)
1.10
(0.23)
kg/kkg equivalent to lbs/1000 Ibs
also Subcategory 8
V-8
-------
ORAI
FIGURE VA 1
CATEGORY A - BOD5 RAW WASTE LOAD
VS
PRODUCTION
10,000
9.000
8,000
7,000
100
5 10
PRODUCTION 1,000 LB/DAY
50
100
V-9
-------
DRAFT
FIGURE VA-2
CATEGORY A COD RAW WASTE LOAD
VS
PRODUCTION
20000
O
0
c
01
Q_
CD
_J
O
O
O
Q
O
(J
CO
Q
O
O
log y = 4.51 - 1.2 log x
5 10
PRODUCTION 1,000 LB/DAY
100
V-10
-------
FIGURE VA-3
CATEGORY A - TOG RAW WASTE LOAD
vs
PRODUCT: ON
; o noo
; ioc J—
< inn l-
tf.OOO
V.OOO
6,000
i I
,
.. - 1
t—
^
r\
r-V- -
V
\-
\
\
4
!
I
<§""]"" J
\ !
i _
i
~~!~
:
1 -i
-r1
J -i
!
i
i
i
i
j
i
L_
1
'
,
1
i r '• i
' t l
. ... p-._^__^.
i
" ~~" --.---f-- p-
--^ I'-f !
I 1 i
-^_..T t.
i i
H
1 -U_M«
100
5 10
PRODUCTION 1,000 IBS/DAY
-------
FSGURE VA-4
PHARMACEUTICAL INDUSTRY
SUBCATEGORY A
FLOW RAW WASTE LOAD
VS
PRODUCTION
800,000
\
100,000
10,000
log v = 5.9 -1.6 log x
V
\
10
100
V-12
-------
For subcategories B, C, D, and E, the RWL values were determined by
averaging the RWL values computed for the plants in each subcategory.
These RWL values are shown in Table VA-1. RWL values for TSS
were not developed for any of the subcategories; instead, allowable
TSS effluent concentrations are proposed. This approach was taken
because of the fact th^t suspended solids will be developed in any
biological wastewater treatment system, and it is, therefore, more
convenient to establish an allowable TSS effluent concentration.
The raw waste loading data for each subcategory are plotted as pollutant
raw waste loading versus contact process wastewater flow loading in
Figures VA-5 through VA-9. This type of plot is a convenient device
for illustrating the quality or strength of the wastewaters generated
by industries in each of the subcategories. Since both the loading
(ordinate) and flow (abscissa) are expressed in terms of production,
dividing the loading by the flow gives a slope which is equivalent
to concentration. Reference lines of constant concent rat ion have been
drawn diagonally across each of the plots. Relating a specific d,i1n
point to one of these lines provides a convenient estimate as to niw
waste concentrations. The individual plant RWL data for subcategory A
are plotted in Figure VA-5. Sufficient data were obtained to establish
general increasing trends between pollutant RWL and flow RWL within the
subcategory. Pollutant data points generally fall into the following
concentration ranges:
BOD5 - ^,000 to 11,000 mg/L
COD - 9,000 to 15,000 mg/L
TSS - 800 to 7,000 mg/L
TOC - 1,800 to 10,000 mg/L
The survey RWL data for the plants grouped in subcategory B are plotted
in Figure VA-6. This plot indicates that no definite relationships
appear to exist between pollutant RWL and flow RWL. The following
pollutant concentration ranges generally characterize this subcategory:
BOD5 - 100 to 600 mg/L
COD - '400 to 1 ,000 mg/L
TSS - 10 to 50 mg/L
TOC - 30 to 200 mg/L
Figure VA-7 graphically illustrates the relationships between pollutant
and flow RWL's for subcategory C. As in subcategory A, pollutant RWL's
V-13
-------
DKATI
FIGURE VA-4
CATEGORY A POLLUTANT RAW WASTE LOAD
VS
FLOW RAW WASTE LOAD
2
O
h-
o
D
Q
O
CC
CL
03
_i
O
O
O
<£
ct
<
O
Q.
O BOD
• COD
A TSS
• TOC
200
100
10,000
50,000 100,000
FLOW RWL GAL/1,000 LB PRODUCTION
500,000
1,000,000
-------
DRAFT
FIGURE VA-B
CATEGORY B POLLUTANT RAW WASTE LOAD
VS
FLOW HA-'V WASTE LOAD
50,000 100,000
FLOW RWL GAL/1,000 LB PRODUCTION
500,000
1,000,000
-------
DRAFT
2
O
H-
O
D
Q
O
CC
Q.
CO
o
O
o
FIGURE VA-6
CATEGORY C POLLUTANT RAW WASTE LOAD
VS
FLOW RAW WASTE LOAD
1,000
900
800
700
600
500 —
400
300
200
C 100
00
tr
O
CL
O BOD
• COD
ATSS
• TOC
10
1,000
5,000
10,000
50,000
100,000
FLOW RWL GAL/1,000 LB PRODUCTION
V-16
-------
DRAFT
generally increase with flow RWL. The pollutant concentration ranges
for subcatecory C genera M/ fat! Into the following ranges-
30Dr - 5QU to 5,000 mg/L
**
COD - '',,000 lo 10,000 mg/L
TSS - '.00 to 900 mg/L
TOC - 900 to 3,000 mg/L
The plant RWL data for subcategory D are plotted in Figure VA-8.
The data indicate that within this subcategory pollutant RWL's remain
fairly constant and are not dependent on flow RWL. The pollutant
data points generally fall into the following concentration ranges:
BOD5 - 250 to 2,000 mg/L
COD - 500 to 4,000 mg/L
TSS - 100 to 500 mg/L
TOC - 200 to 900 mg/L
The RWL data for subcategory E are graphically presented ?n Ffgure VA-9.
The RWL data plotted are insufficient to establish any clear-cut rela-
tionship between pollutant loading and flow loading. The individual
pollutants fall into the general concentration ranges:
BOD5 - 100 to 300 mg/L
COD - 200 to 600 mg/L
TSS - 200 to 500 mg/L
TOC - 50 to 150 mg/L
As expected, plants falling into subcategories A and C generate waste-
waters with the highest pollutant concentrations. In subcategory A,
these high levels are primarily due to spent solvents used in extrac-
tion processes and sewered fermentation beers. In subcategory C, a
myriad of organic chemicals are used as intermediaries in the production
of fine chemicals and contribute significant pollutant loads to plant
wastewater effluents.
Subcategories B, D and E are characterized by generally lower strength
wastes. This is attributable to the limited use of process water by
plants in these three subcategories. The major wastewater source for
these three subcategories is equipment washwater, and these flows are
usually small and intermittent.
V-17
-------
FIGURE VA-7
CATEGORY D POLLUTANT RAW WASTE LOAD
vs
FLOW RAW WASTE LOAD
DRAFT
2
g
h-
O
D
O
O
o:
o_
ca
_i
o
o
C3
§
cc
O
CL
500 1,000
FLOW RWL (GAL7T,OOOTB"PRODUCTION
5,000
10,000
v-ia
-------
DRAFT
FiGURE VA-8
CATEGORY E POLLUTANT RAW WASTE LOAD
VS
FLOW RATE WASTE LOAD
LU
QC
E
O
O
_J
'i_
h-
u.
O
o
o
o
m
. j
f-
D
IJ
O
OBOD
• COD
ATSS
• TOC
9.1
100
500 1,000
FLOW RWL GAL/1,000 SO FT FLOOR AREA
5,000
10,000
V-19
-------
DRAFT
Table VA-2 presents a summary of RWL parameter ranges for each sub-
category, as well as several ratios calculated to determine whether
correlations existed between any of the parameters. From this
table, it can be seen that the pollutant raw waste loadings within
each subcategory were fairly consistent, although the raw waste
loads varied considerably from subcategory to subcategory. This
would verify the subcategorization selected for the Pharmaceutical
Industry. Also, although the COO/BOD- and BOD-XTSS ratios varied
widely within each subcategory as welt as from subcategory to sub-
category, the BOD/TOC ratios within each subcategory were generally
very close and were even fairly consistent from subcategory to
subcategory.
Raw Waste Loads (RWL) for BOD,-, COD, and TOC had to be developed
graphically for subcategory A, because RWL values varied with
production levels; these are presented in Figures VA-1, 2, and 3.
The RWL values for subcategories B, C,, C , D, and E are the
arithmetic average of the raw waste loads (RWL) computed for
each of the plants in the individual subcategories; these are
summarized in Table VA-3. It was felt that this was a logical
approach since the RWL values within subcategories B, C., C~, D,
and E were fairly consistent. This approach is also more reason-
able than selecting the lowest plant RWL value as the RWL for a
sub-category, since this method would be unfair to the other
plants in that sub-category. Raw waste loads (RWL) for all
parameters analyzed in the field survey (except BODj-» COD, TSS,
and TOC) are presented in Table VA-^.
V-20
-------
DRAFT
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V-2
-------
DRAFT
G uin_ a nd Wood Chem i ca 1 s J ndus t _r y_
[he process R^l d or the six subcategories in the Gum and Wood
Chemicals Industry are presented individually in the following text.
Subsequent discuss-'ons 'n this section will relate these data to a
tcnj! '.iata base, and conip
-------
DRAFT
The historical RWL data reported for Plant No. 55 represented the
average of 31 pieces of data while the survey RWL data were developed
from 2 composite samples. The weighted average RWL reported for
Plant No. 55 was developed using the size of the respective data bases
ns the weighting factor.
>
The disparity of the RWL's was discussed with personnel from both
plants. These discussions uncovered several small differences in
operation between the two plants:
1. Plant No. 52 uses much less wash water than Plant No. 55
(106 L/kkg vs. 695 L/kkg) .
2. Plant No. 52 treats the crude gum with oxalic acid in the melter
vat and probably removes much of the insoluble oxalate salt
in the filtration process as a solid waste.
3. Plant No. 55 uses greater quantities of oxalic acid. However,
because small quantities are involved and because oxalic acid
is a highly oxidized compound, it is estimated that items 2
and 3 would account for less than 0.2 Ibs BOD/1,000 Ibs product.
Subcategory C - Wood Rosin, Turpentine
and Pi ne Oil
The manufacturing processes for wood rosin, turpentine and pine oil
illustrated in Figure IVB-3 produce no wastewater discharge from
stump washing. The process wastewater includes stripping and vacuum
jet steam condensates and unit washdown wastewaters. The pertinent.
TOC
kg/kkg
Flow
(L/kkq)
9,^70
Subcategory D -
BODc
kq/kkq
6.1*9
Tall Oil
COD
kq/kkg
12.6
Rosin, Pitch
and Fatty Acids
Figure IVB-4, which depicts the f ract i onat i on and refining of crude
tall oil, shows that the sources of process wastewater include the
acid treatment and overflow, if any, from the recirculated evaporative
cooling system. Additional process loads are contributed by process
washdowns and quality control laboratory wastes. The plant's control
of contact cooling water by means of the recirculated evaporative
cooling system is considered exemplary for the crude tall oil processing
industry. Discussions with plant operating personnel revealed that sep-
arable organics which float to the top of the reci rculation system's
V-26
-------
DRAFT
reservoir are recovered and recycled through the process and that a
net water makeup is usually required to maintain level in the reservoir.
No overflow from the reservoir was observed during the survey and it
is assumed that this is a normal operating condition. Sources of normal
makeup to the reservoir would be vacuum jet steam stripping steam con-
denSotes and rainfall on the pond. These water makeup streams would
tend to minimize dissolved solids buildup.
During the survey substantial contamination of the once-through, non-
contact condenser cooling water was observed. Based on in-plant
sampling performed during the survey, it was determined that part
of the contamination was due to leaks in the she!1-and-tube condensers
on the fractionation columns and the remainder of the contamination
due to an accidental leak or cross connection between the barometric
contact condenser and the noncontact cooling systems. In addition,
numerous sources of other noncontact cooling water and steam condensate
were observed to be discharging to a combined sewer system.
To determine the RWL for the CTO refining and fractionation units, the
plant's total wastewater was measured and sampled for a continuous
2^-hour period. Concurrent grab composite samples were taken in-plant
to determine the accidental contamination of once-through cooling
water by faulty equipment, and this loading was subtracted from the
plant's total effluent load. The flow RWL was computed to be 19,^00
L/kkg. However, based on our understanding of the process, discussions
with industry representatives and the fact that large amounts of water
were used at the plant, but unaccounted for, it was estimated that
approximately 25 percent of the 19,^00 L/kkg flow RWL represented con-
taminated wastewater. Its source, as discussed previously, was the
acid-treating unit, process washdowns and discharges from the quality
control laboratory. The remaining portion of the flow RWL was classi-
fied as noncontact waters and therefore not included. The previous
segregation of noncontact waters did not impact on the BOD, COD or
TOC RWL data but merely effected the RWL concentration.
Based on the above discussion, the pertinent RWL's for Subcategory D are:
Flow 6005 COD TOC
(L/kkq) kq/kkg kq/kkq kg/kkg
if,860 3.11 7.08 1.58
Subcategory E - Essential Oils
The steam used for each batch extraction of oil of cedarwood yields
a contaminated condensate. This represents the only process wastewater
V-27
-------
DRAFT
discharge, however, from essential oils manufacture, and its RWL's
.ire:
Flow
(l/kkg)
62,100
BOD
kq/kkq
70.8
COD
kg/kkg
86.9
TOC
kq/kkg
24.8
The impact of economy of scale on RWL's was evaluated at this facility
by comparing the above figures with loadings which were reported on
the plant's Corps of Engineers Application for Discharge to Navigable
Waters. The latter data represented wastewaters discharged by a much
larger bank of smaller retorts which had a similar production capacity.
The modernization substantially affected extraction steam quantities,
and therefore wastewater quantities, but apparently had little or no
effect on other RWL parameters. A comparison of pertinent RWL data
is provided in Table VB-1.
Table VB-1
Effect of Process Modernization
RWL's 1971 197*+
Flow (L/kkg) 169,000 62,000
BOD (kg/kkg) 24.0 70.8
COD (kg/kkg) 59.4 86.9
TSS (kg/kkg) 10.1 0.37
Subcategory F - Rosin Derivatives
Process wastewaters from the manufacture of rosin derivatives, by the
process shown in Figure IVB-6, include: water of reaction; sparge
steam, if used; and vacuum jet steam. Noncontact cooling water is used
in the kettle overhead condensers, and periodically on the kettle coils.
The once-through cooling water was segregated from process wastewaters
at both plants. Sample analyses confirm no pollutant pickup in the
noncontact cooling water streams. Subcategory F RWL's are presented below:
Flow BODr COD TOC
(L/kkg) (kg/kkg) (kg/kkg) (kg/kkg)
I' I.ml HM ',/ i')', '( . I I
Plant No. 55
Historical 214 4.59
Survey 273 5.26
Weighted Average 222 4.68
Subcategory F Average 309 4.40
Calculated as follows: TOCU. ^ . . = COD,,. . .(TOC/COD),.
Historical Historical^ uwuu 'Survey
V-28
-------
DRAFT
The historical RWL data reported for Plant No. 55 represented the
average of i8 pieces of data, while the survey RWL data were developed
from 3 composite samples. The weighted average RWL reported for
Plant No. 55 was developed using the size of the respective data bases
as the weighting factor.
General Waste Characteristics
Table VB-2 lists the BPCTCA Raw Waste Load values assigned to each
subcategory. These values include the following parameters:
1. Contact Process Wastewater Flow (liters/kkg of product)
2. BOD Raw Waste Load (kg BOD/kkg of product)
3. COD Raw Waste Load (kg COD/kkg of product)
k. TOC Raw Waste Load (kg TOC/kkg of product)
Raw waste load data for all parameters analyzed in the field survey
(except BODc;, COD and TOC) are presented in Table VB-3.
For purposes of comparison, concentrations have been calculated for
the 8005 parameter by dividing the 6005 loading by the corresponding
contact process wastewater flow. Examination of these data indicates
a variability in flows, loadings, and resulting concentrations.
It should be noted that the BODc; concentrations shown are based on
wastewaters coming directly from the process and do not necessarily
represent the waste concentrations which a treatment plant would
receive. If the plant manufactured a single product which generated
concentrated wastes, these might be diluted with contaminated cooling
wastes and steam condensate or other noncontact waters prior to bio-
logical treatment, depending upon concentrations and economic con-
siderations. In a multi-product plant, the concentrated wastewater
might be diluted with less concentrated wastes from other processes.
V-29
-------
DRAFT
OO
-3-'
in
t>
fr 8
a a
•g s
—
§
I
-------
Table VB-3
Miscellaneous Raw Waste Load Data
for the Gum and Wood Chemicals Industry
DRAFT
RWl
Flow
L/kkg
TSS
mq/L
kg/kkg
T05
mg/L
kg/kkg
Oil
mg/L
kg/kkg
Acidity
mg/L
kg/kkg
Alkalinity
mg/L
kg/kkg
TKN-N
mg/L
kg/kkg
mg/L
kg/kkg
N03-N
mg/L
kg/kkg
T-P
mg/L
kg/kkg
Color Units
mg/L
kg/kkg
S04
mg/L
kg/kkg
Phenol
mg/L
kg/kkg
Ca
mg/L
kg/kkg
Mg
mg/L
kg/kkg
Cn
mg/L
kg/kkg
Zn
mg/L
kg/kkg
Cl
mg/L
kg/kkg
Subcategory 8 -
Gum Rosin and
Turpentine
550
138
0.095
3,580
1.92
424
0.233
2,500
1.38
--
21.8
0.012
9.1
0.005
Interference
2.2
0.0012
210
245
0.134
0.65
0.00036
54.5
0.030
2.9
0.0016
0.03
14.9
0.0082
818
0.10
Subc»t»gory C -
Wood Rosin,
Turpentine and
Pine Oil
9,470
31
0.29
702
6.65
50
0.4?
11
0.10
192
1.82
4.2
0.04
0.001
__
0.4
0.0036
93
150
1.42
0.21
0.002
3.5
1.25
15.2
0.14
__
0.25
0.0024
17.7
0.17
Subcategory D -
Tail Oil Rosin,
Pitch and
Fatty Acids
4,860
Negative'
Negative'
654
3.18
325
1.58
82.
0.40
300
1.46
--
Negative'
3.23
0.0157
Negative1
40
131
0.64
20.5
0.10
3.29
0.016
Negative1
—
--
2.1
0.01
Snbc*t«gory E -
Essential
Oils
62,070
6
0.37
55
3.41
0.5
0.03
594
36.8
--
8.4
0.52
0.14
0.01
0.23
0.014
0.01
0.0006
—
1.0
0.06
0.31
0.019
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—
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Subcategory F -
Rosin
Derivatives
319
51
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0.055
Background TSS contributions exceeded the net Increase across the process, resulting in a negative TSS - RWL.
V-31
-------
DRAFT
Pesticides and Agricultural Chemicals Industry
The process RWL data for the five subcategories in the Pesticides and
Agricultural Chemicals industry are presented individually in the
following text. Subsequent discussions in this section will relate
these data to a total data base, and compare waste loadings and con-
centrations between subcategories.
Subcategory A - Halogenated Organic Pesticides
In the manufacturing processes for Halogenated Organic pesticides il-
lustrated in Figures IVC-1, IVC-2, IVC-3, \\IC-k, IVC-5, IVC-6,
the principal sources of high organic wastes are decanting, distil-
lation and stripping operations. In addition spillage, washdowns and
run-off can also be significant sources of high organic and solids
loadings. A summary of pertinent wastewater characteristics for
wastes from processing units utilized in the manufacture of halo-
genated organic pesticides is contained in Table VC-1.
Subcategory B - Organo-Phosphorus Pesticides
Sources of wastewater from the manufacture of organo-phosphorus pes-
ticides by the processes shown in Figures IVC-7 and IVC-8 include:
decanter units, distillation towers, overhead collectors, solvent
strippers, caustic scrubbers, contact cooling, hydrolyzing, product
and equipment washing. Table VC-2 contains a summary of wastewater
characteristics for wastes from processing units commonly used in
the production of organo-phosphorus pesticides.
Subcategory C - Organo-Nitrogen Pesticides
The principal sources of wastewater in the manufacturing processes
for organo-nitrogen pesticides, illustrated in Figures IVC-9 through
IVC-1^ are: decanting operations, extractor/precipitator units,
scrubbing operations, solvent stripping, product purification, vessel
rinsing, spillage and equipment washdown. A summary of the waste-
water characteristics associated with these unit operations is con-
tained in Table VC-3.
Subcateqory D - Metallo-Organic Pesticides
In the manufacturing processes for metallo-organic pesticides illus-
trated in Figures IVC-15 and IVC-16, the principal sources of waste-
water are: by-product stripping, product washing, caustic scrubbing,
tank and reactor clean-out and area washdowns. The wastewater
characteristics associated with these operations are summarized in
Table VC-4.
V-32
-------
DRAFT
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V-36
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DRAFT
Subcategory E - Formujators and Packagers
Washing and clearing operations are the principal sources of waste-
water in formulating and packaging operations illustrated in Figure
IVC-17. Air pollution control devices can also be a significant
source of suspended and dissolved solids. Table VC-5 summarizes
the wastewater characteristics for formulation and packaging opera-
tions.
Factors Affecting Wastewater Characteristics
The characteristics of the wastewater generated by a plant in the
Pesticides and Agricultural Chemicals industry depend a great deal
on various in-plant production procedures. In addition, general
housekeeping reuse and recycle practices affect both the quantity
and quality of wastewater generated by a particular plant. Some
of the factors that can significantly influence a plant's wastewater
characteristics are discussed below:
1. The large fluctuations in flow rates between plants are
generally attributable to the use of scrubbers for air
pollution control and water management techniques employed
in housekeeping and maintenance practices. In addition,
fluctuations in flow within individual plants are common,
due to the batch type of processing employed throughout
the industry. Fluctuations In flow rate are considerable
within the formulation segment of the industry. This is
attributable to the different types of formulations. Dry-
based formulations produce little discharge, while solvent-
based and water-based formulations can contribute signifi-
cant flows.
2. The type of scrubber used for air pollution control can
also affect the wastewater characteristics. Compared to
water scrubbers, caustic soda scrubbers contribute less
flow, but the wastewater typically has high pH and
dissolved-solids levels and low organic content.
3. The use of barometric condensers and vacuum sources can
have a significant effect on the quantity and quality of
wastewater generated within a particular plant, depending
on the nature of the materials entering the discharge
water stream.
k. In subcategories B, C and D, the BOD5 loadings are extremely
low compared to COD values. This can be attributed to the
toxic nature of some of the waste streams.
V-37
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V-38
-------
DRAFT
5. Other sources of wastewater not easily defined are rinse
waters from cleaning of solvent strippers, reactors and
tanks. The quantity of water used for such ch«anincj oper-
ations is highly variable; consequently, the concentration
of soluble organics and by-product salts varied considerably.
General area washdowns are also a source of wastewater,
although generally low in organic content; other parameters,
such as pH, oil, suspended solids and salt content, are
highly variable. Flows for cleanout and washdown operations
are variable and intermittent.
6. Another undefinable quantity is spillage of intermediates
and final products. This type of loss contributes high
organics and dissolved solids.
Raw Waste Loads
Raw Waste Loads (RWL) were computed for each of the plants visited
during the study survey period. Only contact process wastewaters
were used in calculating these loading values. Development of the
Raw Waste Loads (RWL) was accomplished in a stepwise fashion from the
data obtained in the field. The RWL data relating to individual manu-
facturing processes were grouped according to the subcategory to which
the processes were assigned. The RWL values computed for the plants
surveyed are shown by subcategory in Tables VC-6 through VC-10. The RW-
L values were determined by averaging the RWL values computed for the
plants in each subcategory. These RWL values are also shown in Tables
VC-6 through VC-10. RWL values for TSS were not developed for any of
the subcategories. Instead, allowable TSS effluent concentrations are
proposed. This approach was taken because of the fact that suspended
solids will be developed in any biological wastewater treatment system,
and it is, therefore, more convenient to establish an allowable TSS
effluent concentration. Due to the toxic nature of pesticide wastes,
BOD3 raw waste loads have little meaning; consequently, characterization
of pesticide wastes by BOD5 should be avoided. Table VC-11 presents a
summary of RWL parameter ranges for each subcategory.
The raw waste load data presented in Tables VC-6 through VC-10
include wastes handled at incineration, deep-well, an-d disposal
contractor facilities. As such, they are not representative of the
wastewaters normally treated in wastewater treatment facilities,
particularly biological treatment systems.
V-39
-------
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-------
DRAFT
TABLF VC-7
rtaw Waste Loads for Organo-Phosphorus Pesticide Plants
(Subcategory B)
Plant Product Fiow' COD BOD, TOC TSS OM
L/kkgTqal/1 ,000 Its?)' kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L kg/kkg
61
63
61*
65
68
A
B
C
D
E
F
C,
H
1
J
JJ
K
L
M
N
0
P
107,000
8,250
60,500
55,700
1 1 , 900
62,100
7,510
54,400
49,600
42,900
42,900
?,780
12,800
31 ,400
5,340
1 ,490
21 ,100
(12.900)
< 989)
1 7,200)
( 6,680)
( 1,430)
( 7,440)
( 900)
! 6 530)
( 5,950)
( 5,140)
' 5,150)
( 333)
( 1,530)
( 3.760)
( 640)
( 179)
( 2,530)
333
332
192
499
46
192
3' 5
570
108
155
177
45
79
_
-
-
-
3,uo
40,200
3,150
8,910
3,850
3,100
42,000
3,150
2,160
3,600
4,100
19,700
6,100
_
-
-
-
73 1,700
1.5 540
72 R 69,800 ( 8,380)
68
62"
611*-5
64^
Raw Waste
V
S
T
U
Load6
14,800
20,000
46,000
2,780
33,200
( 1,780)
( 2,400)
( 5,510)
( 333)
( 4,000)
5
312
195
JL
188
335
15,600
4,240
12,500
2
27
44
21
135
1,350
955
1.6
77
A3
,9
43
108
3,850
934
6.830
1 .1
1 . 1
0.7
O.I
0.8
73
55
15
li
0.15
0.4
2.7
20
5.8
10
20
59
7,200
Notes
Dash (-): Data not reported.
kg/kkg product is equivalent to lbs/1,000 Ibs. product.
plant data unless otherwise noted
11 process wastewaters, including area washdowns and contaminated run-off.
Data obtained during plant visits via sample collection and analyses.
Includes low quantities of employee showers and washing wastewaters.
Raw waste load values were obtained by giving historical and plant visit data equal weighting. Since historical
data points are generally based on a limited number of individual data points, this is a reasonable method of
data treatment. In the case of duplicated data (i.e., historical as well as plant visit data for the same product
and plant) only the historical data was used to determine the RWL.
1 ncIudes a
4
5
6
-------
lable VC-7 Continued
Plant Product
Flow
IDS
T-P
Plwnol
Chloride
kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L kg/kkg (ng/T kg/kkg mg/L
NHj-N
TKN
61
63
65
A
B
C
0
f
b
H
1
J
JJ
K
L
M
N
0
P
107
8
60
55
II
62
7
54
49
42
42
2
12
31
5
1
21
,000
,250
,500
,700
,900
,100
,510
,400
,600
,900
,900
,780
,800
,400
,340
,490
,100
(12
!
I 7
i 6
I 1
( 1
(
( 6
( r>
( 5
( 5
(
1 1
( 3
(
(
( 2
,900)
989)
,230)
,680)
,430)
,440)
900)
,530)
,950)
,140)
,150)
333)
,530)
,760)
640)
179)
,530)
763
1 ,750
565
2,790
702
1 ,030
941
1 ,040
_
-
814
240
-
_
-
-
-
7,130
210,000
9,420
49,800
58,500
16,600
125,000
19,250
_
-
19,000
86,000
-
.
-
-
-
5.5
57.0
18.6
43.0
14.0
7.2
32.0
1 05 . 0
_
-
9
53
-
_
-
-
-
51
6,900
304
770
1 ,170
115
4,260
1,930
_
-
210
19,000
-
_
-
-
-
242
1,220
394
1 ,830
527
357
563
396
17 340
11 255
0.01 0.3 296
-
-
_
-
-
-
2,260
147,000
6,500
33,000
44,000
5,700
75,000
700
_
_
6,900
-
-
.
-
_
-
_
_
_
295 5,300
242 20,200
_
_
122 2,200
.
_
-
-
-
.
-
_
-
68
72
62^
6."
64'4
Raw Waste Load
14,800 ( 1,780)
69,800 ( 8,380)
20,000 ( 2,400)
46,000 ( 5,510)
2.780 ( 333)
33,200 4,000
620 41,500 0.03 2
1,080 54,000 5 250
682 14,800 28 610
222 79,000 6 2.150
0.01
0.6
0.3
880
24
0.01 0.5 1,480 74,000 17
0.5 II - - 29
0.1 36 _
4.1 700 88.2
2 0.2
850 3 13
630 434 9,400
Notes.
Dash (-): Data not available
kq/kkg product is equivalent to lbs/1,000 1bs product.
Historical plant data unless otherwise noted.
n, a i nphosme thy I, metham i dophos, fensulfothion,
athion, me-parathion or Niran 6-3. K is a compc
Includes all process wastewaters, including area in equipment washdowns and contaminated run-off.
Includes low quantities of employee shower and washing wastewaters.
Raw waste load values were obtained by giving historical and plant visit data equal weighting. Since historical
data points are generally based on a limited number of individual data points, this is a reasonable method of
data treatment. In the case of duplicated data (i.e., historical as well as plant visit data for the same product
and plant) only the historical data was used to determine the RWL.
V-42
-------
Table VC-8
Raw Waste Loads
Organo-Nltrogen Pesticide Plants
(Subcategory C)
DRAFT
1
Plant
61
62
64
72
67
62
67
Literature
oduc t "
Flow3
L/kkg(gai
A
B
C
0
E
K
L
M
N
0
P
Q
R
s
T
U
V
f
E
G
H
J
•/aste Load
85
51
45
47
10
5
35
50
10
4
20
51
33
68
43
116
104
<»5
10
97
90
50
49
,100
,600
,000
,500
,000
,590
.900
,200
,100
,170
,000
,700
,400
,800
,800
,000
,000
,000
,000
,200
,400
,000
,000
(10
( 5
( 5
( 5
( 1
(
( *
( 6
( I
(
( 2
( 6
( <*
( 8
( 5
(14
(12
( 5
( 1
(11
(10
( &
( 5
COD
1,000 Ibs) kg/kkg mg/L
,200)
,180)
,400)
,700)
,200)
670)
,300)
,000)
,210)
500)
,400)
,200)
,000)
,250)
,250)
,000)
,500)
,400)
,200)
,600)
,800)
,000)
,800)
403
77
_
-
8
-
217
195
143
30
53
40
60
116
665
925
1 .560
630
81
222
206
500
323
4
1
6
3
14
7
2
1
1
15
8
15
14
8
2
2
IP.
5
,740
.480
_
-
800
-
,030
,900
,300
,150
,650
770
,800
,680
,100
,000
,000
,000
,100
,300
,300
.000
,800
BOD, TOC TSS Oil
kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L kg/kkg mg/L
_
-
37
40
3
-
_,
.
.
-
-
18
25
&
500
650
200
108
25
112
105
Low
220
- - .
- - - - -
820 - - - - -
840 - - - - -
300 - - - - - -
-
- - - _ .
- - - - _
- - - .
- - .
-
350 - - - - - -
750 - -
495 - - - - -
1 1/tOO - - - - - -
5£00 - - - - -
1 1500 - - - - - -
2,400 234 5,200 83 1,845 0.02 0.5
2,500 42 4,200 2 200 0.09 9
1,155 41 420 1 10
1,160 38 420 1 11 7.3 81
Low - -
3,020 89 2,560 22 517 2.5 30
3
Dash (-): Data not reported
kg/kkg product is equivalent to lbs/1,000 Ibs product
I
Historical plant data unless otherwise noted.
Product identification: A,B-metrlbuzin or benzazlmlde; C,D-atrazine, slmazlne, propazine, ametryne, prometryne,
•slnstryne, Sumitol, terbatryne, prometone, or cyanazlne; E-dlnoseb; F-atrazine; G,H-alachlor or propachior;
J-typlcal organo-nltrogen compound; k-butylate, EPTC, vernolate, cycloate, mollnate, or pebulate; L,M,N,0,P-alachlor,
CDAA, propachior, butachlor; Q,R,S,T,U,V-durlon, dromacll, thiram, methomyl, Iinuron, or terbacil.
Includes all process wastewaters including area and equipment washdowns and contaminated run-off.
Data obtained during plant visits via sample collection and analyses.
5
'The Pesticide Manufacturing Industry - Current Waste Treatment and Disposal Practices": U.S. Environmental
Protection Agency, Water Pollution Control Research Series, January 1972.
6
Raw waste load values were obtained by giving historical and plant visit data equal weighting. Since historical
data points are generally based on a limited number of individual data points, this is a reasonable method of data
treatment. In the case of duplicated data (I.e. historical as well as plant visit data for the same product and
plant) only the historical data was used to determine the RWL.
V-43
-------
Table VC-8
(cont Inued)
DRAFT
.Plant
61
62
64
67
71
72
Product
L
M
N
0
P
a
R
S
T
U
V
Literature J
62
67"
L/kkg
85
51
45
10
35
50
10
4
20
51
33
68
117
104
5
50
45
10
,100
,600
,000
,500
,000
,900
,200
,100
,170
,000
,700
,400
,800
,800
,000
,000
,590
,000
,000
,000
97,200
90.400
FlowJ
(gal
(10
( 6
( 5
( 5
( 1
( 6
( 1
( 2
( 6
( 8
( 5
(14
(12
(
( 6
( 5
( 1
TDS
1,000 Ibs)
,200)
,180)
,400)
,700)
,200)
.300)
,020)
,210)
500)
,400)
,200)
,000)
.250)
,250)
,000)
,500)
670)
,000)
,400)
,200)
( 1,200)
(10.800)
kg/kkg mg/L
3,770
333
897
1,760
200
-
-
-
2,000
2,580
388
203
189
M»,
6,
19,
36,
20,
-
-
-
40,
57.
38,
2,
2,
300
400
900
700
000
000
300
800
000
000
Chloride
kg/kkg
1,170
227
847
1,210
4.5
239
124
239
78
.
-
5
.
26
;
mg/L
13
4
18
25
6
2
23
3
2
,700
,400
,800
.300
450
.600
,500
,000
,900
-
-
100
-
,600
-
NH.-N
kg/kkg-'mg/L
27 318
0.13 13
76 2,100
14.5 288
15 1,500
1.6
80
2.5
67
250
Raw Waste Load
48,900
5,870
123
379
99 1,020
_82 _9JO
32
T-P
kg/kkg mg/L
8 178
9 190
25 500
74 l,64o
2.5 250
23.7
Notes:
Dash (-): Data not reported
kg/kkg os product Is equivalent to lbs/1,000 Ibs product
Historical plant data unless otherwise noted
Product identification: A,B-metrlbuzin or benzazimlde; C,D-atrazlne, simazlne, propazine, ametryne,
prometryne, slnstryne, Sumltol, terbatryne, prometone, or cyanazlne; E-dinoseb; F-atrazine; G,H-a!achlor
or propachlor; J-typlcal organo-nltrogen compound; K-butylate, EPTC, vernolate, cycloate, molinate, or
pebulate; L,M,N,0,P-alachlor, CDAA, propachlor, butachlor; 0_,R,S,T,U,V-dulron, bromacll, thlram, me thorny I,
linuron, or terbacll.
Includes all process wastewaters Including area and equipment washdowns and contaminated run-off.
k
Data obtained during plant visits via sample collection and analyses.
"The Pesticide Manufacturing Industry - Current Waste Treatment and Disposal Practices" U.S. Environ-
mental Protection Agency, Water Pollution Control Research Series, January 1972.
Raw waste load values were obtained by giving historical and plant visit data equal weighting. Since
historical data points are generally based on a limited number of Individual data points, this Is a
reasonable method of data treatment. In the case of duplicated data (I.e. historical as well as plant
visit data for the same product and plant) only the historical data was used to determine the RWL.
V-44
-------
DRATT
tn
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DRAFT
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Table VC-10
Raw Waste Loads
Formulators and Packagers
(Subcategory E)
Plant1
69
Literature^
Literature5«°
Flow2»3
L/kkg1
(gal/1,000 Ibs)
41,700
( 5,000)
3,120
( 374)
420
50)
COD
BODc
TSS
TOC
kg/kkg1mg/L kg/kkgl mg/L kg/kkglmg/L kg/kkglmg/L
252 6,040 67 1.610
1.4 450
2.0 645
0.18 450 0.12 286 0.08 190
Raw Waste
Load?
220
( 26.3)
11,400
( 1,350)
0.1
63
455
0.03
22
136
0.04 101
0.7
0.06 151
0.06
Notes: Data in terms of unit of production of formulated/packaged product.
Dash (-): Data not available.
3
Historical plant data unless otherwise noted.
Includes all process wastewaters including area and equipment washdowns and
contaminated run-off.
kg/kkg of product is equivalent to lbs/1,000 product.
Data obtained during plant visits via sample collection and analyses.
"Pollution Control Technology of Pesticide Formulators and Packagers",
National Agricultural Chemicals Association, Grant No. R-801577,
12 June 1974.
waste loads calculated from basic data presented in literature (Item 4).
Raw waste load values were obtained by giving historical and plant visit data
equal weighting. Since historical data points are generally based on a limited
number of individual data points, this is a reasonable method of data treatment.
In the case of duplicated data (i.e. historical as well as plant visit data for
the same product and plant) only the historical data was used to determine the
RWL.
V-47
-------
Table VC-10
(continued)
Plant
69
Literature
Flow*
CTkkg1
(gal/1,000 Ibs)
41,700
(5,000)
3,120
Literature
4, 5
420
(50)
TDS
T-P
Phenol
kg/kkg1mg/L kg/kkg1mg/L kg/kkg1 mg/L
2.0
0.2
0.2
,645
0.5
663
Raw Waste
Load6
220
(26.3)
11,400
(1,350)
0.2
0.8
1,000
nil
0.2
Notes: Dash (-): Data not available
kg/kkg of product is equivalent to lbs/1 ,000 Product
Historican plant data unless otherwise noted
Includes all process wastewaters including area and equipment washdowns
and contaminated run-off.
Data obtained during plant visits via sample collection and analyses.
"Pollution Control Technology of Pesticide Formulators and Packagers",
National Agricultural Chemicals Association, Grant No. R-801577,
12 June
6
Waste loads calculated from basic data presented in literature (Item 4).
Raw waste load values were obtained by giving historical and plant visit
data equal weighting. Since historical data points are generally based on
a limited number of individual data points, this is a reasonable method of
data treatment. In the case of duplicated data (i.e. historical as well
as plant visit data for the same product and plant) only the historical
data was used to determine the RWL.
V-48
-------
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DMA I
Table VC-12 indicates the distribution of the raw waste COD loadings
between the incineration/deep-wel1 facilities and the more conven-
tional type of wastcwater treatment plant. Nee«uise wrt**tev» handled
by incineration or deep-well facilities are usually very Mtontj and
toxic, BOD analyses are not reliable. Accordingly, COD was Judged
to be the best indication of the raw waste load distribution to
the various treatment facilities operated at the plants visited.
It is difficult to attribute the raw waste loading of the strong,
toxic wastes to the production of individual pesticides, because
records of the strong waste flow and loadings contributions of the
individual processes normally are not maintained. Therefore, Table
VC-12 lists the waste loads only for the basic pesticide subcategories,
i.e. halogenated, phosphorus, etc.
It can be seen from Table VC-12 that the percentage of waste material
handled at incineration or deep well facilities can vary from zero
to 100 percent. The residual raw waste loading to the wastewater
treatment system varies appreciably from one plant to another. This
variation is caused by differences in processing techniques and
water management programs. Obvious examples of this phenomenon
are Plant 66 compared to Plant 69, and Plant 68 versus Plant 62.
Plants that have been historically subject to stringent environmental
enforcement usually implement better end-of-pipe treatment and in-plant
control systems, and both raw waste and final effluent loadings reflect
this. (See Tables VC-7 and VC-10).
V-50
-------
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ment system.
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V-51
-------
DRAFT
D. Adhesive and Sealants Industry
General process flow diagrams (Figures IVD-1, IVD-2, IVD-3, and \\ID-k)
discussed in the previous section have indicated some of the wasU'-
water generation points for the individual processes where inforuui-
tion was readily available. However, physical sewer system layouts
and plant designs prevented the determination of flow rates and
analyses for process wastewater streams at points of origin. In
the past, plants have been concerned principally with the combined
wastewater streams instead of point sources of individual waste
streams. Wastewater may emanate from within the process where it
was required for the process operating conditions, it may be formed
during the course of chemical reactions, or it may be used in wash-
down of process vessels, area housekeeping, and in laboratories.
The main source of wastewater from adhesive manufacturing processes
is the washing of the process vessels and lines. The principal factors
that contribute to high effluent loading rates in the washwater are
related to tank and line clingage.
Analyses of wastewater streams are not normally performed because moni-
toring to provide effluent data for state regulatory bodies has not
been required. Most of the Adhesive industries discharge directly to
municipal sanitary sewer systems and have not had regular analyses
performed on their wastewater discharges. Because of this absence of
historical data within the Adhesive industry, it is difficult to
establish variability in the pollutants discharged in the process
wastewater.
A variety of disposal methods for adhesive waste are in use at the
present time. The waste loads discharged from each of the sub-
categories do not reflect actual raw waste loads because in-plant
pollution abatement measures currently practiced in the industry
have a significant effect on discharges. The pollution abatement
measures practiced by the industry include:
1. Using a small controlled rinsing with subsequent recycling of the
rinse water rather than simple filling and draining of process
vessels and 1ines.
2. Squeegeeing of clingage before rinsing where controlled rinsing
of tanks is not practical.
3. Blowing out the pipe lines and pumping systems where the rinse
cannot be re-worked or recycled.
V-52
-------
DRAFT
k. Cleaning up accidental spills so that they do not get into the
ef f 1uent.
5. Employing some type of holding or settling tank or pond for flow
equalization and removal of suspended solids.
Any combination of these in-plant abatement measures can be found in
the various plants of the.Adhesive industry. This fact makes total
raw wastewater characterization of the subcategories difficult.
Subcategory A - Animal Glue and Gelatin
Characterization of the plant wastewater in Subcategory A is best
typified in the analytical data in Table VD-1. The characteristics
of the raw waste given in Table VD-1 are typical of the strength of
the wastewater from an old animal glue and gelatin plant, where
wastewater flows and concentrations are probably higher than normal,
as a result of old piping and other factors related to plant age, as
well as housekeeping practices and in-plant measures.
The high total Kjeldahl-nitrogen (TKN) level originates in the glue
and gelatin extraction process. Chrome leather scraps are used as
raw material for glue production, and the chromium concentrations in
the range shown would be typical of this waste. The weekly sampling
data indicated that 95 percent of the time the pH was between 11 and
12. There are short periods when dilute sulfuric acid is used to
neutralize finished lime stock, and the pH then may range between k
and 6. However, these isolated incidents can be reduced by scheduling
simultaneous dumping of lime vats. The grease concentration in the
supernatant averaged approximately 10 percent of the total grease.
The wastewater flow of 3 mgd during the sampling period appeared low
when compared to historical flow information. During the early
1970's study, the wastewater flow averaged S.k mgd and ranged between
U.3 and 6.6 mgd. The daily average flow for the period from January
1973 to April 1974 was ^.0 mgd.
Subcateqory B - Water-Based Adhesives
Characterization of the wastewater in Subcategory B is best typified
in the analytical data presented in Table VD-2. The data represent
information collected from three different plants during the sampling
period. Tin- w.islewnler characteristics for these plants producing
water-base emulsions, colloids, and dispersins are remarkably similar.
Typical raw materials used include starches, dextrins, cellulosic
materials, polyvinyl acetate, acrylic polymers, polyvinyl alcohol,
and polyvinyl chloride.
V-53
-------
DRAFT
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-------
Table VD-2
Characterization of Waste Discharges
Subcategory B
DRAFT
Plant
Number
Flow BOD,- COD TOC TSS NH^-N
(mgd) (mg/L) (mg/L) (mg/Lj (mg/L) (mg/L)
29
27
28
0.003
0.01
0.01
2100 16,600 3800 2100
5600 16,200 7660 4280
4200 16,500 5300
3950
3.6
18.0
20.4
Table VD-3
Characterization of Waste Discharge
Subcategory C
Plant
Number
23
Flow
(mgd)
BOD
5.
COD
(mg/t) (mg/L)
0.006 13200 21,900
TOC
(mg/L)
4200
TSS
(mg/L)
36
NH^-N
(mg/L)
18
V-55
-------
DRAFT
Subcategories C and D - Solvent-Based Adhesives
Subcategories C and D include solvent solutions and cements and non-
water-based adhesives. Raw materials include synthetic and natural
resins, rosins, modified rosins, and elastomers. Although the products
are similar, the manufacturing processes may differ slightly. The
manufacturing process used in subcategory C generates contaminated
wastewater, while that used in subcategory D does not. Noncontact
cooling water is discharged in both Subcategories, and process
cleaning water may be discharged or recycled. Wastewater character-
istics for subcategory C are shown in Table VD-3. All of the plants
visited in subcategory D discharged noncontact cooling water only.
Process vessels can be cleaned out with solve it, which can, in turn,
be recycled back into the products.
Subcategory E - Hot Melt Thermoplastic Adhesives
There is no actual process water discharge from the production of hot
melt thermoplastic adhesives (subcategory E). The hot melt adhesives
are neither water- nor solvent-based adhesives, and they are not
compatible with water. The only contaminated wastewater that might
be discharged would be caustic washwater solutions. Two of the four
plants visited in this subcategory never clean their process vessels
with any type of water solution and suggest that this type of clean-
ing is not necessary. Instead of caustic and water, they use a hot
wax solution which can be drummed and recycled back into the pro-
duction of the same type or of similar products. Cleaning of the process
vessels occurs only when changing from a dark-colored to a light-
colored adhesive or when changing to non-compatible adhesives. The
vessels may also be cleaned periodically as part of regular mainten-
ance. During the sampling periods, there were never any discharges
associated with the production of hot melt adhesives from any of the
plants surveyed.
Subcategory F - Dry-Blended Adhesives
There is no process water or washwater discharge from the production
of dry-blended adhesive materials (subcategory F). The dry-blended
materials are completely solids and are neither water- nor solvent-
based materials. The proper formulation and blending of the raw
materials requires that absolutely no water be present in the mixing
compartment. There should never be any discharge associated with
this manufacturing process.
V-56
-------
DRAFT
Summary of Raw Waste Loads
Raw waste loads in pounds per 1,000 pounds of production obtained
during the sampling period for the subcategories of the Adhesives
and Sealants industry are shown in Tables VD-4 and VC-5. Represen-
tative raw waste loads in pounds per 1,000 pounds of production,
used to characterize the subcategories of the Adhesive and Sealants
industry and to establish effluent limitations, are shown in Table
VD-6. The values in Table VD-6 represent measures of central tendency.
The arithmetic mean was chosen as the measure of central tendency to
represent the subcategories in Table VD-6, since it acts as a kind
of fulcrum or center of gravity of a set of observations, and thus
is sensitive to extreme values. All observations of the group are
taken into account, and increases or decreases are included to
maintain a balance. The group of observations represented by the
arithmetic mean in Table VD-6 are well presented because of the close-
ness of the observations in the group. The closeness of the observa-
tions in the group is shown in Table VD-7, which presents measures of
variability for the data in Table VD-6, for subcategory B.
V-57
-------
DRAFT
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DRAFT
E. Explosives Industry
The wastewater sources associated with each subcategory and ranges
for values of select water quality parameters are presented in the
following discussion.
Subcategory Al - Manufacture of Explosives
The following tabulation summarizes the effluent waste load ranges
for subcategory A^.
Parameter Range
Tibs/I,000 Ibs product)
BOD5 0,18 - 6.35
COD 0.30 - 10.6
Nitrates 0,31 - 9-00
Sulfates 0,28 - 116.
TOC 0.2k - ^.t3
The wastes from this subcategory are characteristically high in BODc,
COD, nitrates, sulfates, and TOC.
Highly variable pH is also characteristic of the wastewater from ex-
plosives manufacture.
The manufacture of explosives generally involves the nitrification
of organic compounds. Many of the explosives use nitric acid to serve
as the nitrate source and sulfuric and acetic acids as dehydrating
compounds. Nitrification is followed by product finishing, including
washing, refinement and drying. The major waste loads generally come
from the finishing area, where the crude explosive becomes the final
product.
The raw materials used in the manufacture of explosives explain some
of the wastewater characteristics. The 6005, COD and TOC loads can
be attributed to the organic compounds involved. The high nitrate
levels can be attributed to acid and organic compounds that contain
nitrogen. The sulfate level can be attributed to sulfuric acid, and,
in the case of TNT, the sellite wash used in the purification of TNT.
Initially the wastewaters from explosives manufacture are highly acidic,
and pH values of 1.0 are not uncommon. However, prior to discharge,
neutralization is practiced and, hence, the pH can be as high as 9.0
at discharge. This explains the extreme values of pH.
V-63
-------
DRAFT
Another wastewater problem Is the discharge of trace quantities of
explosives. Discharges of nitroglycerine as high as 1,000 mg/L are
not uncommon, TNT Is of particular Interest since It has been proven
to Inhibit natural biological processes (G-12,21). Discharges of
wastewater containing 100 mg/L of TNT are typical. Concentration of
RDX and HMX can be as high as 25 mg/L.
Subcategory A_2 — Manufactive of Propel lants
The waste loads associated with the manufacture of propellants are
generally higher than those associated with the manufacture of ex-
plosives. The following tabulation summarizes the effluent waste
load ranges for subcategory /\2'
Parameter Range
(lbs/1,000 Ib product)
8005 63.4
COD 35.^1 - 118
Nitrates 0.237 - 66.5
Sulfates 53.5 - 328
TOC 28.8 - 43.6
Suspended solids are a troublesome problem, specifically in the man-
ufacture of nitrocellulose, where NC fines can produce levels of TSS
concentration from 1,000 to 10,000 mg/L, Wide variation in pH is
also a problem.
High 6005, COD and TOC levels can be attributed to the organic com-
pounds and solvents (alcohol and ether) involved in the processes.
High nitrate levels can be attributed to the use of nitric acids and
oraganic compounds with nitrogen as one of the elements. Similarly,
sulfate levels can be attributed to the use of sulfuric acid.
Subcateqory B - Load and Pack Plants
Waste loads from subcategory B are the mildest, but most variable, in
the Explosives industry. The following tabulation summarizes the
range of effluent waste loads for this subcategory:
Parameter Range
(lb/1,000 Ibs product)
BOD5 0 - .01
COD 0.0015 - 1.44
Nitrates .0003 - .053
Sulfates 0.0015 - 1.22
TOC 0.0025 - 4.3
V-64
-------
DRAFT
Waste loads in this subcategory could be almost completely eliminated
by the use of dry cleanup procedures.
Subcategory C - Specialty Plants
The waste loads associated with the manufacture of initiators and
other specialty explosives are the highest of any subcategory of the
Explosives industry. The following tabulation summarizes the efflu-
ent waste load ranges for subcategory C.
Parameter Range
BOD
COD
Nitrates
Sulfates
TOC
High TKN waste loads were also observed.
Very little can be said to explain why waste loads are so much higher
in this subcategory. The cause may have something to do with the total
quantity of specialty products manufactured. In general, specialty
products are sensitive high explosives, used to detonate the more
massive but less sensitive explosives. Therefore, the quantity pro-
duced is small when compared with the more widely-used explosives of sub-
category A. Because of the small quantity, batch processes are used,
recovery of spent materials is not attempted, and a total lack of treat-
ment prevails. For example, it was observed in the field that a
discharge with a pH of 12.1 occurred daily.
Genera 1
(lbs/1,000
378 -
1 , 040 -
.015 -
,006 -
10.1
Ibs Production)
2,210
17,100
5.750
7,180
1,520
Table VE-1 depicts the raw waste loads (RWL) for the Explosives industry.
Tables VE-2 and VE-3 present raw waste load data by plant. As this table
indicates, there are seven parameters whose raw waste loads are significant
BOD5, COD, TOC, TSS, NO.J-N, TKN and SO^.
The statistical methods used to analyze these data involved calcula-
tion of the mean. The mean is very sensitive to the presence or
absence of the extremes in the distribution. This is even more pro-
nounced when dealing with a small sample. In a severely skewed dis-
tribution, the very high or very low scores can exert a considerable
impact on the mean, to the extent that it is no longer a good measure
of central tendency. Hence, the statistical technique of discarding
the largest and smallest value was used in determining the
raw waste load for each subcategory if there were five or more pieces
V-65
-------
DRAFT
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^ulx.it«'<|ury Al - lM'l"*ivi M.inuUi. turr
',1
'ifl
M'
ill 7
V,7
0,'
01
0','
06
O'1
1( /
l,37
lt8
IP
R.iw Wastr Load
(Subcateqory 6 - Load l Pack Plants
50
Ol'
02 '
03'
*3*
itll
*l 7
*35
Raw Waste Load
A
*5
50
50
50 t, OIAZO
B7
A7
Raw Waste Load
?0ata 1 rom Patt rson (197*).
-Due to coding mbiguitles, this Individual
.Excludrs high nd low values
tPropellant ope at Ion
kjtxploslve oper tlon
• Four-plant ava age
ProduU Jon
kkq/rfjiy
1,000 Ih/ft.ty)
59.1,
(1311
1*5
O'O)
128
('83)
1*5.8
(101)
796
(657)
(7)
C")
(?)
(?)
(?)
50.7
(1171
13.1
(28.9)
22.0
(*8.6)
30.3
(66.9)
77.9
(161.0)
3*. 6
(76.3)
**.2
(97.5)
(2)
(2)
(2)
22.1
(1,8.6)
30.3
(66.9)
*5.8
(101)
.63
(1.*)
178
(783)
19. 23
(*2.*)
.119
(.263)
.1*3
(.315)
.0*1
(.090)
.0011
(.0025)
.023
(.051)
.636
(1.*00)
.150
(.330)
.052
(.115 )
Information wai
f
kH 'd«y
(i.»l'0
0.188
(0.05)
0.02*
(0.0063)
0.6?
(0.163)
5.68
(1.50)
28.*
(7.50)
(?)
(71
(71
("
(?)
0.0*1 7
1.37
(.363)
8.29
(2.19)
6.7*
(1.78)
26.8
(7.07)
10.8
(7.85)
.000*
(.0001)
(2)
(?)
(2)
.037
(.0097)
.882
(.733)
.023
(.0052)
.0057
(.0015)
.077
(.0071)
.0263
(.0068)
.0026
(.0007)
.00*2
(.0011)
.019
(.005)
.0019
(.0005)
.011
(.003)
.017*
(.00*6)
.0026
(.0007)
.0091,:
(.007*°)
unavailable
UMf VI • ?
Fxplmlve Industry
ow
L/kkq product
(oal/t ,000 prod) BOOt,
3,190
(3«2) °-"'
t«
(19.7) OJ8'
',.800
(576)
1?lt,000
95,800 , ,
(11,500)
(2) 6.35
(') 0.72
(7) 1.66
(2) 0.360
(?) 0.085
'•I9° ,.*63
105,000
(12.600) **•
376,000
(*5,IOO)
77,700
(7,660)
366,000
(*3,900)
217.000
(2t,000) 63>
8.58 ^OIQ
(2) .000
(2) .0015
(2)
1,660
(199)
29,000
(3. MO)
509
(61.1)
8,920
(1,070)
209
(25.1)
MiS'
22.200
(2.660)
(3**90 37**
<£:£>
1,670,000 . ,.„
(200,000)
1.330,000 , 2,0
(159.000) 2>ZIQ
27,*00
(3.290)
17,700
(7,120)
17*. 000, . }(a
(20,9006) '-260
, however, the average of these num
Raw Wjiir Load (k«/k»ci I'rodj'
COO 1SS TOf Nflj-N ci(l,(
O.V1 0.15' 0.550 3.35 6.55
0.051, 0.71, i.n n.i
0.06? 0.77 o it 10.',
10.7 *.13 -- 116
106 1 .07 1+.05 15
10.3 0.90 -- 9.0 J.7d
3.73 0.550 -- it. 81 l 0',
6.99 7.55 -- 3.60 76.'
1.19 0.53 -- 3.3* 'i "«"-•
.300 0.780 -- .9? 3.15
J.873 0.823 I.633 2.503 6.903
118 ?lt.6 *3.6 .736 53.5
83.5 -- *8.*
35.* 75.; .. 66.5
91.0 12*. 78.8 — 328
118 6*. 5 *3.6 38.* 191
.073 .005 .0270
.0015 — — .025
.0180 .0*70 — .0010
1.** 5.12 -- .03*
.015 .0176 .0065 .000*5
.036* .37 - .053 1.77
.0003 .003
6.75 *.30 — 00*5
.0015 001 .0025 0003 .0015
.0923 .973 .012' 0.0153 O.*09'
5.67 8.16
1,0*0 1,770 521 .015 '5.9
17,100 0.*6* 1,520 .2*1 7.180
2,090 10.0 93* 5,750
5.960 1.96 1.520
17.* 10.1 -- 0.006
10.59 7,770
6.550 9.783 9923 5.503 932!
bers MM available and uted In computing the over-all average
IKN
0, 10
0 '/I
l;.')?l
T.//')
T 31.-
5 n
i o
2 V,
1 060
0.823
13.8
3.51
687
5.98
0.00
--
.078
.079
.003
-
001
..
000
.021
590
1*.?
1 *8
8.85
*6I
._
0.53
6.053
r»gr from plants *+9. 50 only (^9, 50 the only ones visited In this category).
developed from more reliable single source - U7.
V-67
-------
OMFT
Table VE-3
Raw Waste Loads
Raw Waste Load (Ibs/ton Product)
Plant No.
Subcateqory At • Explosive Manufacture
lt8
50
1*3
Joliet
Wt
Patterson's Study
(01)
(02)
(03)
«HO
(06)
(07)
Raw Waste Load
1*7
«
Sunflower
1*2
Raw Waste Load
Subcateqory B - (Lap - Load fr Pack)
Patterson's Study
(01)
(02)
(03)
1*3 (Propellent)
Sunflower
Joliet
Twin Cities
1*3 (TNT)
50
Raw Waste Load
Subcategory C (Specialty Area Initiator)
Lake City
«
50
NHN & 150
LHR
PETN I DIAZO
Twin Cities
Uki- Clt lp«
TDS
19.5
31.8
39.1*
616
1*1.3
13.0
--
98.5
96.8
"17.0
1*3.9
116
502
10,200
—
2,890
It, 520
—
.125
11.9
.263
tit. 2
.51*
143
.035
.028
13.5
..
17.800
19,000
78,1*00
21*, 600
1,390
—
Alkalinity NHVN T-P Oil Na
25.lt .133
6.36 .147
1.85
1*9.2
13.lt
10.1*
—
5.27 -- 0.00
2.06 — 1.09
5.28 -- .09
1.51*
'9.2 3.55 — .72 it. 71
63.9 2.75 1.10 2.75 15lt
2.09 .169
—
.92
63.9 7.W .730 2.75 15lt
.007
—
.129
-
5.38
.168
83.it — -- — 3.19
.011*
.0216
13.2 .068 — 0.000 1.8
118 — .057
18.800 16 31.7 635 17,300
1.02 .093 7W 8,020
WO lit .331* 2,910 15,700
12,300 26.2 — 5,080
668 -- -- - 1.91*
390 -- .30
v-68
-------
DRAFT
of data to work with. If there were fewer than five pieces of data,
a simple mean was determined, and none of the data were discarded.
A significant waste characteristic not represented in Table VE-1
is metals. Information available on heavy metals was not adequate
to promulgate effluent limitations; however, they appear signifi-
cant only in subcategory C. Lead from the production of lead
azide and lead styphinate can be found in significant quantities.
Ouantities of approximately two pounds of lead a day (200 mg/l)
were observed being discharged dai'y at one installation.
Another significant waste characteristic not represented in Table VE-1
is trace quantities of explosives. The following concentrations of
explosives have been reported:
Explos i ves Effluent Concentration
NG 1 ,800 mg/L (E-18)
TNT 70-350 mg/L (E-7)
RDX 7.9 mg/L (E-9)
HMX 2.6 mg/L (E-9)
In addition to these manufactured explosives in the effluent, there
are significant concentrations of unwanted isomers such as DNT
(dinitrotoluene) in the wastewater. The possibility of these small
concentrations accumulating in the environment and the toxicity of
these wastes necessitates adequate treatment prior to discharge (E-12).
Ranges of Concentration
A key waste characterization is the range of concentration for signifi-
cant pollutant parameters. Average concentrations are presented in
Table VE-^-. These concentrations can be very misleading, since non-
contact cooling waters cannot be distinguished from process waters in
every case. To help visualize the ranges observed in the field, the
raw waste load data for each subcategory has been plotted as pollutant
raw waste load versus contact process wastewater flow load in Figures
VE-1 through VE-4. This type of plot is a convenient device for illus-
trating the strength of the wastewaters generated by industries in each
of the subcategories. Since both the loading (ordinate) and flow
(abscissa) are expressed on a production basis, dividing the loading
by the flow gives a slope which is equivalent to concentration. For
orientation, reference lines of constant concentration have been drawn
diagonally across each of the plots. Relating specific data points
to one of these line provides a convenient estimate of the raw waste
concentrations.
-------
DRAFT
Table VE-4
Concentration of Pollutants
Explosives Industry
:egory
A1
A2
B
C
Boq-
mg/L
871
7001
3
7,230
COD
mg/L
2,310
1 .2501
70
37,600
TKN
mg/L
489
ISO2
2k
35
Nitrates
mg/L
1>90
132
112
32
SQk
mg/L
4,120
4301
307
5,354
TOC
mg/L
972
4802
9
5,700
TSS
mg/L
489
2701
690
56
'(Historical Dates Plant No. 47
o
Survey Dates Plant No. 47
V-70
-------
DRAFT
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DRAFT
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z
.001
DRAFT
FIGURE VE-3
SUBCATEGORY B LOAD AND PACK: POLLUTANT RWL VS RAW WASTE FLOW
y
w
8 r
SOD •
COO O
TSS O
TOC A
N03 •
TKN •
SO. A
10
SO 100
600 1,000
5,000 10,000
60,000 100,000
RAW WASTE FLOW GAL/1, 000 # OF PRODUCT
V-73
-------
DRAFT
FIGURE VE-4
SUBCATEGORV C SPECIALTY MANUFACTURE POLLUTANT RWL VS RAW WASTE FLOW
5,000 10,000
50,000 100,000 500,000 1.000.000
RAW WASTE FLOW GAL/1,000 # PRODUCT
v-71*
5.000.000
-------
DRAFT
The individual plant RWL data for subcategory AI are plotted in Figure
VE-1 (explosives) and VE-2 (propel lants) . The data do not clearly
establish any trends between pollutant RWL and flow RWL within the
subc'ategory . Pollutant data points for subcategory AI generally fall
into the following concentration ranges:
6005 - 20.0 to 1,100 mg/L N0.3-N - 20.0 to 6,800 mg/L
COD - 60 to 3,500 mg/L TKN - 5.0 to 3,700 mg/L
TSS - 8.0 to 1,300 mg/L SO/+ - 50 to .2,100 mg/L
TOC - 12.0 to 1,500 mg/L
The following pollutant concentration ranges generally characterize
subcategory A! :
8005 - 200 mg/L N03-N - 1.0 to 4,000 mg/L
COD - 200 to 1,200 mg/L TKN - 1.8 to 60 mg/L
TSS - 100 to 1,000 mg/L SOz^ - 300 to 900 mg/L
TOC - 30 to 130 mg/L
Figure VE-3 graphically illustrates the relationships between pollutant
and flow RWL's for subcategory B. The pollutant concentration ranges
for subcategory B generally fall into the following ranges:
BOD5 - 1,000 mg/L N03-N - 0.4 to 12 mg/L
COD - 8.0 to 8,500 mg/L TKN - 2.0 to 6.0 mg/L
TSS - 1 to 700 mg/L SO/^ - 50 to 85 mg/L
TOC - 5.0 to 550 mg/L
The plant RWL data for subcategory C are plotted in Figure VE-4. The
data indicate an increasing relationship between pollutant RWL and
flow RWL within this subcategory. The pollutant data points generally
fall into the following concentration ranges:
BOD5 - 900 to 12,000 mg/L N03~N - 0.5 to 5,000 mg/L
COD - 11,000 to 50,000 mg/L TKN - 4.0 to 1,000 mg/L
TSS - 1.0 to 60,000 mg/L SO^ - 600 to 120,000 mg/L
TOC - 50 to 15,000 mg/L
Plants in subcategory AI appear to use similar amounts of water per
1,000 pounds of product while generating different amounts of wastes
er 1000 ounds of roduct.
,
per 1,000 pounds of product
Plants falling in subcategory A2 show a similar but not so pronounced
trend. It is evident that the concentrations for subcategory A2 appear
similar to AI ; however, the amounts of pollutant per 1,000 pounds of
product differ greatly. Tables VE-1 and VE-2 provide more detailed
data to substantiate this observation.
V-75
-------
DRAFT
Plants falling in subcategory B appear to be widely scattered with
regard to pollutant concentration. It should be noted that the
average flow in this category was about 30,000 gpd, even though the
concentrations are still very small.
Wasteloads from plants in subcategory C appear to be variable in
concentration. This is borne out by the nature of this category.
For example, if a sample extracted when the batch process was being
dumped, it would have a high concentration. Also, a plant that
discharges a specific process effluent once every three weeks was
sampled, and the result was extremely high concentrations of pollu-
tants; however, these periods of high concentration are mitigated by
long periods of low concentration.
V-76
-------
DRAFT
Carbon Black Industry
Unlike the other industries listed under Miscellaneous Chemicals,
the Carbon Black industry manufactures only a single major product
type. The various production processes for manufacturing carbon
black were used as a basis for subcategorization of the industry.
Because the discharges from these processes are intermittent and
highly dependent upon the immediate situation, no wastewater
sampling was performed for this industry. Available industrial
data, however, were acquired for waste categorization for the
thermal black process.
The major process wastewater stream for subcategory B (thermal
process) is the recirculated dehumidifier stream. The thermal
plant visited for this project had no blowdown from this source.
The dehumidifier stream was ponded and recirculated as quench
water in the process. Data obtained from the plant are presented
in Table VF-1.
Table VF-1
Raw Waste Loads
Carbon Black Industry
Process Flows TSS
(L/kkg) (kg/kkg)
Thermal Black 72,100 8.9
This waste stream is probably representative of a blowdown stream
that could be expected from other dehumidifier/quench systems; how-
ever, the quantity would be only 1 percent (approximately) of the
total flow. The solids concentrations should remain approximately
the same.
No definable process waste stream is discharged from subcategory A
(furnace black process). This process is a net user of water.
Only miscellaneous discharges occur, on an unscheduled basis. There-
fore, sampling was not practical.
Carbon black spills are generally vacuumed dry, and are therefore not
a source of contamination. Dry vacuuming is used to allow recovery
of uncontaminated dry carbon black and prevent wastewater contamination.
V-77
-------
DRAFT
G. Photographic Processing Industry
The raw waste loadings (RWL) for the photo-processing industry presented
in Table VG-1 were determined from analyses of samples collected during
plant visits. These data formed the data base and generally were con-
sistent with existing plant data. The RWL in each case represents an
average of four values: one each from two black-and-white film and
paper operations and two color film and paper operations. The pollu-
tant loadings from these four operations compared well in order-of-
magnitude, and this formed the basis of categorization.
Concentrations of the various parameters were determined from grab
samples collected from the combined wastewater overflows and wash
waters from each process (C-22, C-^1, C-^2, Ektaprint 3, etc.). The
concentration values for a specific pollutant were found to vary on
each of the same machines. Because of this variation in results, direct
comparison of the concentrations was not possible.
The constituents of the wastewater for which RWL were determined were
those parameters which are frequently present in the wastewater and
may have significant ecological consequences once discharged. Other
parameters which are considered toxic to municipal treatment plants,
such as cadmium, chromium and cyanide, were generally found In trace
quantities below the level of analytical detection and are not found
in concentrations which would exceed the limits set in the pretreat-
ment guide!ines.
V-78
-------
DRAFT
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DRAFT
H. Hospitals
The primary sources of Wftstewoter stream* from hlnpltdl* Include
sanitary wastewaters from surgical rooms, laboratories, laundries,
X-ray departments, cafeterias, and glassware washing. Wastewaters
from hospitals can be characterized as containing BOD_, COD, and
TSS concentrations comparable to normal domestic sewage and amenable
to biological treatment.
Specific contaminants which may appear in hospital wastewater in-
clude mercury, silver, barium, and boron. Mercury is used primarily
in hospital laboratories, but also appears in various forms in
medicines, disinfectants, and mildew inhibitors. Silver contami-
nation comes from spent developer solutions discarded by hospital
X-ray departments. These developers are used in processing X-ray
films. Boron is another contaminant which may appear in X-ray
department wastes. This element is found in fixer solutions used
in automatic film processing equipment. Barium injections are used
for diagnostic purposes, and this metal may appear in a hospital's
sanitary wastes.
The characteristics of the wastewater generated by a hospital can be
affected by various pollution control practices inside the hospital.
Programs to eliminate or reduce the discharge of mercury, solvents,
and various strong reagents have been initiated by some hospitals.
These wastes are collected in special containers and periodically
disposed of by a private contractor. Boron has been eliminated from
some hospital wastes by switching to boron-free film developing
chemicals. A common practice at many hospitals is the recovery of
silver from film developing wastes. This can be accomplished by
the use of silver recovery equipment on-site or by collecting the
waste and having a contractor periodically pick up the waste for
s i1ver recovery.
Five major parameters were considered while analyzing hospital waste-
water characteristics:
1. 6005 Raw Waste Loading (expressed as Ibs BOD5/1000 occupied beds)
2. COD Raw Waste Loading (expressed as Ibs COD/1000 occupied beds)
3. TSS Raw Waste Loading (expressed as Ibs TSS/1000 occupied beds)
k. TOC Raw Waste Loading (expressed as Ibs TOC/1000 occupied beds)
5. Wastewater Flow Loading (expressed as gals/1000 occupied beds)
The raw waste load (RWL) figures computed for the plants studied are
presented in Table VH-1. The raw waste load (RWL) values
for hospitals were developed by averaging the RWL values computed
for individual hospitals. These RWL values are also shown in Table VH-1
The RWL for all other parameters (except BOD5, COD, TSS, and TOC)
computed from the field survey data and the historical data are pre-
sented in Table VH-2.
V-80
-------
IH'AI
Table VH-1
Raw Waste Loads - Hospitals
Kaw Woble Load
Hosp i tn 1
No.
91
92
93
94
95
96
97
98
99
100
101
1 02'""
SRWL
Number
Occup ied
Beds
268
183
835
577
1374
165
1054
319
,460
681
314
398
KKL/Day
( mqd)
0.560
(0.148)
0.171*
(0.046)
1 .098
(0.290)
0.927
(0.245)
0.776
(0.205)
0.265
(0.070)
0.636
(0.168)
0.405
(0.107)
1.525
(0.403)
0.458
(0.121)
0.409
(0.108)
0.587
O.155)
F low
L/ 1000 Beds
(gal/1000 Beds)
2,020,000
(533,000)
954,000
(252,000)
1,310,000
(347,000)
1 ,610,000
(425,000)
564,000
(149,000)
1,610,000
(424,000)
602,000
(159,000)
1,270,000
(335,000)
1 ,050,000
(276,000)
670,000
(177,000)
1,310,000
(345,000)
1,470,000
(389,000)
1,210,000
(319,000)
BOD COD
kg/1 ,000 Beds
mg/L mg'L
124 313
(550) (1460)
321 785
(674) (1650)
224 596
(646) (1720)
223
(789)
396
(494)
183
(647)
244
(325)
190
(532)
282
(649)
239
(351+)
232
(666)
220
(715)
221 605
(587) (1610)
roc i^s
(lbs/1 ,000 Beds)
mg/L m(j/L
96 69
(425) (306)
245 81
(515) (169)
148 158
(428) (455)
92
(326)
199
(248)
170
(647)
161
(165)
171
(478)
234
(538)
21
(31)
194
(556)
204
(662)
171 171
(456) (378)
Hospitals not visited - values based on average yearly values.
V-81
-------
Table VH-2
Hospitals
Raw Waste toads
Number of Occupied Beds
Flow - llters/1,000 beds'
(gallons/1,000 beds')
Raw Waste Loads
TOS - kg/ 1,000 beds1
(lbs/1,000 beds')
TKN
N03-NI trogen
Total Phosphorus
Oil E Grease
Cyanide
Phenol
1 ron
Lead
Mercury
Copper
Chromium (Total)
Arsenic
Bar 1 urn
SI Iver
Boron
Manganese
Sulfate
Hospital
No. 91
268
2,020,000
(533,000)
1,480
(3,260)
55.8
(123)
0.0
(0.0)
16.1
(35.5)
67.6
(1*9)
0.0
(0.0)
3.63
(8.00)
2.97
(6.55)
0.0
(0.0)
0.018
(0.040)
0.29
(0.64)
0.17
(0.37)
0.0
(0.0)
7.62
(16.8)
0.59
(1.3D
0.98
(2.17)
(-)
(-)
Hospital
No. 92
183
954,000
(252,000)
790
(1,740)
24.7
(54.5)
0.37
(0.82)
21.1
(46.6)
73.5
(162)
0.0
(0.0)
0.12
(0.26)
2.49
(5.48)
0.0
(0.0)
0.0018
(0.004)
0.60
(1.33)
0.0
(0.0)
(-)
0.0
(0.0)
0.22
(0.48)
0.48
(1.07)
0.17
(0.38)
(-)
Hospital
835
1,310,000
(347,000)
540
(1,190)
60.4
(133)
1.45
(3.2)
6.86
(15.1)
(-)
0.0
(0.0)
(-)
(-)
(-)
(-)
(-)
(-)
(-)
(-)
0.41
(0.90)
0.91
(2.0)
(-)
52.2
(115)
SWP.L
937
(2,060)
47.0
(103)
0.61
(1.34)
14.7
(32.3)
70.6
(155)
0.0
(0.0)
1.88
(4.13)
2.73
(6.01)
0.0
(0.0)
0.01
(0.022)
0.44
(0.98)
0.085
(0.19)
0.0
(0.0)
0.0
(8.39)
0.41
(0.90)
0.79
(1.74)
0.17
(0.38)
52.2
(115)
Occupied Beds
V-82
-------
DRAFT
The raw waste loading data are plotted as pollutant raw waste loading
versus wastewater flow loading in Figure VH-1. This type of plot is
a convenient device for illustrating the quality or strength of the
wastewaters generated by hospitals. Since both the loading (ordinate)
and flow (abscissa) are expressed on a 1,000-bed basis, dividing the
loading by the flow gives a slope which is representative of waste
concentration. For orientation, reference lines of constant concen-
tration have been drawn diagonally across each of the plots. Relating
n specific data point to one of these lines provides a convenient
estimate of raw waste concentrations. This plot Indicates that no
definite relationships appear to exist between pollutant RWL and
flow RWL. Pollutant data points generally fall into the following
concentration ranges:
BODr - 100 to 400 mg/L
COD - 300 to 800 mg/L
TSS - 60 to 200 mg/L
TOC - 100 to 300 mg/L
These narrow ranges of concentration indicate that the character-
istics of the hospital wastes surveyed were fairly uniform.
The average quantity of wastewater generated per total number of
beds was 228 gallons/occupied bed. This compares favorably with the
value of 242 gallons/occupied bed reported by the American Hospital
Associat ion.
The correlation between BODr and COD, BOD^ and TOC, and 6005 and TSS
raw waste loads were checked to see if any apparent relationships
existed. A close correlation was observed between BOD5 and COD, and
between and BODj and TOC RWL's. The COD/BOD^ and BOD/TOC ratios
ranged between 2.4 and 2.7, and 1.3 and 1.5 respectively. The
correlation between BODr and TSS RWL's were not as close. The BODc/
TSS ratios observed varied from 1.0 to 2.4.
V-83
-------
DRAFT
§
o
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a
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K
V-8A
-------
UKAM
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
General
From review of NPDES permit applications for direct discharge of waste-
waters from various industries grouped under Miscellaneous Chemicals
and examination of related published data, twelve parameters (listed in
Table VI-1) were selected and examined for all industrial wastewaters
during the field data collection program. In addition, several specific
parameters were examined for each individual industry. All field
sampling data are summarized in Supplement B.
The degree of impact on the overall environment has been used as a basis
for dividing the pollutants into groups as follows:
1. Pollutants of Significance.
2. Pollutants of Limited Significance.
3- Pollutants of Specific Significance.
The rationale and justification for pollutant categorization within the
foregoing groupings, as discussed herein, will indicate the basis for
selection of the parameters upon which the actual effluent limitations
guidelines were postulated for each industrial category. In addition,
particular parameters have been discussed in terms of their validity
as measures of environmental impact and as sources of analytical insight,
in the light of current knowledge.
Pollutants observed from the field data that were present in sufficient
concentrations so as to interfere with, the incompatible with, or pass
with inadequate treatment through publicly owned treatment works are
discussed in Section XI I.
Pollutants of Significance
Parameters of pollution significance for the Miscellaneous Chemicals
industry are BOD^, COD, TOC, and TSS.
BODj, COD, and TOC have been selected as the pollutants of significance
because they are the primary measurements of organic pollution. In the
survey of the industrial categories, almost all of the effluent data
collected from wastewater treatment facilities were based upon BODr,
because almost all the treatment facilities were biological processes.
If other processes (such as evaporation, incineration, or activated
carbon) are utilized, either COD or TOC may be a more appropriate
measure of pollution.
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TABLE VI-I
Miscellaneous Chemicals industry
List of Pollutants to be Examined
Biochemical Oxygen Demand
Chemical Oxygen Demand
Total Organic Carbon
Total Dissolved Solids
Total Suspended Sol ids
Total Kjeldahl Nitrogen
Ammonia Nitrogen
Nitrate Nitrogen
pH
Alkalinity
Acidity
Total Phosphorus
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BOD
Biochemical oxygen demand (BOD) is usually defined as the amount of
oxygen required by bacteria while stabilizing decomposable organic
matter under aerobic conditions. The term "decomposable" may be inter-
preted as meaning that the organic matter can serve as food for the
bacteria and that energy is derived from this oxidation.
The BOD does not in itself cause direct harm to a water system, but it
does exert an indirect effect by depressing the oxygen content of the
water. Organic effluents exert a BOD during thefr processes of decom-
position which can have a catastrophic effect on the ecosystem by de-
pleting the oxygen supply. Conditions are reached frequently where
all of the oxygen is used, and the continuing decay process causes the
production of noxious gases, such as hydrogen sulfide and methane.
Water with a high BOD indicates the presence of decomposing organic
matter and subsequent high bacterial counts that degrade its quality
and potential uses.
Dissolved oxygen (DO) is a water quality constituent that in appropriate
concentrations, is essential not only to keep organisms living but also
to sustain species reproduction, vigor, and the development of popula-
tions. Organisms undergo stress at reduced DO concentrations that make
them less competitive and less capable of sustaining their species with-
in the aquatic environment. For example, reduced DO concentrations
have been shown to interfere with fish population through delayed hatch-
ing of eggs, reduced size and vigor of embryos, production of deformities
in the young, interference with food digestion, acceleration of blood
clotting, decreased tolerance to certain toxicants, reduced food effic-
iency and growth rate, and reduced maximum sustained swimming speed.
Fish food orgnisms are likewise affected adversely in conditions with
suppresed DO. Since all aerobic aquatic organisms need a certain amount
of oxygen, the consequences of total lack of dissolved oxygen due to a
high BOD can kill all inhabitants of the affected area.
If a high BOD is present, the quality of the water is usually visually
degraded by the presence of decomposing materials and algae blooms due
to the uptake of degraded materials that form the foodstuffs of the
algal populations.
The BOD test has been used to gauge the pollutional strength of a waste-
water in terms of the oxygen it would demand if discharged into a water-
course. Historically, the BOD test has also been used to evaluate the
performance of biological wastewater treatment facilities and to estab-
lish effluent limitation values. However, objections to the use of the
BOD test have been raised. The major objections are:
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1. The standard BODj test takes five days before the results are
available, which negates its use as an operational indicator.
2. At the start of the BOD test, a seed culture (microorganisms)
is added to the BOD bottle. If the seed culture were not
acclimated (i.e., exposed to a similar wastewater in the past),
then it may not readily biologically degrade the waste, and a
low BOD value will be reported. THis situation is very likely
to occur when dealing with complex industrial wastes, for
which acclimation is required in most cases. The necessity
of using "acclimated bacteria" makes it very time-consuming
for reviewing agencies to duplicate industrial BOD values
unless great care is taken in seed preparation.
3. The BOD test is sensitive to toxic materials, as are all bio-
logical processes. Therefore, if toxic materials are present
in particular wastewater, the reported BOD value may very
well be erroneous. This situation can be remedied by running
a microorganism toxicity test, i.e., subsequently diluting
the sample until the BOD value reaches a plateau indicating
that the material is at a concentration which no longer inhibits
biological oxidation.
However, some of the previously cited weaknesses of the BOD test also
make it uniquely applicable. It is the only parameter now available
which measures the amount of oxygen utilized by microorganisms in
metabolizing organics (wastewater). The use of COD or TOC to monitor
the efficiency of BOD removal in biological treatment is possible only
if there is a good correlation between COD or TOC and BOD. Under normal
circumstances, two correlations would be necessary, one for the raw
wastewater and one for the treated effluent. During the field data
analysis, varying correlations between COD or TOC and BOD^ were evident
within each industry and subcategory, and between industry and sub-
categories. In spite of its disadvantages, the Miscellaneous Chemicals
industry should continue to use the BODr parameter as one of its pollu-
tional indicators.
The BODtj test is essentially a bioassay procedure involving the measure-
ment of oxygen consumed by living organisms while utilizing the organic
matter present in a waste under conditions as similar as possible to
those that occur in nature. The problem arises when the test must be
standardized to permit its use (for comparative purposes) on different
samples, at different times, and in different locations. Once "Stand-
ard Conditions" have been defined, as they have for the BOD_ test, then
the original assumption that the analysis simulates natural conditions
in the receiving water applies, except only occassionally.
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In order to make the test quantitative, the samples must be protected
from the air to prevent reaeration as the dissolved oxygen level di-
minishes. In addition, because of the limited solubility of oxygen
in water (about 9 mg/L at 20 C), strong wastes must be diluted to
levels of demand consistent with th'is value to ensure that dissolved
oxygen will be present throughout the period of the test.
Since this is a bioassay procedure, it is extremely important that
enviornmental conditions be suitable for the living organisms to func-
tion in an unhindered manner at all times. This requirement means that
toxic substances must be absent and that accessory nutrients needed for
microbial growth (such as nitrogen, phosphorus and certain trace elements)
must be present. Biological degradation of organic matter under natural
conditions is brought about by a diverse group of organisms that carry
the oxidation essentially to completion (i.e., almost entirely to carbon
dioxide and water). Therefore, it is important that a mixed group of
organisms commonly called "seed" be present in the test. For most
industrial wastes, this "seed" should be allowed to adapt to the par-
ticular waste (acclimate") prior to introduction of the culture into
the BODr bottle.
The BODr test may be considered as a wet oxidation procedure in which
the living organisms serve as the medium for oxidation of the organic
matter to carbon dioxide and water. A quantitative relationship exists
between the amount of oxygen required to convert a definite amount of
any given organic compound to carbon dioxide and water, which can be
represented by a generalized equation. On the basis of this relation-
ship, it is possible to interpret BODc data in terms of organic matter
as well as in terms of the amount of oxygen used during its oxidation.
This concept is fundamental to an understanding of the rate at which
BODc is exerted.
The oxidative reactions involved in the BODc test are the result of
biological activity, and the rate at which the reactions proceed is
governed to a major extent by population numbers and temperature.
Temperature effects are held constant by performing the test at 20°C,
which is more or less a median value for natural bodies of water.
The predominant organisms responsible for the stabilization of most
organic matter in natural waters are native to the soil. The rate
of their metabolic processes at 20°C and under the conditions of the
test (total darkness, quiescence, etc) is such that time must be
reckoned in days. Theoretically, an infinite time is required for
complete biological oxidation of organic matter, but for all practical
purposes the reaction may be considered to be complete in 20 days. A
BOD test conducted over the 20 day period is normally considered a good
estimate of the "ultimate BOD." However, a 20-day period is too long
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to wait for results in most instances. It has been found by experience
with domestic sewage that a reasonably large percentage of the total
BOD is exerted in five days. Consequently, the test has been developed
on the basis of a 5~day incubation period. It should be remembered,
therefore, that 5~day BOD values represent only a portion of the total
BOD. The exact percentage depends on the character of the "seed" and
the nature of the organic matter, and can be determined only by experi-
ment .
COD
The Chemical Oxygend Demand (COD) test represents an alternative to the
BOD test, and in many respects it is superior to the BOD test. COD is
widely used and allows measurement of a waste in terms of the total
quantity of oxygen required for oxidation to carbon dioxide and water
under severe chemical and physical conditions. It is based on the
fact that all organic compounds, with a few exceptions, can be oxi-
dized by the action of strong oxidizing agents under acid conditions.
Although amino nitrogen will be converted to ammonia nitrogen, organic
nitrogen in higher oxidation states will be converted to nitrates; that
is, it will be oxidized.
During the COD test, organic matter is converted to carbon dioxide and
water regardless of the biological assimi 1abi1ity of the substances;
for instance, glucose and lignin are both oxidized completely. As a
result, COD values are greater than BOD values and may be much greater
when significant amounts of biologically-resistant organic matter is
present. i
One drawback of the COD test is that its results give no indication
of the rate at which the biologically active material would be stabilized
under conditions that exist in nature. Another drawback is analogous
to a problem also encountered with the BOD test, that i.s, high levels
of chloride interfere with the analysis. Normally, 0.4 grams of mer-
curic sulfate are added to each sample being analyzed for chemical
oxygen demand. This eliminated the chloride interference in the
sample up to a chloride level of 40 mg/L. At concentrations above this
level, further mercuric sulfate must be added.
The major advantage of the COD test is the short time required for
evaluation. The determination can be made in about 3 hours rather
than the 5 days required for the measurement of BOD. Furthermore, the
COD test requires less sophisticated equipment, smaller working area,
and less investment in laboratory facilities, and does not require as
high a degree of training as does the BOD test. Another major advantage
of the COD test is that there is no seed acclimation problem. With the
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BOD test, the seed used to inoculate the culture should have been
acclimated for a period of several days, using carefully prescribed
procedures, to assure that the normal lag time (exhibited by all micro-
organisms when subjected to a new substrate) can be minimized. No
acclimation, of course, is required in the COD test.
TOC
Total organic carbon (TOC) is a measure of the amount of carbon in the
organic material in a wastewater sample. The TOC analyzer withdraws a
saml1 volume of sample and thermally oxidizes it at 150°C. The water
vapor and carbon dioxide from the combustion chamber (where the water
vapor is removed) are condensed and sent to an infrared analyzer, where
the carbon dioxide is monitored. This carbon dioxide value corresponds
to the total inorganic value. Another portion of the same sample is
thermally oxidized at temperatures above 950°C, which converts all the
carbonaceous material; this value corresponds to the total carbon value.
TOC is determined by subtracting the inorganic carbon (carbonates and
water vapor) from the total carbon value.
TSS
Total suspended solids discharged in the biological treatment system
efflent consist of biological solids and other suspended solids carried
over through the treatment facilities. Total suspended solids, when
discharged to a watercourse, settle to the bottom and can blanket spawn-
Ing grounds and interfere with fish propagation. In addition, the solids
which are organic will be metabolized and exert an oxygen demand (which
can be appreciable) on the body of water. Total suspended solids, in
large concentrations, can impede light transmittance and interfere with
aquatic photosynthesis, thereby affecting the oxygen content of a body
of water.
TSS RWL's vary significantly within each industry and between industries.
The problem Is compounded because much of the TSS eventually discharged
to surface waters are biological solids which have been produced in the
end-of-pipe biological treatment facilities and only partly removed before
discharge. To minimize this problem, the effluent limitations will be
based on a concentration value which will be attainable with adequate
solids separation facilities.
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Pollutants of Limited Significance
The following parameters, which were investigated in particular cases,
have significant effects on the applicability of end-of-pipe treatment
technologies.
Arsenic
Arsenic is found to a small extent in nature in the elemental form.
It occurs mostly in the form of arsenites of metals or as pyrites.
Arsenic is normally present in sea water at concentrations of 2 to 3
mg/L and tends to be accumulated by oysters and other shellfish. Con-
centrations of 100 mg/kg have been reported in certain shellfish. Ar-
senic is a cumulative poison with long-term chronic effects on both
aquatic organisms and on mammalian species, and a succession of small
doses may add up to a final lethal dose. It is moderately toxic to
plants and highly toxic to animals especially as AsH,.
Arsenic trloxide, which also !s exceedingly toxic, was studied in con-
centrations of 1.96 to ^0 mg/L 'and found to be harmful in that range to
fish and other aquatic life. Work by the Washington Department of Fish-
eries on pink salmon has shown that at a level of 5-3 mg/L of As_0, for
8 days was extremely harmful to this species: on mussels, a level of
16 mg/L was lethal in 3 to 16 days.
Severe human poisoning can result from 100 mg/L concentrations, and 130
mg/L has proved fatal. Arsenic can accumulate in the body faster than
it is excreted and can build to toxic levels, from small amounts taken
periodically through lung and intestinal walls from the air, water and
food.
Arsenic is a normal constituent of most soils, with concentrations ranging
up to 500 mg/kg. Although very low concentrations of arsenates may actually
stimulate plant growth, the presence of excessive soluble arsenic in irri-
gation waters will reduce the yield of crops, the main effect appearing
to be the destruction of chlorophyll in the foliage. Plants grown in
water containing one mg/L of arsenic trioxides showed a blackening of the
vascular bundles in the leaves. Beans and cucumbers are very sensitive,
while turnips, cereals, and grasses are relatively resistant. Old orchard
soils in Washington that contained k to 12 mg/kg of arsenic trioxide in
the topsoil were found to have become unproductive.
Cadmium
Cadmium in drinking water supplies is extremely hazardous to humans, and
conventional treatment (as practiced in the United States) does not remove
it. Cadmium is cumulative in the liver, kidney, pancreas, and thyroid
of humans and other animals. A severe bone and kidney syndrome in Japan
has been associated with the ingest ion of as little as 600 g/day of cad-
mium.
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Cadmium is an extremely dangerous cumulative toxicant, causing Insidious
progressive chronic poisoning in mammals, fish, and probably other animals
because the metal is not excreted. Cadmium could form organic compounds
which might lead to mutagenic or teratogenic effects. Cadmium Is known
to have marked acute and chronic effects on aquatic organisms also.
Cadmium acts synergistically with other metals. Copper and zinc substan-
tially increase its toxicity. Cadmium is concentrated by marine organ-
isms, particularly molluscs, which accumulate cadmium in calcareous tissues
and in the viscera. A concentration factor of 1,000 for cadmium in fish
muscle has been reported, as have concentration factors of 3,000 in marine
plants, and up to 29,600 in certain marine animals. The eggs and larvae
of fish are apparently more sensitive than adult fish to poisoning by cad-
mium, and crustaceans appear to be more sensitive than fish eggs and larvae.
Copper
Copper salts occur in natural surface waters only in trace amounts, up
to about 0.05 mg/L; consequently, their presence generally is the result
of pollution. This is attributable to the corrosive action of the water
on copper and brass tubing, to industrial effluents, and frequently to
the use of copper compounds for the control of undesirable plankton organ-
i sms.
Copper is not considered to be a cumulative systemic poison for humans,
but it can cause symptons of gastroenteritis, with nausea and intestinal
irritations, at relatively low dosages. The limiting factor in domestic
water supplies is taste. Threshold concentrations for taste have been
generally reported in the range of 1.0 to 2.0 mg/L of copper, while 5 to
7.5 makes the water completely unpalatable.
The toxicity of copper to aquatic organisms varies significantly, not
only with the species, but also with the physical and chemical character-
istics of the water, including temperature, hardness, turbidity, and
carbon dioxide content. In hard water, the toxicity of copper salts is
reduced by the precipitation of copper carbonate or other insoluble com-
pounds. The sulfates of copper and zinc, and of copper and calcium, are
synergistic in their toxic effect on fish.
Copper concentrations less than 1 mg/L have been reported to be toxic
(particularly in soft water) to many kinds of fish, crustaceans, molluscs,
insects, phytoplankton, and zooplankton. Concentrations of copper, for
example, are detrimental to some oysters above 0.1 ppm. Oysters cultured
in sea water containing 0.13 to 0.5 ppm of copper deposited the metal in
their bodies and became unfit as food.
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Chromium
Chromium, in its various valence states, is hazardous to man. It can
produce lung tumors when inhaled and induces skin sens!ttzations. Large
doses of chromates have corrosive effects on the intestinal tract and
can cause inflammation of the kidneys. Levels of chromate ions that
have no effect on man appear to be so low as to prohibit determination
to date.
The toxicity of chromium slats toward aquatic life varies widely with the
species, temperature, pH, valence of the chromium, and synergistic or an-
tagonistic effects, especially that of hardness. Fish are relatively tol-
erant of chromium salts, but fish food organisms and other lower forms of
aquatic life are extremely sensitive. Chromium also inhibits the growth
of algae.
In some agricultural crops, chromium can cause reduced growth or death
of the crop. Adverse effects of low concentrations of chromium on corn,
tobacco, and sugar beets have been documented.
Cyanide
Cyanides in water derive their toxicity primarily from undissolved hy-
drogen cyanide (HCN) rather than from the cyanide ion (CN~). HCN disso-
ciates in water into H and CN in a pH-dependent reaction. At a pH of
7 or below, less than 1 percent of the cyanide is present as CN ; at a pH
of 8, 6.7 percent; at a pH of 9, ^2 percent; and at a pH of 10, 87 per-
cent of the cyanide is dissociated. The toxicity of cyanides is also
increased by increases In temperature and reductions In oxygen tensions.
A temperature rise of 10 C produced a two to three-fold increase in the
rate of the lethal action of cyanide.
Cyanide has been shown to be poisonous to humans, and amounts over 18 ppm
can have adverse effects. A single dose of about 50 to 60 mg is reported
to be fatal.
Trout and other aquatic organisms are extremely sensitive to cyanide.
Amounts of small as 0.1 ppm can kill them. Certain metals, such as
nickel, may complex with cyanide to reduce lethality, especially at
higher pH values, but zinc and cadmium cyanide complexes are exceedingly
toxic. When fish are poisoned by cyanide, the gills become considerably
brighter in color than those of normal fish, owing to the inhibition by
cyanide of the oxidase responsible for oxygen transfer from the blood
to the tissues.
Dissolved Sol ids
In natural waters, the dissolved solids are mainly carbonates, chlorides,
sulfates, phosphates, and to a lesser extent, nitrates ot calcium, magnesium,
sodium, and potassium, with traces of iron, manganese and other substances.
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Many communities in the United States and in other countries use water
supplies containing 2,000 to 4,000 mg/L of dissolved salts, when no
better water is available. Such waters are not palatable, may not quench
thirst, and may have a laxative action on new users. Waters containing
more than 4,000 mg/L of total salts are generally considered unfit for
human use, although in hot climates such higher salt concentrations can
be tolerated. Waters containing 5,000 mg/L or more are reported to be
bitter and act as a bladder and intestinal irritants. It is generally
agreed that the salt concentration of good, palatable water should not
exceed 500 mg/L.
Limiting concentrations of dissolved solids for fresh-water fish may range
from 5,000 to 10,000 mg/L, according to species and prior acclimatization.
Some fish are adapted to living in more saline waters, and a few species
of fresh-water forms have been found in natural waters with a salt con-
centration of 15,000 to 20,000 mg/L. Fish can slowly become acclimatized
to higher salinities, but fish in waters of low salinity cannot survive
sudden exposure to high salinities, such as those resulting from discharges
of oil-well brines. Dissolved solids may influence the toxicity of heavy
metals and organic compounds to fish and other aquatic life, primarily
because of the antagonistic effect of hardness on metals.
Waters with total dissolved solids concentrations higher than 500 mg/L
have decreasing utility as irrigation water. At 5,000 mg/L, water has
little or no value for irrigation.
Dissolved solids in industrial waters can cause foaming in boilers and
can cause interference with cleanliness, color, or taste of many finished
products. High concentrations of dissolved solids also tend to accelerate
corrosion.
Specific conductance is a measure of the capacity of water to convey an
electric current. This property is related to the total concentration
of ionized substances in water and to the water temperature. This pro-
perty is frequently used as a substitute method of quickly estimating
the dissolved solids concentration.
Fecal Coliform
Fecal coliforms are used as an indicator since they have originated from
the intestinal tract of warm-blooded animals. Their presence in water
indicates the potential presence of pathogenic bacteria and viruses.
The presence of coliforms, more specifically fecal coliforms, in water is
indicative of fecal pollution. In general, the presence of fecal coliform
organisms indicates recent and possibly dangerous fecal contamination.
When the fecal coliform count exceeds 2,000 per 100 ml there is a high
correlation with increased numbers of both pathogenic viruses and bacteria.
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Many microorganisms, pathogenic to humans and animals, may be carried
in surface water, particularly that derived from effluent sources which
find their way into surface water from municipal and industrial wastes.
The diseases associated with bacteria include baclllary and amoebic dysen-
tery, Salmonella gastroenteritis, typhoid and paratyphoid fevers, lepto-
spirosis, cholera, vibriosis, and infectious hepatitis. Recent studies
have emphasized the value of fecal coliform density in assessing the
occurrence of Salmonella, a common bacterial pathogen in surface water.
Field studies involving irrigation water, field crops, and soils indicate
that when the fecal coliform density in stream waters exceeded 1,000 per
100 ml, the probability of occurrence of Salmonella was 53-5 percent.
Fluorides
As the most reactive non-metal, fluorine is never found free in nature
but as a constituent of fluorite, fluorspar, or calcium fluoride (in
sedimentary rocks) and also of cryolite or sodium aluminum fluoride
(in igneous rocks). Owing to their origin only in certain types of
rocks, and only in a few regions, fluorides in high concentrations are
not a common constituent of natural surface waters, but they are not a
common constituent of natural surface waters, but they may occur in det-
rimental concentrations fn ground waters.
Fluorides are used as insecticides, for disinfecting brewery apparatus,
as a flux in the manufacture of steel, for preserving wood and mucilages,
for the manufacture of glass and enamels, in chemical industries, for water
treatment, and for other uses.
Fluorides in sufficient quantity are toxic to humans, with doses of 250
to ^50 mg giving severe symptoms or causing death.
There are numerous articles describing the effects of fluoride-bearing
waters on dental enamel of children; these studies lead to the genrali-
zation that water containing less than 0.9 to 1.0 mg/L of fluoride will
seldom cause mottled enamel in children, to cause endemic cumulative
fluorosis and skeletal effects. Abundant literature is also available
describing the advantages in drinking water to aid in the reduction of
dental decay, especially among children.
Chronic fluoride poisoning of livestock has been observed in areas where
water contained 10 to 15 mg/L fluoride. Concentrations of 30 to 50 mg/L
of fluoride in the total ration of dairy cows is considered the upper
safe limit. Fluoride from waters apparently does not accumulate in soft
tissue to a significant degree, and it is transferred to only a very small
extent into the milk and to a somewhat greater degree into eggs. Data for
fresh water indicates that fluorides are toxic to fish at concentrations
above 1.5 mg/L.
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Lead
Some natural waters contain lead in solution, as much as 0.^ to 0.8 mg/L
where mountain limestone and galena are found. In the U.S.A., lead con-
centrations in surface and ground waters used for domestic supplies range
from traces to O.Qk mg/L, averaging about 0.01 mg/L.
Foreign to the human body, lead is cumulative poison. It tends to be
deposited in bone as a cumulative poison. The intake that can be regarded
as safe for everyone cannot be stated definitely, because the sensitivity
of individuals to lead differs considerably. Lead poisoning usually re-
sults from the cumulative toxic effects of lead after continuous consump-
tion over a long period of time, rather than from occasional small doses.
Lead is not among the metals considered essential to the nutrition of ani-
mals or human beings.
Lead may enter the body through food, air, and tobacco smoke as well as
from water and other beverages. The exact level at which the intake of
lead by the human body will exceed the amount excreted has not been
established, but it probably lies between 0.3 and 1.0 mg per day. The
mean daily intake of lead by adults in North America is about 0.33 mg per
day are derived from water used for cooking and drinking.
Lead in an amount of 0.1 mg ingested daily over a period of years has
been reported to cause lead poisoning. On the other hand, one reference
considered 0.5 mg per day safe for human beings, and a daily dose of
0.16 mg/L over long periods of time have apparently been non-poisonous.
The mandatotry limit for lead in the USPHS Drinking Water Standards is
0.05 mg/L. Several countries use 0.1 mg/L as a standard.
Traces of lead in metal-piating baths will affect the smoothness and
brightness of deposits. Inorganic lead salts in irrigation water may be
toxic to plants and should be investigated further. It is not unusual
for cattle to be poisoned by lead in their water: the lead need not
necessarily be in solution, but may be in suspension, as, for example,
oxycarbonate. Chronic lead poisoning among animals has been caused by
0.18 mg/L of lead in soft water. Most authorities agree that 0.5 mg/L
of lead is the maximum safe limit for lead in a potable supply for animals.
The toxic concentration of lead for aerobic bacteria is reported to be
1.0 mg/L, and for flagellates and infusoria, 0.5 mg/L. The bacterial de-
composition of organic matter is inhibited by 0.1 to 0,5 mg/L of lead.
Studies indicate that in water containing lead salts, a film of coagula-
ted mucus forms, first over the gills, and then over the whole body of
the fish, probably as a result of a reaction between lead and an organic
constituent of mucus. The death of the fish is caused by suffocation
due to this obstructive layer. In soft water, lead may be very toxic:
in hard water equivalent concentrations of lead are less toxic. Concen-
trations of lead as low as 0.1 mg/L have been reported toxic or lethal
to fish. Other studies have shown that the toxicity of lead toward rain-
bow trout increases with a reduction of the dissolved-oxygen concentration
of the water.
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Manganese
The presence of manganese may interfere with water usage, since manganese
stains materials, especially when the pH is raised as in laundering, scour-
ing, or other washing operations. These stains, if not masked by iron,
may be dirty brown, gray or black in color, and usually occur in spots
and streaks. Waters containing manganous bicarbonate cannot be used in
the textile industries, in dyeing, tanning, laundering, or in hosts of
other industrial uses. In the pulp and paper industry, waters containing
above 0.05 ppm manganese cannot be tolerated except for low-grade products.
Very small amounts of manganese — 0.2 to 0.3 ppm — may form heavy en-
crustations in piping, while even smaller amounts may form noticeable
black deposits.
Nickel
Elemental nickel seldom occurs in nature, but nickel compounds are found
in many ores and minerals. As a pure metal, it is not a problem In
water pollution because it is not affected by, or soluble in, water.
Many nickel salts, however, are highly soluble in water.
Nickel is extremely toxic to citrus plants. It is found in many soils
in California, generally in Insoluble form, but excessive acidification
of such soil may render it soluble, causing severe injury or death to
plants. Many experiments with plants in solution cultures have shown
that nickel at 0.5 to 1.0 mg/L is inhibitory to growth.
Nickel salts can kill fish at very low concentrations. Data for the
fathead minnow show death occurring in the range of 5 - ^3 mg, depending
on the alkalinity of the water.
Nickel Is present in coastal and open ocean concentrations in the range
of 0.1 - 6.0 mg.L, although the most common values are 2-3
Marine animals contain up to ^00 /L, and marine plants contain up to
3,000 /L. The lethal limit of nickel to some marine fish has been re-
ported as low as 0.8 ppm. Concentrations of 13.1 mg/L have been reported
to cause a 50 percent reduction of the photosynthetic activity in the
giant kelp (Macrocystis pyrifer) in 96 hours, and a low concentration was
found to kill oyster eggs.
Nitrogen
Ammonia nitrogen (NH.-N) and Total Kjeldahl nitrogen (TKN) are two
parameters which have received a substantial amount of interest in the
last decade. TKN is the sum of the NH,-N and organic nitrogen present
in the sample. Both NH^ and TKN are expressed in terms of equivalent
nitrogen values in mg/L to facilitate mathematical manipulations of
the values.
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Organic nitrogen may be converted in the environment to ammonia by
saprophytic bacteria under either aerobic or anaerobic conditions. The
ammonia nitrogen then becomes the nitrogen and energy source for auto-
trophic organisms (nitroflers). The oxidation of ammonia to nitrite
and then to nitrate has a stoichiometric oxygen requirement of approxi-
mately ^.6 times the concentration of NhU-N. The nitrification reaction
is much slower than the carbonaceous reactions, and, therefore, the dis-
solved oxygen utilization is observed over a much longer period.
Ammonia is a common product of the decomposition of organic matter.
Dead and decaying animals and plants along with human and animal body
wastes account for much of the ammonia entering the aquatic ecosystem.
Ammonia exists in its non-ionized form only at higher pH levels and is
the most toxic In this state. The lower the pH, the more ionized am-
monia is formed and Its toxiclty decreases. Ammonia, in the presence
of dissolved oxygen, is converted to nitrate (NO,) by nitrifying bacteria.
Nitrite (N02), which is an intermediate product between ammonia and
nitrate, sometimes occurs in quantity when depressed oxygen conditions
permit. Ammonia can exist in several other chemical combinations, in-
cluding ammonium chloride and other salts.
Nitrates are considered to be among the poisonous ingredients of mineral-
ized waters, with potassium nitrate being more poisonous than sodium
nitrate. Excess nitrates cause irritation of the mucous linings of the
gastrointestinal tract and the bladder; the symptoms are diarrhea and
diuresis. Drinking one liter of water containing 500 mg/L of nitrate
can cause such symptoms.
Infant methemoglobinemla, a disease characterized by certain specific
blood changes and cyanosis, may be caused by high nitrate concentrations
in the water used for preparing feeding formulae. While it is still im-
possible to state precise concentration limits, It has been widely recom-
mended that water containing more than 10 mg/L of nitrate nitrogen (NOo-N)
should not be used for infants.
Nitrates are also harmful in fermentation processes and can cause disagree-
able tastes in beer. In most natural water the pH range is such that
ammonium ions (NH.+) predominate. In alkal1ne waters, however, high
concentrations of non-ionized ammonia in undissociated ammonium hydroxide
increase the toxiclty of ammonia solutions.
In streams polluted with sewage, up to one-half of the nitrogen in the
sewage may be in the form of free ammonia, and sewage may carry up to
35 mg/L of total nitrogen. It has been shown that at a level of 1.0
mg/L non-ionized ammonia, the ability of hemoglobin to combine with
oxygen is impaired and may cause fish to suffocate. Evidence Indicates
that ammonia exerts a considerable toxic effect on all aquatic life
within a range of less than 1.0 to 25 mg/L, depending on the pH and
dissolved oxygen level present.
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DRAFT
Ammonia can add to the problem of eutrophication by supplying nitrogen
through Its breakdown products. Some lakes In warmer climates, and
others that are aging quickly, are sometimes limited by the nitrogen
available. Any Increase will speed up the plant growth and decay process.
011 and Grease
Oil and grease exhibit an oxygen demand. Oil emulsions may adhere to the
gills of fish or coat and destroy algae or other plankton. Deposition
of oil in the bottom sediments can serve to exhibit normal benthlc
growths, thus Interrupting the aquatic food chain. Soluble and emul-
sified material ingested by fish may taint the flavor of the fish flesh.
Water-soluble components may exert toxic action on fish. Floating oil
may reduce the re-aeration of the water surface and in conjunction with
emulsified oil may interfere with photosynthesis.
Water insoluble components damage the coats of water animals and the
plumage fowls. Oil and grease in water can result in the formation of
objectionable surface slicks preventing the full aesthetic enjoyment
of the water. Oil spills can damage the surface of boats and destroy
the aesthetic characteristics of beaches and shorelines.
pH. Acidity and Alkalinity
Acidity and alkalinity are reciprocal terms. Acidity is produced by
substances that yield hydrogen Ions upon hydrolysis, and alkalinity is
produced by substances that yield hydroxyl ions. The term "total
acidity" and "total alkalinity" are often used to express the buffer-
ing capacity of a solution.
Acidity in natural waters is caused by carbon dioxide, mineral acids,
weakly dissociated acids, and the salts of strong acids and weak bases.
Alkalinity is caused by strong bases and the salts of strong alkalies
and weak acids.
The term pH is a logarithmic expression of the concentration of hydrogen
ions. At a pH of 7, the hydrogen and hydroxyl ion concentrations are
essentially equal and the water is neutral. Lower pH values indicate
acidity, while higher values indicate alkalinity. The relationship
between pH and acidity or alkalinity is not necessarily linear or
direct.
»
Waters with a pH below 6 are corrosive to waterwork structures, distri-
bution lines, and household plumbing fixtures, and can thus add such
constituents to drinking water as iron, copper, zinc, cadmium, and lead.
VI-16
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DRAFT
The hydrogen Ion concentration can affect the "taste" of water. At a
low pH water tates "sour". As pH Increases, the bacterical effect of
chlorine is weakened, and it is advantageous to keep the pH close to
7. This is very significant to providing safe drinking water.
Extremes of pH or rapid pH changes can exert stress conditions or kill
aquatic life outright. Dead fish, associated algal blooms, and foul
stenches are aesthetic liabilities of any waterway. Even moderage
changes from "acceptable" criteria limits of pH are deleterious to
some species. The relative toxicity to aquatic life of many materials
is increased by changes in the water pH. A drop of 1.5 units Metallo-
cyanide complexes can increase a thousandfold in toxicity. The avail-
ability of many nutrient substances varies with the alkalinity and
acidity. Ammonia is more lethal with a higher pH.
The lacrimal fluid of the human eye has a pH of approximately 7, and
a deviation of 0.1 pH unit from the norm may result in eye irritation
or severe pain for the swimmer.
Phenols
Phenols and phenolic wastes are derived in the petroleum, coke, and
chemical industries; from wood distillation; and from domestic and
animal wastes. Many phenolic compounds are more toxic than pure
phenol; their toxicity varies with the combinations and general nature
of total wastes. The effect of combinations of different phenolic
compounds is cumulative.
Phenols and phenolic compounds are both acutely and chronically toxic
to fish and other aquatic animals. Also, chlorophenols produce an un-
pleasant taste in fish flesh, destroying their reactional and commercial
value.
It is necessary to limit phenolic compounds in the raw water used for
supplying drinking water, as conventional treatment methods used by
water supply facilities do not remove phenols. The ingestion of con-
centrated solutions of phenols will result in severe pain, renal ir-
ritation, shock, and possibly death.
Phenols also reduce the utility of water for certain industrial uses,
notably food and beverage processing, where It creates unpleasant
tastes and odors In the product.
Phenols In wastewater present the following two major problems:
1) At high concentrations, phenol acts as a bactericide.
2) At very low concentrations, when disinfected with chlorine,
chlorophenols are formed, producing taste and odor problems.
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DRAFT
Past experience has indicated that biological treatment systems may be
acclimated to phenol concentrations of 300 mg/L or more (A-18). How-
ever, protection of the biological treatment system against slug loads
of phenol should be given careful consideration In the design. Slug
loadings as low as 50 mg/L could be Inhibitory to the biological popu-
lation, especially if the biological system is not completely mixed.
Phosphorus
During the past 30 years, a formidable case has developed, supporting
the belief that Increasing standing crops of aquatic plant growths,
which often interfere with water uses and are nuisances to man, fre-
quently are caused by increasing the supply of phosphorus. Such
phenomena are associated with a condition of accelerated eutrophication
or aging of waters. It is generally recognized that phosphorus is not
the sole cause of eutrophication, but there is evidence to substantiate
that it Is frequently the key element in all of the elements required
by fresh water plants and is generally present in the least amount
relative to need. Therefore, an increase in phosphorus allows the use
of other, already present, nutrients for plant growths. For this reason,
phosphorus Is usually described as a "limiting factor".
When plant life is stimulated and attains a nuisance status, a large
number of associated liabilities are immediately apparent. Growths of
pond weeds make swimming dangerous. Boating, water skiing, and some-
times, fishing may be eliminated because the mass of vegetation phys-
ically impedes such activities. Dense plant populations have been as-
sociated with causing stunted fish populations and poor fishing. Plant
nuisances emit vile stenches, impart tastes and odors to water supplies,
reduce the efficiency of industrial and municipal water treatment, im-
pair aesthetic beauty, reduce or restrict resort trade, lower water-
front property values, cause skin rashes to man during water contact,
and serve as a desired substrate and breeding-ground for flies.
Phosphorus in the elemental form is particularly toxic, and subject to
bioaccumulation in much the same way as mercury. Colloidal elemental
phosphorus will poison marine fish (causing skin tissue breakdown and
discoloration). Also, phosphorus is capable of being concentrated and
will accumulate in organs and soft tissues. Experiments have found
concentrations of phosphorus in marine fish from water containing as
little as 1 mg/L.
Radioactivity
Ionizing radiation is recognized as injurious when absorbed in living
tissue in quantities substantially above that of natural background
levels. It is necessary, therefore, to prevent any living organism -
VI-18
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DRAFT
humans, fishes, and Invertebrates - from being exposed to excessive
radiation. Beyond the fact that radioactive wastes emit ionizing
radiation, they are also similar in many respects to other chemical
wastes. Man's senses cannot detect radiation until It Is present
in massive amounts.
To be a significant factor in the cycling of radionuclides in the
aquatic environments, plants and animals must accumulate the radio-
nucl ide, retain it, be eaten by another organism, and be digested.
However, even if an organism with radionuclide is not eaten before
it dies, its radionuclide can enter the "biological cycle" through
organisms decomposing the dead organism into elemental components.
Plants and animals which become radioactive in this way do, thus,
pose a health hazard when eaten by man.
Aquatic life may receive radiation from radionuclides present in the
water and substrate, and also from radionuclides that may accumulate
with their tissues. Humans can acquire radionuclides through many
different pathways. Among the most important are by drinking con-
taminated water and eating fish and shellfish containing concentrated
nuclides. When fish or other fresh or marine products which have
accumulated radioactive materials are used as food by humans, the
concentrations of the nuclides in the water must be furthe restricted,
in order to provide assurance that the total intake of radionuclides
from all sources will not exceed the recommended levels.
In order to prevent dangerous radiation exposure to humans, fish, and
other important organisms, the concentrations of radionuclides in
water, both fresh and marine, must be restricted.
Sulfldes
Sulfides are oxidizable, and therefore can exert an oxygen demand on
the receiving stream. Their presence in amounts which consume oxygen
at a rate exceeding the oxygen uptake of the stream can produce a con-
dition of insufficient dissolved oxygen in the receiving water. Sul-
fides also impart an unpleasant taste and odor to the water and can
render the water unfit for other uses.
Sulfides are constituents of many industrial wastes, such as those from
tanneries, paper mills, chemical plants, and gas works. They are also
generated in sewage and some natural waters by the anaerobic decompos-
ition or organic matter. When added to water, soluble sulfide salts,
such as Na2S dissociate into sulfide ions, which in turn react with the
hydrogen ions in the water to form HS- or H2S, the proportion of each
depending upon the resulting pH value. Thus, when reference is made to
sulfides in water, note that the sulfide is probably in the form of HS-
or H2S.
VI-19
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Owing to the unpleasant taste and odor that result when sulfides occur
in water, it is unlikely that any person or animal will consume a harm-
ful dose. The threshold of both taste and smell was reported to be
0.2 mg/L of sulfldes in pulp mill wastes. For industrial uses, however,
even small traces of sulfides are often detrimental. Sulfides in Ir-
rigation waters are of little significance.
For fish, the toxicity of solutions of sulfides increases as the pH value
is lowered, i.e., the hUS or HS-, rather than the sulfide ion, appears
to be the principal toxic agent. In a test in water containing 3.2 mg/L
of sodium sulfide, trout overturned in two hours at 9 pH, in 10 minutes
at 7.8 pH, and in four minutes in 6 pH. Inorganic sulfides have proved
fatal to sensitive fishes, such as trout, at concentrations between
0.5 and 1.0 mg/L of sulfide, even in neutral and somewhat alkaline
solutions.
Temperature
Temperature is one of the most important and influential water quality
characteristics. Temperature determines what species may be present;
activates the hatching of young, regulates their activity, and stimu-
lates or suppresses their growth and development; attracts, and may
kill when the water becomes too hot or becomes chilled too suddenly.
Colder water generally suppresses development. Warmer water generally
accelerates activity and may be a primary cause of aquatic plant
nuisances when other environmental factors are suitable.
Temperature is a prime regulator or natural processes within the water
environment. It governs physiological functions in organisms and,
acting directly or indirectly in combination with other water quality
constituents, affects aquatic life with each change. These effects
include chemical reaction rates, enzymatic functions, molecular move-
ments, and molecular exchanges between membranes within and between
the physiological systems and the organs of an animal.
Chemical reaction rates vary with temperature and generally increase
as the temperature is increased. The solubility of gases in water
varies with temperature. Dissolved oxygen is decreased by the decay
or decomposition of dissolved organic substances, and the decay rate
increases as the temperature of the water increases, reaching a maxi-
mul at about 30 C (86°F). The temperature of stream water, even
during summer, is below the optimum for pollution-associated bacteria.
Increasing the water temperature increases the bacterial multipli-
cation rate when the environment is favorable and the food supply
is abundant.
Reproduction cycles may be changed significantly by increased temperature
because this function takes place under restricted temperature ranges.
VI-20
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DRAFT
Spawning may not occur at all when temperatures are too high. Thus, a
fish population may exist in a heated area only by continued immigration.
Disregarding the decreased reproductive potential, water temperatures
need not reach lethal levels to decimate a species. Temperatures that
favor competitors, predators, parasites, and disease can destroy a
species at levels far below those that are lethal.
Fish food organisms are altered severely when temperatures approach or
exceed 90°F. Predominant algal species change; primary production is
decreased; and bottom-associated organisms may be depleted or altered
drastically in numbers and distribution. Increased water temperature
may cause aquatic plant nuisances when other environmental factors are
favorable.
Synergistic actions of pollutants are more severe at higher water temper-
atures. Domestic sewage, refinery wastes, oils, tars, insecticides, de-
tergents, and fertilizers deplete oxygen In water more rapidly at higher
temperatures, and the respective toxicities are likewise increased.
When water temperatures increase, the predominant algal species may
change from diatoms, to green algae, then at high temperatures blue-
green algae finally because of species temperature preferentials.
Blue-green algae can cause serious odor problems. The number and dis-
tribution of benthic organisms decreases as water temperature increases
above 90 F, which is close to the tolerance limit for the water's popu-
lation. This could seriously affect certain fish that depend on benthic
organisms as a food source.
The cost of fish mortalities resulting from their returning to cooler
water after being attracted to heated waters in winter may be consider-
able.
Rising temperatures stimulate the decomposition of sludge, formation of
sludge gas, multiplication of saprophytic bacteria and fungi (particularly
in the present of organic wastes), and the consumption of oxygen by putre-
factive processes, thus affecting the aesthetic value of a water course.
In general, marine water temperatures do not hcange as rapidly or range
as widely as those of fresh waters. Marine and estuarine fishes, there-
fore, are less tolerant of temperature variation. Although this limited
tolerance is greater in estuarine than in open water marine species,
temperature changes are more important to those fishes in estuaries
and bays than to those in open marine areas, because of the nursery
and replenishment functions of the estuary that can be adversely af-
fected by extreme temperature changes.
VI-21
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DRAFT
Zinc
Occurring abundantly in rocks and ores, zinc is readily refined into a
stable pure metal and is used extensively for galvanizing, in alloys,
for electrical purposes, in printing plates, for dye-manufacture and
for dyeing processes, and for many other industrial purposes. Zinc
salts are used in paint pigments, cosmetics, Pharmaceuticals, dyes,
insecticides, and other products too numerous to list here. Many of
these salts (e.g., zinc chloride and zinc sulfate) are highly soluble
in water; hence, it is to be expected that zinc might occur in many
industrial wastes. On the other hand, some zinc salts (zinc carbonate,
zinc oxide, zinc sulfide) are insoluble in water; and consequently, it
is to be expected that some zinc will precipitate and be removed readily
in most natural waters.
In zinc-mining areas, zinc has been found in waters in concentrations
as high as 50 mg/L. In effluents from metal-plating works and small-
arms ammunition plants, it may also occur in significant concentrations.
In most surface and ground waters, it is present only in trace amounts.
There is some evidence that zinc ions are adsorbed strongly and perma-
nently on silt, resulting in inactivation of the zinc.
Concentrations of zinc in excess of 5 mg/L in raw water used for drink-
ing water supplies cause an undesirable taste which persists through
conventional treatment. Zinc can have an adverse effect on man and
animals at high concentrations.
In soft water, concentrations of zinc ranging from 0.1 to 1.0 mg/L have
been reported to be lethal to fish. Zinc is thought to exert its toxic
action by forming insoluble compounds with the mucous that covers the
gills, by damage to the gill epithelium, or possibly by acting as an
internal poison. The sensitivity of fish to zinc varies with species,
age and condition, as well as with the physical and chemical charactei—
isties of the water. Some acclimatization to the presence of zinc is
possible. It has also been observed that the effects of zinc poisoning
may not become apparent immediately, so that fish moved from zinc-
contaminated (after k to 6 hours of exposure) to zinc-free water may
die bS hours later. The presence of copper in water may increase the
toxicity of zinc to aquatic organisms, but the presence of calcium or
hardness may decrease the relative toxicity.
Observed values for the distribution of zinc in ocean waters vary widely.
The major concern with zinc compounds in marine waters is not one of
acute toxicity, but rather of the long-term sublethal effects of the
metallic compounds and complexes. From an acute toxicity point of view,
invertebrate marine animals seem to be the most sensitive organisms
tested. The growth of the sea urchin, for example, has been retarded
by as little as 30 mg/L of zinc. Zinc sulfate has also been found to
be lethal to many plants, which could impair its agricultural use.
VI-22
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DRAFT
To^al Dissolved Solids
Total dissolved solids consist mainly of carbonates, bicarbonates,
chlorides, sulfates, nitrates, and phosphates. Sulfate concentrations
of 500 mg/L have been reported to be Inhibitory to anaerobic digestion,
and NaCl concentrations of 10,000 mg/L are reported to be inhibitory
to biological treatment.
Pollutants of Specific Significance
In addition to the parameters already discussed, there are pollutants
specific to various individual industry categories of the Miscellaneous
Chemicals industry. These will be covered as applicable to the industry
di scussions.
VI-23
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DRAFT
A. Pharmaceut i ca1 Indust ry
Review of Raw Waste Load (RWL) data indicates that the pollutants of
special significance to the Pharmaceutical industry in addition to
BODj-, COD, TOC, TSS and NH,-N, are: mercury, cyanide, ammonia nitrogen,
organic nitrogen, and total phosphorus. The raw waste loads computed
for all parameters analyzed in the field are presented in Table VA-4,
except for BOD-, COD, TOC, TSS, and NH,-N (which are presented in
Table VA-1). 5 ^
Mercury and Cyanide
Numerous synthetic mercuric salts are used by the Pharmaceutical
industry to produce medicinal products and disinfectants. Cyanide
salts are used by the industry as catalysts in certain chemical
synthesis processes (amination). The presence of mercury and/or cyanide
in wastewaters from these processes may have toxic effects on the
biological unit operations of a wastewater treatment plant, and thus
cause it to be ineffective.
Toxicity is classified as either acute or chronic. Acute toxicity is
characterized by the rapid onset of negative physiological effects
upon exposure, whereas chronic toxicity is usually manifested by the
appearance of negative physiological effects after a prolonged dosage
of a chemical at concentrations below the acute level. The latter
effect is often the result of the accumulation of the toxic compound
in the tissues of the organism. One complicating factor in trying to
understand toxicity is the synergistic or antagonistic effect of various
chemicals. For example, mature fish have been killed by 0.1 mg/L of
lead in water containing 1 mg/L of calcium, but have not been harmed
by this concentration of lead in water containing 50 mg/L of calcium.
'The U.S. Public Health Service (USPHS) Drinking Water Standards"
specify a maximum allowable cyanide concentration of 0.01 mg/L, as CN~.
"U.S. Environmental Protection Agency Preliminary Draft of Interim
Primary Drinking Water Standards" proposes a limit of 0.002 mg/L of
mercury.
Only minimal concentrations of mercury and cyanide were observed in
most of the RWL data. This is attributed to the various in-plant
pollutant abatement measures currently practiced in the Pharmaceutical
industry (i.e., metals recovery, cyanide destruction). It is emphasized
that the end-of-pipe treatment models proposed in this study should be
used in conjunction with these in-plant practices. Their expanded
use, wherever feasible, and improvement of current in-plant contaminant
reduction systems are also encouraged.
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DRAFT
Nitrogen
Ammonia nitrogen and organic nitrogen have been previously discussed
as "pollutants of limited significance." High concentrations of
organic and inorganic nitrogen were observed in the RWL data for the
Pharmaceutical industry. As Federal, state, and local effluent dis-
charge standards become more stringent, it is inevitable that maximum
allowable discharge limitations will be adopted for the various forms
of nitrogen, and that nitrogen removal will become a major requirement
of the Pharmaceutical Industry. However, the selection of ammonia and
organic nitrogen discharge standards shall be related to local con-
ditions.
Phosphorus
Phosphorus compounds are used by some segments of the Pharmaceutical
industry. High total phosphorus concentrations were observed in the
raw water from subcategories A, Ci, and Co plants. Phosphorus is often
a limiting nutrient in many water courses; consequently, elevated
phosphorus concentrations often lead to algae blooms and steady de-
gradation of impounded waters. The selection of standards for discharge
of phosphorus shall be related to local conditions.
VI-25
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DRAFT
B. Gum and Wood Chemicals Industry
Review of RWL data indicates that the pollutants of special signifi-
cance to Gum and Wood Chemicals industry are: oil, phenol, total
dissolved solids, and heavy metals. Tables VB-2 and VB-3 contain
RWL data for five of the six subcategories in the Gum and Wood
Chemicals industry (excluding the Char and Charcoal Briquet sub-
category, which involves no discharge of process wastewater
pollutants).
Oil
Oil RWL data for the following subcategories reflect relatively high
concentrations for the Gum and Wood Chemicals industry. The follow-
ing RWL data are summarized from Table VIB-1.
Subcategory Product RWL Concentration
mg/L
B Gum Turpentine and Rosin kk]
D Tall Oil, Pitch and Fatty
Acids 325
F Rosin Derivatives 356
The oil RWL consists mainly of oil of vegetable origin and not
petroleum-based free oil. Oils of vegetable origin at significant
concentrations have been reported as being not inhibitory to bio-
logical treatment. However, efficient reduction of TSS (which is
necessary for effective biological treatment) would require prior
reduction of any oils to low concentrations.
Phenol
The following are phenol RWL's which were found to be of significance
in this industry:
Subcategory Product RWL Concentration
mg/L
D Tal1 Oi1, Pitch and Fatty
Acids 20.5
F Rosin Derivatives 61.5
Equalization of the wastewater before biological treatment will
minimize slug loads and the consequent inhibition of the biological
population.
Vl-26
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DRAFT
Total Dissolved Sol ids
Total dissolved solids in Gum and Wood Chemicals wastcwatcrs vary
dramatically from one category to another. The following is a summary
of TDS, SO^, and Cl data from Table VIB-1:
Subcategory Product RWL Concentration
TDS SOU Cl
mg/L mg/L mg/L
B Gum Turpentine & Rosin 3,6^0 2$k 189
F Rosin Derivatives 7,^80 12.9 178
Metals
Metals such as zinc were found in the wastewaters from subcate-
gories B and F. The following zinc RWL data are summarized from
Table VIB-1.
Subcategory Product Zinc RWL Concentration
mg/L
B Gum Turpentine and Rosin 15.5
F Rosin Derivatives 6.80
The zinc in Subcategory F is attributed to catalyst losses, but no
such zinc catalyst is used in Subcategory B. Consequently, it
would appear that the presence of the zinc in Subcategory B indicates
a cross contamination between the gum turpentine and rosin derivative
production areas within one of the plants surveyed.
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DRAFT
C. Pesticides and Agricultural Chemicals Industry
The raw waste loads computed for all parameters analyzed are presented
in Tables VIC-1 through VIC-5, except for 8005, COD, TOC, oil and
grease, and TSS (which are presented in Tables VC-6 through VC-10).
Pollutants of special significance, in addition to those above, are:
Subcateqory A -_ Halogenated Organic Pesticides
Of the pollutants examined, oil and grease and phenol are significant
parameters for subcategory A process wastewaters. Oil and grease
exist in process wastewaters due to organics scrubbed from vapor
streams, entrainment in decanted aqueous layers, as well as washdown,
run-off, spills and leakage in the process areas. Loadings in the
plants visited ranged from less than 0.1 kg/kkg to ^3 kg/kkg of final
product. Since oil wastes result from intermittent flows, instantaneous
values could at times be, much higher. The phenol raw waste loads appear
minor and since biological treatment will effectively remove phenol,
concentrations in the final plant effluent should be minimal.
.Subcategory B - Organo-Phosphorus Pesticides
Review of RWL data indicates that the pollutants of special significance
to subcategory B are: oil and grease, phenol, cyanide, tota1-phosphorus,
NH3~N, and TKN. Besides lubricating oils and process separable organics
washed into the sewer system during area washdowns, sources of oil and
grease common to this category are organics scrubbed from vapor streams.
Oil loadings vary from plant to plant, but tend to be low. However,
oil wastes are often carried to the sewer system by intermittent flows;
accordingly, instantaneous concentrations can be high. As the pesticides
in this subcategory are phosphorus-based, the presence of high amounts
of total-phosphorus in the process wastewaters is not unexpected. The
total nitrogen concentrations in raw process wastewaters were considered
significant. Analytical results showed ammonia nitrogen to be the major
contributor to the total nitrogen loading. Significant cyanide concen-
trations were not observed in all subcategory B process wastewaters;
however, it was found to be present in significant concentrations in
certain individual plants,
Subcateqory C - Organo-Nitrogen Pesticides
Significant pollutants for subcategory C wastewaters are: oil and
grease, cyanide, and Nh^-N. Oil and grease is present in varying con-
centrations in process wastewaters. It is attributable to carryover
of separable organics into the wastewater system from various process
VI-28
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DRAFT
units. The presence of cyanide (CN) concentrations above 0.02 ppm
was observed In the process waters of some of the plants in the sub-
category. Although not a problem for the subcategory as a whole, it
is significant for specific products, depending on raw materials used
and products manufactured. Analyses for nitrogen show that the major
portion of the total nitrogen is due to ammonia (NH3-N).
Subcategory D - Metallo-Orqanic Pesticides
Of the pollutants examined, oil and grease and heavy metals are the
most significant parameters when considering process wastewaters
from the metallo-organic pesticides industry. Oil and grease exist
in process wastewaters due to organic carryover, and rinse and washdown
operations. Limited data are available on composite oil loadings, but
actual instantaneous concentrations can be high since most oily wastes
result from intermittent flows. Various heavy metals are used in the
production of subcategory D pesticides. In most instances, the heavy
metal used will show up in the process wastewater and will require
control.
Subcategory E -Formulators and Packagers
Of the pollutants examined, significant parameters vary according to
the particular category of formulation process. Significant character-
istics for water-based formulators include oil and grease, total-
phosphorus, TKN, and, in some cases, cyanide and heavy metals. For
solvent-based and dry formulators, significant characteristics include
tota1-phosphorus, TKN, and, in some cases, cyanide and heavy metals.
Although the available oil and grease data for this sector of the
industry is very limited, knowledge of the processing techniques indi-
cates that oil and grease can potentially enter the plant sewer system.
Principal sources are cleanout and washdown wastes. Oil loadings tend
to be more of a consideration with water-based formulations rather
than with the other categories. Although data was limited, total-
phosphorus, cyanide, and heavy metal loadings can be significant for
certain product formulations.
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DRAFT
Adhesive and Sealants Industry
Parameters of significance in the Adhesive and Sealants industry are
BODr. COD, and TSS. Additional pollutants which were found to be
of Specific significance in this industry were phenol, oil, chromium,
and TKN. The raw waste loads computed for all the parameters analyzed
have been presented in Tables \ID-k and VD-5 in Section V of this report.
In Subcategory A chromium, TKN, and oil may be present in signifi-
cant quantities in the wastewaters from the manufacture of animal
glue. Phenol may be present in significant quantities in the
wastewaters from the manufacture of phenol formaldehyde resins
(Subcategory B or C).
The plants visited during the field survey did not generate sig-
nificant quantities of these pollutants. Nevertheless, the
possibility of discharge of large quantities of these materials
still exists at certain types of plants.
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DRAFT
Explosives Industry
General parameters of significance in the Explosives industry are
BOD,-, TOC, TSS, TKN, lead, nitrates, and sulfates. Of special
significance to the Explosives industry is the problem of trace
quantities of the explosive products themselves.
Explosives such as TNT, NG, RDX, and HMX can all be considered
significant, because of their potential hazard, toxicity, or in-
hibitory effect on microorganisms (E-12). NG has been shown to
be amenable to biological treatment by some investigators (E-ll,
E-15), while others have found little success with biological
treatment (E-13).
Of particular interest to the industry are the pollutants associ-
ated with the manufacture of TNT, the production of which far
exceeds any other explosive in the military segment. These in-
clude color, sulfates, and saturation levels of TNT. The color
problem is manifested in the Red and Pink water previously dis-
cussed in Section IV. The sulfate problem is associated with the
Red-water condition. Saturation concentration of TNT in the
effluent is an obvious problem and must be abated.
The major problem with NC is NC fines, which generally are present
in quantities large enough to cause a significant TSS problem.
VI-31
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DRAFT
F. Carbon Black Industry
As discussed in Section V, only subcategory B involves a discharge
of process contact wastewater. In this subcategory, the process
quench water contacts a hot process stream of carbon black and
hydrogen formed by cracking natural gas. The quench water is
later condensed in a dehumidifier by further cooling by active
sprays. This contact water contains a relatively small amount
of carbon black as TSS. Since carbon black consists of elemen-
tal carbon (which exerts no oxygen demand), the only pollutant of
significance is TSS. TSS is measured by the organic and inorganic
solids removed when filtered through a preformed glass filter mat
in a Gooch crucible.
The thermal plant that was visited had a TSS concentration of
approximately 125 mg/L in the recirculated dehumidifier system,
and had no blowdown. Normally, a blowdown is taken from such a
closed-loop system. The TSS concentration of the blowdown would
probably be similar to the concentration measured in the closed
loop that was investigated.
The nature of the solids that are discharged is primarily elemen-
tal carbon. Therefore, the solids will exhibit no oxygen demand,
either chemical or biochemical, and will have no toxic effect on
any organisms within the receiving body, whether it be a stream
or a municipal treatment system.
VI-32
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DRAFT
G. Photographic Processing Industry
Review of analytical data indicate that the pollutants of special
significance in the Photographic Processing industry are ferro-
cyanide and silver.
Ferrocyan ide
Ferrocyanide concentrations were determined through a visual de-
termination method developed by American National Standards Insti-
tute (G-7). This analysis is not a standard method, but the results
do serve as a reasonable guide for differentiating between the
various forms of cyanide when used in conjunction with the results
from the total cyanide determination.
_i^
The ferrocyanide ion, Fe(CN)£ , comes from the bleach used in
most color processes, i.e. ferricyanide bleach. Ferrocyanide is
one of the most objectionable pollutants resulting from photographic
processing. Primarily, the complexed ion is potentially harmful
because it is converted to free, highly toxic cyanide in the presence
of sun light (G-8). Ferrocyanide concentration was k.7 mg/L in the
effluent from Plant 3^. A noteworthy finding at two particular plants
was that free cyanide had already evolved from the complexed form
when measured in the plant effluents.
SiIver
Silver is by far the most prevalent among the heavy metals in photo-
graphic wastewaters. Most of the silver enters the wastewater stream
from either the fix or bleach-fix bath overflow. At this point,
silver is in a soluble complex form as silver thiosulfate, which is
innocuous to secondary waste treatment plants and is much less toxic
than ionic silver (G-3). As reported in one study, essentially no
free silver ion results from photographic processing operations.
Silver measured in the effluent from Plant 3^ was 0.26 mg/L.
Vl-33
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DRAFT
H. HospitaIs
The pollutant raw waste loads computed for the Hospitals category
are presented in Tables VH-1 and VH-2.
Pollutants of special concern in the hospital category are silver
and mercury; these compounds in large enough concentrations will
have significant effects on the applicability of end-of-pipe treat-
ment technologies. Other pollutants of concern are barium and
boron.
The possibility of discharge of significant quantities of these
four materials from hospitals exists. However, the hospitals
visited during the sampling period discharged very small quantities
of these materials. Through proper handling, reduction of use,
and proper disposal and recovery techniques, the discharge of these
materials to the wastewater stream can be greatly reduced.
S i1ve r
Silver discharge is associated with the development of x-rays. If
the silver level is above the minimum, the silver recovery system
should be carefully reviewed. The most efficient method is to
collect all effluent from the processors and physically remove the
liquid from the hospital. Several service companies are equipped
to do this.
There are also in-line recovery units that basically work on the
principle of an electro-plating system. Disposal of scrap x-ray
film is also closely related to the scrap silver recovery. A de-
finite economic advantage can also be realized in hospitals devel-
oping large quantities of x-rays.
Mercury
Hospitals utilize mercury in its elemental form in manometers,
thermometers, and some electronic switches; the laboratories are
the biggest users of these items in hospitals.
Mercurous and mercuric compounds are used for medicinal purposes
in: diuretics, cathartics, and antiseptics; disinfectants for
cleaning; amalgams for dental procedures; and in tissue fixatives
in laboratories. Some mildew inhibitors containing mercury are
used by laundries.
VI-
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DRAFT
Ba r i urn
Many hospitals have been following a procedure of draining the
barium with a catheter into a plastic bag, which almost eliminates
the barium from the hospital's sewage. However, the possibility
exists for accidental discharge of barium into the waste stream.
Boron
Boron can be discharged into the sewer system via the automatic
processors in the x-ray department. The fixer has been found to
yield the greatest quantity of boron, but the developer also con-
tains significant quantities. In order to minimize the boron dis-
charged into the sewer system, boron-free fixers and developers
have been introduced by reformulation of the chemistry to eliminate
boron.
VI-35
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DRAFT
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
General
The entire spectrum of wastewater control and treatment technology is at
the disposal of the Miscellaneous Chemicals industry. The selection of
technology options depends on the economics of that technology and the
magnitude of the final effluent concentration. Control and treatment
technology may be divided into two major groupings: in-plant pollution
abatement and end-of-pipe treatment.
After discussing the available performance data for each of the industries
covered under Miscellaneous Chemicals, conclusions will be made relative
to the reduction of various pollutants commensurate with the following
distinct technology levels:
I. Best Practicable Control Technology Currently Available (BPCTCA)
II. Best Available Technology Economically Achievable (BATEA)
III. Best Available Demonstrated Control Technology (BADCT)
To assess the economic impact of these proposed effluent limitation guide-
lines on each of the industries, model treatment systems have been proposed
which are considered capable of attaining the recommended RWL reduction.
It should be noted and understood that the particular systems were chosen
for use in the economic analysis only, and are not the only systems capable
of attaining the specified pollutant reductions.
There are many possible combinations of in-plant and end-of-pipe systems
capable of attaining the effluent limitation guidelines and standards of
performance suggested in this report. The complexity of the Miscellaneous
Chemicals industry, however, dictated the use of only one treatment model
for each subcategory for each effluent level.
It is the intent of this study to allow the individual manufacturer within
the Miscellaneous Chemicals industry to make the final decision about what
specific combination of pollution control measures is best suited to his
situation in complying with the limitations and standards presented in
this report.
VI 1-1
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DRAFT
A. Pharmaceutical Industry
General
Pharmaceutical wastewaters vary in quantity and quality depending on
the type of manufacturing activities employed by the various segments
of the industry. However, in general, the wastes are readily treat-
able. The results of an industry survey indicate that a variety of
in-plant abatement techniques are utilized by pharmaceutical plants,
and, overall, in-plant wastewater control measures are being practiced
throughout the industry. The survey has shown that biological treat-
ment methods are the most prevalent end-of-pipe wastewater treatment
systems utilized by the industry.
In-Plant Pollution Abatement
It is within the manufacturing facility itself that maximum reduction,
reuse, and elimination of wastewaters can be accomplished. In-plant
practices are the major factor in determining the overall effort re-
quired in end-of-pipe wastewater treatment. A complete evaluation of
the effectiveness of in-plant processing practices in reducing waste-
water pollution requires detailed information on the wastewater flows
and pollution concentrations from all types of processing units. With
such information one could determine the pollutional effect of substi-
tution of one alternative subprocess for another, or of improving
operating and housekeeping practices in general. Unfortunately, this
kind of information is not available, as the survey contractor in most
instances was not permitted to review manufacturing processes in suf-
ficient detail to develop such information.
Despite this lack of specific process wastewater data, there is infor-
mation of a more general nature which indicates substantial wastewater
pollution reduction through in-plant control. Specific in-plant tech-
niques that are important in controlling waste discharge volumes and
pollutant quantities are discussed below:
Housekeeping and General Practices
In general, operating and housekeeping practices within the Pharmaceu-
tical industry are excellent. The competitive nature of the industry,
combined with strict regulations from the Food and Drug Administration,
requires most producers to operate their plants in the most efficient
manner possible. There are numerous examples of good housekeeping
practices utilized throughout the industry; a few of the better prac-
tices used by exemplary plants are described in the following discussion
1. All of the plants visited in subcategory D (mixing/compounding
and/or formulation) carried out their routine cleaning most
efficiently by vacuum cleaning. Most facilities utilized "house"
VI 1-2
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DRAFT
vacuum systems equipped with bag filters. This practice has
resulted in a substantial reduction in the concentration of pol-
lutants and volume of wastewater generated.
2. The use of portable equipment in conjunction with central wash
areas is a common practice by many plants throughout the industry.
This practice provides better control over the possibility of
haphazard dumping of "tail ends" of potentially harmful pollut-
ing material to the sewer.
3. Quality control laboratories are an integral part of the Pharm-
aceutical industry, and solvent and toxic substance disposal
practices within the laboratories are further evidence of the
apparent industry-wide commitment to good housekeeping. Standard
practice throughout the industry is to collect toxic wastes and
flammable solvents, especially low-boiling-point solvents like
ethyl ether, in special waste containers located within the lab-
oratories. Disposal of these wastes varies within the industry,
but the most prevalent practice is to have the wastes disposed of
by a private contractor or by on-site incineration.
I*. Spills of both liquid and solid chemicals, not only inside produc-
tion areas, but in general plant areas such as roads and loading
docks, can lead to water pollution. In most of the pharmaceutical
plants visited a comprehensive spill prevention and cleanup pro-
cedures program was an integral part of the plant's good house-
keeping procedure. Several plants visited during the survey had
excellent spill prevention programs and have efficiently reduced
the amount of water used for spill cleanup through the use of
vacuum collection devices and "squeegees".
5- Stormwater runoff from manufacturing areas, under certain circum-
stances, contains significant quantities of pollutants. One exem-
plary technique for controlling such discharges, observed at
several plants during the survey visitations, consisted of con-
tainment and monitoring of Stormwater for pH. If the stormwater
pH exceeds present limits it is then automatically diverted to
the waste treatment facility. Uncontaminated stormwater is dis-
charged without further treatment.
6. The survey indicated that disposal of off-specification batches
to the sewer system is not a wide-spread practice because of the
high value of the product. Most of the subcategory D plants
visited reprocessed their off-specification liquid formulation
batches and either discharded the off-specification solid .products
in a landfill or reformulated them when possible. Plants in
other subcategories, when reprocessing is not possible, either
incinerate off-specification batches or collect them in drums
and dispose of them via a private disposal contractor.
VI 1-3
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DRAFT
Process Technology
Many of the newer pharmaceutical plants are being designed with
reduction of water use and subsequent minimization of contamination
as design criteria. Improvements which have been implemented in
existing plants are primarily dedicated to better control of manu-
facturing processes and other activities with regard to their
environmental aspects. Examples of the kinds of changes which
have been implemented within plants surveyed are:
1. The use of barometric condensers (Figure VIIA-l) can result
in significant water contamination, depending upon the nature
of the materials entering the discharge water stream. This
could be substantially reduced by substituting an exchanger
for water sprays as shown on Figure VIIA-l. As an alternative,
several plants are using surface condensers to reduce hydraulic
or organic loads.
2. Water sealed vacuum pumps often create water pollution problems.
Several plants are using a recirculation system as a means of
greatly reducing the amount of water being discharged. These
systems often require the recycle water to be cooled.
3. The recovery of waste solvents is a common practice among plants
using solvents in their manufacturing processes (subcategory A -
Fermentation Products; subcategory C - Chemical Synthesis
Products; and to a lesser extent subcategory B - Biological
Products). However, several plants have instituted further
measures to reduce the amount of waste solvent discharge. Such
measures include incineration of solvents that cannot be re-
covered economically and "bottoms" from solvent recovery units
and design and construction of solvent recovery columns to strip
solvents beyond the economical recovery point.
A. One plant (19) producing large amount of organic arsenic elimi-
nated the discharge of this toxic substance by recovering the
arsenic. Arsenic-laden waste streams are segregated and concen-
trated before being reused. Non-recoverable arsenic residues
are drummed and shipped to an approved landfill.
5. Several techniques have been employed by various subcategory A
plants in an effort to reduce the volume of fermentation wastes
discharged to end-of-pipe treatment systems. These include
concentration of "spent beer" wastes by evaporation and dewater-
ing and drying of waste mycellia. The resulting dry product in
some instances has sufficient economic value as an animal feed
supplement to offset a part of the drying cost.
6. One plant (01) has installed automatic COD monitoring instru-
mentation, and others have utilized pH and TOC monitoring to
permit early detection of process upsets which may result in
excessive discharges to sewers.
VN-/f
-------
DRAFT
FIGURE VIIA-1
BAROMETRIC CONDENSER
CUSTOMARY
WATER VAPOR IN
/ I »
COOLING WATER
FOR 10-MILLION-BTU/HR DUTY,
COOLING WATER AT 85°,
OUTLET TEMPERATURE AT 125°
PROCESS WATER 10,000 LB/HR
COOLING WATER 250,000 LB/HR
TOTAL 260,000 LB/HR
CONTAMINATED WATER
SUBSTITUTION OF AN AIR FAN
WATER VAPOR IN
1
PROCESS WATER
COOLING WATER
TOTAL
i !
10,000 LB/HR
0
10,000 LB/HR CONTAMINATED WATER
L"
-------
DRAFT
7. Several plants (08, 12, 17) in subcategory B (Biological Products)
segregate the spent eggs used In virus production and the waste
plasma or blood fractions used in blood fractionation procedures.
These were disposed of by incineration at all plants.
8. Substitution of chemicals in this industry may be possible; how-
ever, the research program required to obtain FDS approval can
cost as much as the original studies to obtain approval of the
product.
9. Some plants practice ocean discharges or deep-well injection
following a pretreatment to dispose of process wastewater. Recent
regulations tend to limit the use of ocean discharge and deep-well
injection because of the potential long-term detrimental effects
associated with these disposal procedures.
Recycle/Reuse Practices
Recycle/reuse can be accomplished either by returning wastewater to
its original use, or by using it to satisfy a demand for lower quality
water. The recycle/reuse practices within the pharmaceutical industry
are varied and only a few examples are described briefly below:
1. Reduction of once-through cooling water by recycling through
cooling towers is used in numerous plants and results in tre-
mendously decreased total effluents.
2. Dilute waste scrubber waters are collected by one pharmaceutical
(01) plant and are used to wash equipment. Although this
practice is not applicable to all segments of the industry it
can lead to a substantial reduction in water usage and should be
considered in situations where it does not pose a serious threat
to product contamination.
3. Several plants (17) reuse waste deionized rinse water for cooling
tower makeup.
I*. Waste cooling water from one plant (18) was collected in an
aesthetically located pond and held as a source of water for
fire protection.
At-Source Pretreatment
The survey indicated that at-source pretreatment was practiced by
very few plants on an industry-wide basis. Those manufacturing
plants utilizing at-source pretreatment were all in subcategory C.
The particular pretreatment processes utilized are discussed below:
Cyanide Destruction
The purpose of the cyanide treatment is to reduce high levels of
cyanide from raw waste streams by alkaline chlorination prior to
VI I-6
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DRAFT
discharging the waste into an activated sludge treatment system.
The treatment of cyanide wastes by alkaline chlorination involves
the addition of chalorine to a waste of high pH. Sufficient
alkalinity, usually Ca(OH)2 or NaOH, is added prior to chlorin-
ation to bring the waste to a pH of about 11. Violent agitation
must accompany the chlorination, to prevent the cyanide salt from
precipitating out prior to oxidation and hydrolysis. About 7 to
9 pounds each of caustic soda and chlorine are normally required
to oxidize one pound of CN to N£ and CO-2. However, variation
can be expected, depending on the COD and alkalinity of the
waste. Destruction of 99-7 percent of cyanide has been achieved
by one plant (11).
Cyanide removal can also be accomplished by electrolytic de-
struction (A-26) and by ozonation (A-27). Mercury removal can
also be accomplished by other techniques (A-18) such as sulfide
precipitation, ion exchange, reduction or adsorption.
Mercury Removal
One manufacturing plant (02) in subcategory C produces a product
requiring the use of mercury. The waste from this process
contains about 25 mg/L of mercury. In order to protect the
biological treatment system utilized to treat the plant's chemi-
cal wastes, the mercury-contaminated wastewater is pretreated.
Pretreatment consists of exposing the waste to zinc under the
proper chemical conditions to permit the amalgamation of the
two metals. The mercury concentration has been reduced to less
than 5 mg/L, the contents of the holding tank are mixed with
other chemical wastes to further reduce the mercury concen-
tration before it is discharged to activated sludge treatment.
The mercury-zinc sludge is disposed of by a private disposal
contractor.
Ammonia Removal
Two plants (05, 11) in subcategory C uses ammonia compounds in
its manufacturing process resulting in waste streams containing
2.5 to 3-0 percent ammonia. A steam stripping column is utilized
to reduce this concentration to about 0.6 percent after which it
is mixed with other chemical waste streams to dilute it before
treatment by an activated sludge system. The stripped ammonia
is returned to the process and reused.
Sewer Segregation
Wastewater quantity is one of the major factors that affect the cost
of waste treatment facilities. In order to provide efficient treat-
ment to the wastes originating within a pharmaceutical plant it is
VI 1-7
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DRAFT
important to consider segregation of concentrated waste streams,
since it frequently simplifies waste treatment problems. Preferably,
the wastewaters should be segregated into several streams to econo-
mize treatment of the following various types of wastewater:
1. Strong waste streams.
2. Weak waste streams.
3. Contaminated stormwater from padded process areas and tank farms.
*». Special wastes such as spent caustics, spent acids, waste solvents
and metal-bearing wastes.
Segregation and incineration of strong waste stream is being practiced
by many pharmaceutical plants; however, potential for further segre-
gation still exists. It is conceivable that plant utilizing a variety
of manufacturing processes could further separate their waste streams
to optimize the overall treatment efficiency of their waste treatment
program. For example, some plants might find that the most cost-
effective waste treatment program would include incineration of
extremely concentrated waste, biological treatment of intermediate
strength waste, and dilution of weak strength wastes with the effluent
from the biological treatment plant. The feasibility of such an
approach should be examined by plants when considering treatment
systems for achievement of BATEA effluent limitations.
Separation of stormwater runoff is practiced through the industry
and, as discussed previously, this practice often facilitates the
isolation and treatment of contaminated run-off. The isolation of
wastes containing pollutants that may require specialized treatment
is also a demonstrated practice in the Pharmaceutical Industry which
permits effective removal of such pollutants as metals, arsenic,
ammonia, cyanide and other chemicals that may be toxic or inhibitory
to biological treatment systems.
Segregation of non-contact cooling water is also practiced within
the industry. This practice not only reduces the quantity of waste-
water that must be treated, but also facilitates water reuse either
prior to or after treatment.
End-of-Pipe Control Technology
Table VIIA-1 indicates the types of wastewater treatment technology
observed during the survey and the treatment systems identified by
consultation with Regional EPA Offices. End-of-pipe control tech-
nology in the Pharmaceutical Industry relies heavily upon the use
of biological treatment methods. When used, pretreatment most often
consists of equalization basins to minimize shock organic loads,
VI 1-8
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neutralization to insure optimum environmental conditions are present,
and clarifiers for removal of solids. Other pretreatment systems
observed include cooling of waste to reduce temperatures and use of
roughing filters to reduce organic loadings. Efluent polishing was
utilized by many plants, and systems observed included polishing
ponds, cascades and sand filters. Odor control and phosphate re-
moval systems were also observed. One pharmaceutical plant (01)
manufacturing subcategory A and C products utilized thermal oxidation
and a liquid evaporation process to treat their wastewaters. No
activated carbon adsorption systems were observed.
Though the present practice is to select a biological treatment method
as an end-of-pipe treatment, other treatment techniques are emerging
with good potential. The evaporation and the thermal oxidation of
strong wastestreams are becoming more attractive for those waste-
waters which have significant fuel value. In some case, high fuel
requirement would discourage the use of such techniques. Deep well
injection and ocean disposal are being practiced for strong chemical
wastes, but the recent regulation trend limits the use of ocean dis-
charge and deep-well injection because of the potential long-term
detrimental effects associated with these disposal procedures. As
a result of Public Law 93~523, EPA is in the process of developing
guidelines which cover deep-well injection of potentially hazardous
wastewaters. Other techniques including reverse osmosis, ultrafil-
tration, ozonation and ion exchange are being studied and have good
potential. For treating strong pharmaceutical wastewater, an acti-
vated sludge system using pure oxygen system is utilized by a pharma-
ceutical plant. The pure oxygen system has an additional advantage of
odor control.
One of the initial criteria used to screen pharmaceutical plants, for
the field survey, was the degree of treatment provided by the waste-
water treatment facilities. During the survey program historical
wastewater treatment plant performance was obtained when possible.
The historical data were analyzed statistically, and the individual
plant's performance evaluated.
After this evaluation, a group of exemplary plants were selected on
the basis of operation and performance. The historical treatment
data from the exemplary plants were analyzed statistically to formu-
late the basis for developing BPCTCA effluent criteria. A summary
of these statistical analyses is presented in Table VIIA-2. The
amount of analytical data used in the statistical analyses are in-
dicated in the "data base" column of Table VIIA-2, and the removal
efficiencies and effluent concentrations shown correspond to 90, 50
and 10 percent probability of occurrence.
During the survey program, 24-hour composite samples of influent and
effluent of the wastewater treatment plant over a two to five day
VI 1-10
-------
O.HC
-------
DRAFT
period were collected in order to verify the plants' historical
performance data, as well as to provide a more complete wastewater
analytical profile. The performance characteristics which were
observed during the survey are presented in Table VIIA-3.
Of the fourteen biological treatment plants visited, five treated
multiple subcategory wastes (Plant Nos. 02, Qk, 05, 09, 19). The
summary table above illustrates that there is no significant differ-
ence in the removal efficiencies for exemplary plants treating
multiple subcategory wastes and those treating single subcategory
wastes.
Historical treatment plant data was reviewed so that it would be
possible to quantify BPCTCA reduction factors, which would then be
applied to raw waste load values for each subcategory in order to
develop effluent limitations guidelines. On the basis of historical
performance data for the exemplary biological treatment plants, the
following treatment efficiencies were selected as being applicable
for the development of BPCTCA treatment technology, on the basis of
data presented in Table VIIA-3-
Subcategori es
Parameters A, B, Ci, D, & E Subcategory C2
BOD5 93% 99%
COD 89% 99%
TOC 81% 99%
Selection of the reduction factors for subcategory C2 was based on
observed performance of one thermal oxidation plant. The plant
observed obtained BOD5, TOC and COD removal in excess of 99 percent;
however, in order account for the miscellaneous streams being dis-
charged separately, 99 percent removal was selected as being appli-
cable for BPCTCA technology.
In addition to BOD5, COD and TOC the other major pollutant to be
considered is total suspended solids (TSS). As indicated in
Tables VIIA-2 and VIIA-3, limited historical TSS removal data were
available and survey TSS removal data exhibited a wide range in re-
moval efficiency. As previously mentioned, the majority of treat-
ment plants surveyed were biological treatment systems.
Such treatment systems generate biological solids which must be re-
moved before discharge of the effluent and unless one is thoroughly
familiar with a particular plant's operation, it is difficult to
interpret TSS data. For this reason, recommendation concerning TSS
will be based on effluent concentration.
Since flocculator-clarifiers with polymer addition have been used in
other industries to reduce TSS in effluents, this process can also
VI1-12
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VII-IJ
-------
DRAFT
be applied in the Pharmaceutical Industry as a demonstrated tech-
nology capable of achieving low effluent TSS concentrations. On
this basis a BPCTCA TSS effluent limitation of 50 mg/L is recom-
mended for subcategories A, Cj and C- and 20 mg/L for subcategories B,
D and E.
In order to measure the economic impact of the proposed effluent
standards, model biological treatment systems were developed for
each subcategory. The end-of-pipe treatment models were designed
for each subcategory based on Raw Waste Loads (RWL) . The prime
design parameter in BPCTCA and BADCT treatment models is BOD,- re-
moval , whereas COD and TOC removal were considered as secondary
design parameters. In the case of BATEA treatment models, COD and
TOC were the prime design parameters.
The use of biological treatment models for BPCTCA is done only to
facilitate the economic analysis and is not to be thought of as the
only technology capable of meeting the effluent limitation guide-
lines and standards of performance presented in this report.
Activated Carbon Adsorption
No activated carbon treatment systems were observed during the
survey; consequently, to investigate the possibilities of using
activated carbon technology on the effluents from biological treat-
ment plants treating pharmaceutical wastewaters, a series of carbon
isotherms were run at standard conditions using a contact time of
30 minutes. The results of the carbon isotherm tests are presented
in Tables VIIA-4, VIIA-5, and VIIA-6. Average performance values
for subcategories A and C, are as follows:
Highest
Parameter Carbon Exhaustion Rate Pollutant Removal Observed
(Ibs removed/1 b carbon) (percent)
COD 0.69 80
BODr 0.02 77
TOC 0.48 80
Ideally, pilot-plant continuous column studies should be run in order
to generate design data. However, inspection of the data in Tables VIIA-9
and VIIA-10 indicates carbon adsorption has potential for subcategories A
and C., with regard to cost-effective wastewater treatment. The treatment
facilities were sized using general conservative criteria from operating
systems.
In order to develop BATEA effluent criteria the following treatment
efficiencies were judged to be reasonable based on the available data,
data presented in process Design Manual for Carbon Adsorption (A-24)
and the experience of the contractor.
VI 1-1
-------
DRAFT
Table VI IA-k
Summary of COD Carbon Isotherm Tests
Performed on Biological Treatment Plant Effluent
Pharmaceutfcal Industry
Plant No. Subcategory Carbon Exhaustion Rate Highest Soluble BOD
Removal Observed
Ibs. COP
Removed
Ib. Carbon
19
08
14
11
20
05
A&CI 1.22
B Test Not
E Test Not
G! 0.45
A 0.40
D&E Test Not
Conclus
Cone 1 us
Conclus
Ibs.
1000
2
ive
i ve
11
5
i ve
Carbon
gal
.98
.3
.4
,
8k
71
81
VI I-15
-------
DRAFT
Table VUA-5
Summary of BQDs Carbon Isotherm Tests
Performed On Biologtcal Treatment Plant Effluent
Pharmaceutical industry
Plant No. Subcatecjory Carbon Exhaustion Rate Highest Soluble BOD
19
08
14
11
20
05
A&C
B
E
C1
A
D&E
Ifas. BOD5 Removed Ibs. Carbon
Ib. Carbon 1000 gal .
0.021 8. Jk
0.011 3.79
Test not conclusive
Test not conclusive
Test not conclusive
Test not conclusive
Removal Observed
(.%}
77
80
I
VII-16
-------
DRAFT
Table VllA-6
Summary of TQC Carbon tsotherm Tests
Performed on Biological Treatment Plant Effluent
Pharmaceutical Industry
Plant No. Subcategory Carbon Exhaustion Rate Highest Soluble TOC
Ibs. TOC Removed 1bs. Carbon Removal Observed
1b. Carbon 1000 gal. (%1
11 Ci 0.68 2.8 83
20 A 0.25 2.3 77
05 D&E Test not conclusive
VI1-17
-------
DRAFT
Pol 1utant Subcategories A, B, C1, D and E
Removal Efficiency!
(Percent)
COD 80
BOD5 77
TOC 80
'incremental over BADCT filtration effluent.
Dual-Media Filtration
Effluent filtration by use of dual-media filters cannot be considered
a demonstrated technology for the Pharmaceutical Industry. During
the plant survey visit use of this technology was not observed.
Consequently, historical data needed to quantify the effectiveness
of effluent filtration were not available.
In order to quantify the effectiveness of effluent filtration, samples
of biological treatment plant effluents were collected and filtered,
using filter paper, to determine the fraction of effluent BOD5, COD
and TOC attributable to suspended solids. Results of these tests
are presented in Table VIIA-7. Based on this data, the experience
of the contractor, and information contained in the literature, the
following suspended pollutant to TSS relationships were selected for
the purpose of determining BODj, COD and TOC removals obtainable by
dual-media filtration:
BOD5 - COD _ TOC
TSS ~ ' ' TSS" " 1' ; TSS" °" 2
These valves are based on 1.^2 Ibs COD, 0.53 1 bs TOC, . „__ _ 0 __-
—ib~vss— and vss = °-8 TSS
VI1-18
-------
DRAFT
Table VIIA-7
Results of Filtratic-n Tests
on Biological Treatment Plant Effluent
Pharmaceutical Industry
Plant Subcategory TSS A BODq A COD A TOC A BOD^ A COD A TOC
mgTL mg/L mg/L mg/L TSS TSS TSS
114 0.21 3.7 0.30
1.6 2.8
1.4
1.5
5 0.33 3-0 0.83
20
19
1/4
08
05
A
A,c,
E
B
D,E
380
80
14
25
6
81
128
0
0
2
1398
220
19
38
18
A Pollutant = Total effluent pollutant concentration - soluble pollutant
concentration
VII-19
-------
DRAFT
B. Gum and Wood Chemicals Industry
In-Plant Pollution Abatement
The Gum and Wood Chemicals industry is characterized by relatively sophisti-
cated process equipment which has been developed to maximize product yield
and reduce air and water pollution. The fact that a number of the plants
discharge to municipal treatment facilities has no doubt also influenced
both water usage and pollutant levels.
Water management and plant age are the two major factors to be considered
when discussing in-plant pollution abatement. As a whole, the industry
practices good water management. However, instances of poor water manage-
ment were observed, with resulting high wastewater flows. Age of equipment
primarily has an impact on the cost-effectiveness of modifying process equip-
ment to minimize pollution or to segregate storm and process wastewaters.
Since it is not possible, at the present time, to quantify the effects of
water management and equipment age, in general terms, these factors should
be handled on a case by case basis. This is particularly feasible in light
of the fact that less than five percent of the plants in the Gum and Wood
Chemicals industry discharge to surface waters.
End-of-Pipe Treatment
During the study, seven plants in the Gum and Wood Chemicals industry were
surveyed and a summary of the treatment technology observed is presented in
Table VIIB-1. Plants 59 and 5** provide their own wastewater treatment facili-
ties, while Plants 58 and 55 discharge to municipal treatment plants after pre-
treatment.
VII-20
-------
DRAFT
Table VIIB-1
Treatment Technology Survey
Gum and Wood Chemicals Study
Plant
Type of Treatment or Disposal Facility Code No.
Physica1/ChemicaI - Aerated Lagoon -
Oxidation Pond 59
Oil/Water Separation - Trickling
Filter - Oxidation Pond1 5/4
Lime Treatment (Odor Control) -
Evaporation Pond 52
To Municipal Treatment Plant -
No Pretreatment 58
To Municipal Treatment Plant -
Pretreatment includes equalization,
neutralization, and filtration 55
Wastewaters Drummed and Sent to
Industrial Landfill 57
No discharge of process wastewater pollutants 51
TOTAL
No. of Plants
Observed
1
Trickling Filter was not operational during the field survey, nor
was performance data available for the historic period reported in
Table VIIB~3.
VI1-21
-------
DRAFT
Biological Treatment^
During the plant survey program, 2l»-hour composite samples were obtained to
verify historical performance data which was made available by the plants.
The results of the plant survey data are presented in Table VIIB-2. Plant
No. 59 had experienced a shutdown before the plant visit resulting in the
measurement of abnormally high organic removals. Plant No. 5*» in contrast,
had low pollutant removals since the trickling filter was not operational.
The TDS and oil concentrations measured in the plant effluents in Table VIIB-2
are of such magnitude that they should not impact on the effluent TSS levels
which are attainable.
The historical wastewater treatment plant performance data obtained from
Plants No. 59 and Sk are presented in Table VIIB-3. The amount of data used
in the performance evaluation is indicated in the Data Base column of Table
VIIB-3. Influent pollutant concentrations were not recorded for Plant No. 59;
therefore, it was not possible to quantify its removal efficiency. The
historical data reported for Plant No. 5^ was the design basis proposed in
a consulting engineer's report which was developed from bench scale biological
treatability studies.
Table VIIB-3 also contains design criteria proposed for two plants producing
tall oil by-products, which were summarized from two other individual con-
sulting engineers' reports. The design criteria in these reports were also
developed from bench scale biological treatability studies simulating aerated
lagoon technology. Plants A and B were not visited during the field survey
program; however, the information is pertinent and was therefore included
in this plant evaluation phase.
The relative biodegradabi1ity of the wastewaters from Plant No. $kt A and B
were compared using WESTON's mathematical formulation for BOD5 removal rate
and loading ratios.1 The results of the comparison indicated that these
three wastewaters had relatively similar BOD5 removal rates and therefore
could be equitably compared in an evaluation of exemplary treatment plants.
Based on the previous analysis and the performance data in Table VIIB-3, it
was concluded that Plants 2, A and B are exemplary in the industry and that
the following average reductions can be achieved by exemplary treatment plants;
COD removal - 73 percent
BO05 removal - 95 percent
Effluent TSS - 50 mg/L
Process Design Manual for Upg_rajing_ Existing Wastewater Treatment Plants,
U.S. Environmental Protection Agency.October 197A, pp. 5-22.
VU-22
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VII-2^*
-------
DRAFT
Biological Treatment Plant Effluent Filtration
Filtration of biological treatment plant effluent is one method of providing
supplemental removal of solids and organic material. In addition, the use
of polishing ponds after biological treatment is a common method in the in-
dustrial wastewater treatment field for reducing effluent pollutants.
BODr Is reduced by filtration mostly by removing suspended solids. Therefore,
the percentage reduction of BOD will be significantly affected by the sus-
pended solids level in the treated effluent to be filtered.
The following analysis was developed to equitably quantify the expected BOD
reduction attributable to biological treatment plant effluent filtration:
Plant No. 54 Calculated
Biological Treatment Filtration Effluent
Pollutant (mg/L) Effluent Design Data From Plant No. 5*t
Total BOD5 187 172
Soluble BODq 162 162
Suspended 8005 25 10
TSS 50 20
The data for previous biological treatment effluent is taken from Table VIIB-3
and the consulting engineer's report referred to therein. The calculated
effluent concentrations were determined by calculations based on 60 percent
removal of the TSS and the corresponding suspended BOD component, resulting
in an overall BOD<- reduction of 8 percent. This 60 percent removal factor is based
on the contractor1^ experience in filtration of industrial wastewaters at
typical effluent TSS levels under discussion.
A corresponding analysis was performed using COD data and the results are
shown below:
Calculated
Plant No. 54 Filtration Effluent
Pol lutant (mg/L) Survey Data From Plant No. 54
Total COD 590 510
Soluble COD 457 457
Suspended COD 133 53
Soluble COD data was not available to correspond to the BOD^ values used in
the previous analysis; therefore, survey data from Table VIIB-2 was used.
An overall COD reduction of 13 percent would result with the use of effluent
fi1trat ion.
VII-25
-------
DRAFT
In summary, it is expected that the application of effluent filtration to bio-
logical treatment would result in the following average reductions:
COD removal - 13 percent
BOD5 removal - 8 percent
Effluent TSS - 20 mg/L
Carbon Adsorption
During the plant survey program, a sample of treatment plant effluent from
Plant No. 5^ was evaluated using a carbon isotherm. The results of the iso-
therm are presented in Table VIIB-4. The maximum soluble COD removal was
99 percent, which corresponds to an exhaustion rate of 0.59 pounds COD/
pound carbon.
In the past, Plant No. 59, which produces products in subcategories B and
F, evaluated the applicability of carbon adsorption for treatment of bio-
logical effluent. The results of the evaluation are summarized in Table
VIIB-5. Only 31 percent of the soluble TOC was removed with a carbon dose
of 100 gm/L. The fact that carbon did not prove cost-effective led to the
eventual recommendation that incineration be considered for their highly
concentrated waste streams. These two cases merely illustrate that carbon
adsorption is not universally applicable to all wastewaters in the Gum
and Wood Chemicals industry. However, alternative wastewater treatment
technology is available on a cost-effectiveness basis.
BPCTCA Treatment Systems
Biological treatment plant data was reviewed so that it would be possible
to quantify BPCTCA reduction factors. These factors, applied to standard raw
waste load figures for each subcategory, make it possible to generate recom-
mended effluent limitation guidelines. The previous discussions of biological
treatment indicate that the following pollutant reduction factors are con-
sistent with BPCTCA treatment technology:
Reduction Factors
Applied to Average BPCTCA
Parameter RWL
BOD,} 95 percent
COD 73 percent
TSS 50 mg/L
^Controlling Parameter.
VII-26
-------
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\l\ 1-27
-------
DRAFT
The BPCTCA effluent discharge recommendations will be made only for BOD. T5S
is expressed as a concentration limitation because BPCTCA raw waste loads are
minimal (as indicated in Section VI). The major source of TSS is biological
treatment plant effluents is biological solids.
BADCT Treatment Systems
Based on the previous discussion of biological treatment plant effluent fil
tration, the following equitable waste reduction factors commensurate with
BADCT treatment technology have been developed:
Reduction Factors
Applied to BPCTCA
Parameter Effluent Limitations
BOD1 8 percent
COD 13 percent
TSS 20 mg/L
^Controlling Parameter.
BATEA Treatment Systems
The quantity and quality of the data available for establishing BATEA reduc-
tion factors for the Gum and Wood Chemicals industry is sparse. Therefore,
a-\y recommendations made must be based on general experience in related in-
dustries. As additional performance data becomes available from the EPA
National Environmental Research Center and various EPA-funded demonstration
grants within the Gum and Wood Chemicals industry, the existing data base
will be expanded and updated. However, at this point in time the following
reduction factors are considered to be commensurate with BATEA treatment
technology:
Reduction Factors Minimum Monthly
Applied to BPCTCA Average Effluent
Parameter Effluent Limitation Concentration
(rngTU
BOD 70 percent 10
COD 70 percent
TSS 20 mg/L 10
VII -28
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
The characteristics of wastewaters generated within the Pesticides
and Agricultural Chemicals industry are highly variable and, in
general, require substantial pretreatment before they can be oxidized
by biological treatment systems. A variety of in-plant abatement
techniques are utilized by the industry. The most prevalent end-
of-pipe wastewater treatment facilities utilized by the industry
are biological oxidation systems.
In-plant Control
It is not possible to recommend a general list of process modifica-
tions or controls which would be applicable to all processes within
the Pesticide industry or even within one subcategory. Therefore,
the following discussion deals with individual techniques which have
general application to most instances where a particular unit pro-
cess or waste type is encountered.
The techniques described are based on both the practices observed
during the sampling visits as well.as those which have been de-
scribed in the literature. In most cases, they can be implemented
with existing processes or be designed into new ones.
The general effect of these techniques is to reduce both the pol-
lutant RWL and the volume of contact process water discharged for
end-of-pipe treatment.
Waste segregation is an important and fundamental step in meeting
the needs of the proposed standards of treatment. The following
factors generally form the primary basis for waste segregation,
containment, and isolation.
1. Wastewaters with high organic loadings frequently require
stripping or incineration as opposed to conventional end-
of-pipe treatment.
2. Wastewaters with high acidity or alkalinity should be
neutralized prior to being mixed with the rest of the
process wastewater.
3. Wastewaters with separable organics or solids should be
decanted or settled separately.
k. Wastewaters with high BOD loadings or toxic characteristics
reauire storage and gradual bleed-in facilities.
VII-29
-------
DRAFT
Dry or non-water techniques can be substituted for water-based tech-
niques. Potential areas where this type of substitution are pos-
sible are:
1. Substitution of an organic solvent for water in the synthesis
and separation steps of the production process. The solvent
can be recovered, whereas water used in these applications
is most frequently discharged.
2. Substitution of dry cleanup methods for water washdowns. This
is applicable for situations where liquid or solid materials
have been spi1 led.
In many cases decanter systems do not perform satisfactorily. This
can be caused by overloading, poor design, or flow surge charac-
teristics. In many cases, however, the problem is not so much in
the design but rather the decanter does not perform adequately
owing to the inherent characteristics of the waste stream. In such
instances, satisfactory overall organics removal can be obtained by
installing a coalescer downstream of the decanter.
Many pesticide products, intermediates, or wastes are recovered
via filtration and the filtrate is then discharged. In some
cases, the filtrate contains residual suspended solids owing to
incomplete filtration, and additional filtration of the filtrate
stream is called for.
Steam jet ejectors and barometric condensers can be replaced in
most cases with vacuum pumps and surfact condenser systems.
Barometric condenser systems are a major cource of organic con-
tamination and high hydraulic loads in pesticide plant effluents,
Specific In-Plant Control Technologies
Subcategpry A - Halogenated Organic Pesticides
Many of the chlorinated organic pesticides are manufactured via c
direct chlorination process. Residual chlorine and by-product
hydrogen chloride gases are frequently vented from this process;
the common technique of control involves water or caustic soda
scrubbing, resulting in a wastewater discharge. An alternative
approach applicable to some situations is to recycle the vented
chlorine gas and to recover the hydrogen chloride, as dry gas or
munatic acid.
Subcategory B - Organo-Phosphorus Pesticides
Preferably, detoxification of organo-phosphorus wastes should be
carried out at-the-source prior to combination with other plant
wastewaters. Following are several reasons for this.
VI1-30
-------
DRAFT
1. Detoxification can be more readily taken to a high degree of
conversion on a concentrated, segregated waste stream than
can be accomplished on a dilute, combined effluent.
2. The size of detoxification equipment can be minimized.
3. Higher temperatures, necessary for fast detoxification, can
be maintained more readily.
k. Lime addition, lime solids disposal, and acid back-neutralization
requirements are less for a concentrated waste stream.
High ammonia levels are a problem in some sectors of the organo-
phosphorus industry. Although ammonia stripping is not a proven
technology for this industry as a whole, there is potential for
ammonia stripping on those isolated waste streams with high am-
monia loadings. In most cases, it is necessary to recover the
stripped ammonia in order to avoid creating an air pollution prob-
lem. This latter requirement is generally the reason that ammonia
stripping is considered very costly as a solution to wastewater
ammonia problems.
Subcategory C - Organo-Nitrogen
Potentially some sectors of the organo-nitrogen industry can pro-
duce cyanide-laden waste streams. In such cases, the cyanide-
laden streams should pass through a cyanide removal unit where
the toxic cyanide group is oxidized with chlorine in an alkaline
medium to the significantly less toxic cyanate species. This tech-
nology is proven and, although not common to the Pesticide industry
(because of need rather than applicability), it is used in other
industries where cyanide wastes are encountered.
Subcategory D - Meta1lo-Organic
The manufacture of many of the metaMo-organic pesticides, partic-
ularly the carbamate-type products, generage wastewaters containing
metals. These metals require removal from the concentrated and
segregated process wastes prior to dilution with the other plant
effluents. Generally, the most appropriate meta1s-remova1 technology
is lime precipitation followed by sedimentation. If metals removal
is carried out on the concentrated individual stream as opposed to
the combined effluent, lime addition and disposal requirements are
minimized, acid back-neutralization needs are generally reduced, and
better overall metal removals can be achieved.
VII-31
-------
DRAFT
Subcateqory E - Formulators and Packagers
Formulation and blending operations are generally batchwise, and
equipment is multi-product in nature. Vessels are cleaned out
between batches to avoid cross-contamination. Many plants now
employ wash liquid storage tanks to hold vessel wash liquids in
order that they can be used for makeup purposes at the next formu-
lation of the same product. This procedure reduces the total
quantity of wastewater discharged and minimizes product losses.
This approach can be applied in plants where both water- and solvent-
based products are manufactured.
End-Of-Pipe Treatment
Table VIIC-1 summarizes the types of wastewater treatment tech-
nology observed during the survey. End-of-pipe control technology
within the Pesticides and Agricultural Chemicals industry generally
consist of biological oxidation systems such as activated sludge
or aerated lagoons.
Table VIIC-2 summarizes the characteristics of the final effluent
from the treatment plants of various pesticide facilities. The
data were obtained from historical records and analyses of samples
taken during plant visits (see Table VIIC-3). These data are used
as the basis for effluent limitations.
For the most part, the recorded values reflect good wastewater
management and practicable and appropriate in-plant or at-the-source
controls. The end-of-pipe treatment processes are appropriate for
their specific waste types and, in most cases, include biological
oxidation systems such as activated sludge or aerated lagoons.
Where possible, the data were based on current operations, but in
some cases, supplemented with data from well-designed pilot-plant
studies. Where a plant manufactures more than one subcategory of
pesticides, the combined effluent loadings are presented since it
was difficult to realistically separate the contributions of the
individual subcategories.
The use of biological treatment models is done only to facilitate
the economic analysis and is not to be thought of as the only
technology capable of meeting the effluent limitation guidelines
and standards of performance presented in this report.
VI1-32
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VII-34
-------
DRAFT
Table VIIC-3
Source of Historical Data - RWL
Pesticides and Agricultural Chemicals Industry
Plant No. Source
61 1) Pilot plant study February 1973, average of 6 samples.
2) In-house report, 26 September
62 Undated data supplied by plant personnel.
63 Average of k samples between March and April 197^.
6k Daily samples April 1972 to March 1973.
65 Monthly average, April 197^.
66 Undated data supplied by plant personnel.
67 Undated data supplied by plant personnel.
68 Based on plant-developed material balance.
69 Daily samples, 12-day period November 197^
70 Daily samples, January through May 197*+.
71 Based on plant-developed material balance.
72 Estimates by plant personnel.
VII-35
-------
DRAFT
D. Adhesives and Sealants Industry
In-Plant Pollution Abatement
In-plant control technology is dependent upon two major considerations:
1. Process requirements for water usage and the pollutants resulting
from these operations, such as unreacted raw materials, partially
reacted by-products which must be removed to meet major product
specifications, catalysts or accelerators required for controlling
the reactions, and additives necessary to provide the appropriate
chemical characteristics; and
2. Emission of pollutants into water streams due to poor housekeep-
ing practices, excessive use of water for control of hazardous
conditions such as fires, leaks, and spills due to inadequate
equipment maintenance, and accidental occurrences due to equip-
ment failure or personnel errors. The major way to control the
emission of pollutants from spills and leaks is to recognize the
potential that exists in various areas of the plants.
The process modifications and control measures discussed below are
applicable to all of the processes within the Adhesives and Sealants
industry because of the fact that all adhesive manufacturing proc-
esses are similar. The techniques described are based on both the
practices observed during the sampling visits and those which have
been described in the literature. In most cases, they can be either
implemented with existing processes or designed into new ones.
The reduction or elimination of water-borne pollutants in the Adhesives
and Sealants industry depends upon the following factors:
1. The replacement of present technology with technology which
generates fewer water-borne pollutants.
2. The age of the plant and equipment.
3. Process operational changes.
k. Maintenance and housekeeping.
Some of the specific in-plant pollution abatement measures which could
be adopted are:
1. Segregate discharge lines to reduce the quantity of wastewater to
be treated. This includes separate drainage systems for process
water, sanitary wastewater, and non-contact water and storm water.
VM-36
-------
DRAFT
2. Replace old piping and pumping systems with new ones.
3. Instead of simply filling and draining vessels and lines, use a
small controlled rinsing with subsequent recycling of the rinse
into the product.
k. Where controlled rinsing of tanks is not practical, manual
squeegeeing of clingage before rinsing can be practiced.
5. Pipe lines and pumping systems, where the rinse cannot be re-
worked or recycled, can be blown out with an air or inert gas
purge clingage in the final rinse.
6. Recirculate and reuse cleaning water and rinse water by treating
the water to remove solids.
7. Implement recovery systems for by-products from the process
stream (for example, grease recovery from animal glue manufactur-
ing). Good recovery practices depend on segregated collection
systems, proper plant piping systems, good housekeeping and
employee awareness.
8. One adhesive plant visited during the survey practiced complete
reuse of all contaminated washwater. The plant manufactured
urea formaldehyde and phenol formaldehyde resin adhesives and
recycled all washwater back into the products. Reuse systems for
contaminated wastewaters from other types of adhesive manufactur-
ing should be tried where they are not presently being employed.
Important in a complete reuse system is reduction in volume of
washwater, which can be achieved through better in-plant practices.
9. The Adhesives and Sealants industry should investigate the appli-
cability of the technology currently used by the Timber Products
industry in handling their glue washwater, which achieves zero
discharge. This technology has been applied to protein glues,
phenolic formaldehyde glues and urea formaldehyde glue. The
various in-plant operational and equipment modifications adopted
by the Timber Products industry have included:
a. Some plants wash process vessels several times a day, and
some wash only once a week. Less frequent washings can
reduce the amount of water to between 10 and 30 percent of
the original volume.
b. The use of steam to clean the process vessels and lines also
reduces water usage considerably. This is quite significant
since the frequency of washing for protein glue lines cannot
be reduced to the same extent as when synthetic resins are used.
VM-37
-------
DRAFT
c. The use of high pressure water lines and nozzles can reduce
the amount of water used.
d. The use of washwater for glue preparation and the reuse of
remaining washwater to wash process vessels will reduce
wastewater flows. Since part of the washwater is used in
the preparation of the glue, a volume of fresh water can
be added as final rinse in the washing of the process
vessels without increasing water use. A typical recycle
system is shown in Figure VIID-1.
Any combination of these modifications can be used to completely
recycle the washwater and eliminate discharge from protein, phenol
formaldehyde, and urea formaldehyde adhesive manufacturing processes.
End of Pipe Treatment
End-of-pipe treatment and control technology in the Adhesive industry
is not extensive. This is due in part to the fact that the water
pollution problems In the industry are usually relatively minor when
compared to other industries, and to the fact that a very large
percentage of the adhesive plants discharge directly to municipal
wastewater treatment facilities. The major efforts made by the
industry to reduce wastewater discharge have been to reduce the
amount of wastewater produced by reuse, conservation of water, and
containment of wastewaters that cannot be reused.
Many different methods for disposal of adhesive wastewater are
currently in use. Some treatment plants employ some type of settling
or holding pond or tank for the removal of suspended solids and, in
some cases, floating solids. During the industrial survey, no ad-
hesive plants which conducted complete treatment of their wastewater
discharges were found. The only type of treatment observed was
physical treatment for suspended solids removal. Therefore, there
are no exemplary treatment plants associated with the Adhesive
category of the Miscellaneous Chemicals industry with which to
determine the Best Practical Control Technology Currently Available
(BPCTCA).
Biological treatability studies have been undertaken to determine
the feasibility of this method for the treatment of protein, urea,
and phenolic glue wastewaters (D-9). It was found that protein and urea
glues possessed adequate nutrients for biological treatment, while
phenolic glue required supplemental additions of nitrogen and phos-
phorus. At detention times of 8, 12, and 16 hours, BOD removals of
90 percent and more were achieved at loadings as high as 50 pounds
VII-38
-------
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VII-39
-------
DRAFT
of BODc per 100 pounds of mixed liquor suspended solids for protein
glue wastes. Urea glue wastes were more slowly biodegraded and re-
quired longer detention times to achieve high degrees of BODr
removal.
Physical-chemical treatment studies involving neutralization and
settling of protein and phenolic glue wastewaters using alum,
sulfuric acid, or hydrochloric acid removed 99 percent or more of
the COD and TOC (D-9). However, these good removals were accompanied
by the production of large amounts of sludge. Glue solids can be
burned at high temperatures producing only small percentages of ash.
However, problems involving transportation of the glue waste to the
incinerator, injection of the waste into the furnace, air pollution
problems, and scaling of burners must be solved before incineration
can be an acceptable method of disposal.
Synthetic resins are used extensively in the Adhesive industry for
the production of synthetic resin adhesives (subcategories B and C).
Wastewater treatment technology for synthetic resins relies heavily
upon the use of biological treatment methods. These are supplemented
by appropriate initial treatment, especially by pH controls and
equalization, to insure that proper conditions are present in the
feed to the biological system.
Biochemical-oxygen-demanding pollutants in the wastewaters from
this industry are amenable to varying degrees of removal depending
upon the usual parameters associated with the specific biochemical
oxidation rates of the wastewaters. Table VIID-1 records average
BODc;, COD, and TSS wastewater concentrations found among wastewater
treatment plants selected as exemplary of practical technology in
the Synthetic Resin industry during the study to establish effluent
limitations guidelines and new-source performance standards for that
industry (D-ll). All the types of synthetic resins listed in
Table VIID-1 are used as raw materials in the Adhesives industry for
the production of synthetic resin adhesives. Although all 19 of the
wastewater treatment plants visited in the synthetic resin study employed
biological systems, the treatability of the different wastewaters un-
doubtedly influenced both the design and established operational
modes of practical wastewater treatment systems.
The treatment efficiencies selected as being applicable to sub-
category A for the determination of BPCTCA effluent limitations
are as follows:
Parameter Treatment Efficiency
Percent
BOD5 93
COD 93
Similar removals have been observed in pilot studies with similar
wastewaters.
VI I 40
-------
DRAFT
The increase in treatment efficiencies selected as being
applicable for the determination of BATEA effluent limitations
are as follows:
Parameter Treatment Efficiency
Percent
BODr ^9
COD ^9
The increase in treatment efficiencies over BPCTCA selected
as being applicable for the determination of BADCT effluent
limitations are as follows:
Parameter Treatment Efficiency
Percent
BODr 2
COD ^
Many factors govern the selection of treatment processes for a
particular industrial wastewater: the ability of the selected
system to provide adequate and consistent treatment; the
flexibility of the system; and the capital and operating costs
of the systems. An economic evaluation was undertaken for the
following treatment alternatives, all of which are considered
to have great potential in treating this type of wastewater:
1. Biological Treatment
2. Evaporation
3. Liquid Incineration
k. Activated Carbon
Taking both economics and the nature of the wastewater generated
by subcategories B and C (which has low, intermittent flow and
high concentrations of pollutants) into consideration, the
evaporation process was chosen.
The types of wastewaters generated by subcategories B and C have
been shown to be amenable to biological treatment with high
degrees of removal. However, evaporation proved to be the most
economical process for wastewater treatment. Also, the evaporation
process would attain higher degrees of BODr, COD, and TSS removals
VI I-
-------
DRAFT
than biological treatment. Due to lack of data on evaporation of
this type of wastewater, removals attainable by biological treatment
were applied to determine effluent limitations, as shown below:
Parameter Treatment Efficiency
Percent
BODr 93
COD 93
These treatment efficiencies should be conservative values when
liquid evaporation processes are applied.
V I I -42
-------
DRAFT
E. Explosives Industry
In-Plant Pollution Abatement
A significant amount of pollution abatement can be accomplished in the
Explosives industry simply by consistent adherence to good housekeeping
practices. Many of the final products such as ANFO and NCN are dry
mixed, while others involve only limited water use such as water gels
and slurries. Wastes generated from these products are primarily from
.spills, careless handling, leaks, and washdown of machinery and floors.
Such wastes have the potential to be almost completely eliminated by
dry cleanup, i.e. procedures involving sweeping and vacuum cleaning.
Process changes to reduce hydraulic loadings do not have much potential
in the commercial segment of the Explosives industry but because of
high volume have shown promise in the military manufacturing area.
In the manufacture of propellents, large quantities of waters are used
to transport them safely and to purify the product from one process step
to another. For this task, high-quality water is not required. Hence,
water reuse with perhaps slight treatment has a tremendous potential to
reduce the hydraulic loading. For example, such wastewater reductions
for nitrocellulose production in one of the plants visited could reduce
total plant discharge by 95 percent and overall propellent area discharge
by 87 percent; this change is in the planning stage. (E8)
The production of TNT is another area where significant reduction of
hydraulic loading can be attained. As a part of the military modern-
ization program, 100 percent reduction of current process water use
is possible and will be implemented within the near future at a large
army ammunitions plant. (E*f) (E5)
In general, good water management, whose focus is recycling process and
cooling water, can have a significant effect on hydraulic loading and
would significantly reduce treatment costs. For example at one AAP
in the current study, an overall plant water reduction (including cooling
as well as process water) reached 6 percent. This saved an estimated
$900,000 per year in pumping and treatment costs. Such substantial
savings show that water conservation practices can be economical as well
ecologically favorable. (E^t)
Separation of process and non-contact waters is not practiced universally.
This is technically feasible and would greatly reduce the hydraulic loadir
to a treatment plant, thereby reducing the cost, and is an essential first
step in economical pollution abatement.
Studies documented in Section XV have shown explosive wastes to be
treatable with present technology. However, prior to end-of-pipe
treatment, certain in-plant control measures will be mandatory.
VI I-
-------
DRAFT
Such measures are neutralization facilities, catch tanks on finishing
explosive lines, and other pretreatment techniques to ensure compat-
ability of raw waste load with the subsequent treatment system.
Treatment and Control Technology
In developing potential treatment technology for each subcategory,
sources of information will be laboratory studies, pilot plants,-
demonstration projects, facilities under construction, and fa-
cilities in operation. First, control technology will be dis-
cussed from the viewpoint of effluent water quality. After re-
viewing what has been accomplished and what is feasible, control
technology will be designed for each subcategory for BPCTCA, BATEA,
and BADCT.
The control technology for pH is neutralization. The pH of a dis-
charge can vary over extreme ranges; from plant visits it was
observed to range from 1 to 12. An example of such ranges can
be seen from the manufacture of NG, where the initial washing of
NG produces an acidic wastewater and subsequent sodium carbonate
washings yield an alkaline flow.
The problem of high-alkaline flows is significant in subcategory C,
e.g. the discharges from PETN, lead azide, and diazo production.
The problems of acidic flows are generally associated with the
manufacture of nitric and sulfuric acids as raw materials in the
production of explosives. However, as these materials are not
explosives they are covered under major inorganic industrial
category.
There are many acceptable methods for treating either acidic or
alkaline wastes, including: mixing acids and alkaline wastes and
the use of chemicals, such as lime, caustic or sulfuric acid to
neutralize the wastewaters.
BOD,, and COD
Current emphasis in treatment technology for both these areas is
on biological treatment. Activated sludge lagooning and spray
-------
DRAFT
irrigation are combinedat one commercial plant treating propellent
wastewater and this treatment technique attains excellent and
consistent results. One military installation is currently finalizing
the design of biological treatment facilities based on pilot plant
test data. (E1)
Solids
High dissolved solid concentrations come from the high nitrate,
sulfate and carbonate levels, and these will be addressed sep-
arately. Suspended solid generally are low in the Explosives in-
dustry. However, catch tanks and sumps are usually employed to
catch trace explosives prior to discharge. An exception to low
suspended solids in Explosives industry wastewaters is in the
manufacture of nitrocellulose. Here, large concentrations of NC
fines are present in the waste discharge from the purification
process. Treatment technology focuses on sedimentation, dissolved
air flotation, flocculation, granular filtration, and centrifugation.
Centrifuging has produced excellent results in pilot studies at a
military installation and will be implemented shortly. (E-^0
Nitrates
The U. S. Army has investigated several methods for abatement of nitrates.
Among these methods are biodenitrificat ion, algae harvesting, ion exchange,
and reverse osmosis, distillation, and land application. After initial
feasibility studies, the Army selected biodenitrification, ion, exchange,
and reverse osmosis as having the most potential. Current engineering
emphasis is placed on biological denitrificat ion. At least two plants
have plans for design. Pilot plant treatability studies of biodenitrifi-
cation on nitrocellulose waste have indicated 80 to 90 percent reduction
of nitrates on a consisten basis. Influent nitrate values ranged from
600 to 800 mg/L and the detention time was about one day.
Additional engineering studies have been performed utilizing reverse
osmosis and ion exchange. Excellent removal rates of 90 percent have
been obtained at a pilot plant level using reverse osmosis. Reverse
osmosis can be used to treat sulfates as well. At neutral pH, re-
moval rates of 90 to 99 percent for nitrates and sulfates, respectively,
were observed during this same pilot investigation. For nitrates
it appears that the economical limit of nitrates in the effluent is
approximately 20 mg/L as NO,-N. Hence, reverse osmosis could be a
means of nitrate recovery, while an additional step such as biodenitrifi-
cation may be necessary to reduce the smaller concentration of nitrates
to more acceptable levels.
VI I
-------
DRAFT
Problems associated with reverse osmosis are acid sensitive membranes
and concentrate disposal. (Elk). Ion exchange studies have shown
wastewater effluent with concentrations as high as 1,200 mg/L to
remove 99 percent, resulting in an effluent of 10 mg/L. (E2) (E3)
(E4) (E8). Chemicals used for regeneration of the resin are nitric
acid and ammonium hydroxide. Ammonium nitrate, a raw material in
certain explosives (ANFO, NCN, etc.) can be recovered in the
regeneration step.
Sulfates
Present in the water because of the use of sulfuric acid or, in the
case of TNT production, the sellite wash (red water), sulfates have
only recently received any attention as a pollutant. Hence, abate-
ment studies are only in the initial assessment stages. Existing
abatement involves incineration. However^ incineration leads
to air pollution (SO ), and the sodium sulfate ash disposed of in
landfill causes leacning problems. Several chemical processes
are being considered for reusing the ash. The most promising
involves a fluidized-bed reduction system which utilizes a
reducing gas to liberate hydrogen sulfide from the ash. The
hydrogen sulfide can then be used to manufacture sellite and,
hence, complete recycling. Additional methods under consideration
for controlling high sulfate discharge are reverse osmosis, ion
exchange, evaporation (combined with reverse osmosis to reuse
sulfuric acid), and calcination (precipitation with lime then
heating to recover sulfuric acid and lime).
Reverse osmosis has been investigated at the pilot scale, in com-
bination with nitrate removal. High sulfate removal efficiences
(99 percent or better) are reported even at acidic pH. However,
membrane hydrolysis at low pH greatly decreases useful membrane
life. In the absence of more resistant membranes, neutralization
would likely be required for the reverse osmosis feed stream.
This may result in precipitation and fouling of the membranes
by solids. (E-11)
The most technically feasible method of sulfate treatment appears
to be calcination. However, the solubility of calcium sulfate
is high (approximately 470 mg/L of sulfate), and lime treatment
may not be feasible for more stringent effluent requirements.
The use of barium to precipitate sulfate has been suggested in
the literature, but cost and the possiblity of exceeding ef-
fluent barium levels appear to be major disadvantages. (Ell)
The economic and technical difficulties associated with treatment
for pollutants such as sulfate have led to several applications
of waste disposal by land irrigation in the Explosives industry.
One such plant that goes through biological activated sludge,
lagooning and spray irrigation is presented achieving 95 percent
removal of sulfates. (Historical Data)
VI 1-46
-------
DRAFT
Trace Quantities of Explosives
Unique pollutants such as NG, TNT, and RDX can be hazardous and
toxic. (12)
Nitroglycerin (NG)
Treatment technology universally used for NG washwaters is catch
tanks. The catch tanks make it possible to recover by sedimentation
any NG that comes out of solution. However, this leaves the super-
natant waters at their saturation point upon discharge. At room
temperature, 20°C, the solubility of NG is recorded as 1,800 mg/L.
(See Table VIIE-1.) Therefore, during warm summer weather without
further treatment, NG wastewater could pose a safety problem,
especially if discharged into a cool mountain stream. If cooling
water is available, the cooling of NG prior to discharge could
recover additional product and decrease the waste load significantly.
Additional technology for the treatment of wastes high in nitro-
glycerin is only in the experimental stage. NG wastes containing
900 to 2,100 mg/L have been shown to be amenable to activated
sludge treatment. In one study, Koziorowski and Kucharski report
consistent success in treatment of influent wastes containing ^00
to 500 mg/L of NG at a detention time of 16 hours. (E14) It
has been demonstrated by Koziorowski and Kucharski that NG can
also be destroyed by quicklime. (E1^) Lime (up to 200 mg/L) was
added to the wastewater and allowed to react for three days; the
result was a non-explosive sludge, but the effluent was highly
alkaline. (E11) The Army has conducted experiments on the treata-
bility of NG by biological, physical/chemical, and ozonation methods.
With wastewater containing concentrations of NG and DNG (dinitroglycerin)
of 1,500 mg/L and 850 mg/L, respectively, the results show that NG
can be treated biologically and chemically, although with varying
degrees of success. It is generally considered that NG waste be
handled biologically together with other plant waste. (E11)
TNT
TNT has been shown to interfere with biochemical oxygen demand,
and implies an inhibiting or toxic effect. Klausmeier has con-
firmed this inhibiting, but not toxic, effect on soil micro-
organisms. (E21) Biological treatment of wastes high in TNT and
DNT (red and pink water) was performed by the Navy (1972). Reduction
has been successful only in the laboratory using specific cultures
and nutrients. At Crane Naval Ammunition Center, treatability
studies using activated sludge proved unsuccessful. Numerous other
treatability studies at Crane Naval Ammunition Center included
activated carbon, aerated lagoon, trickling filtration, and physical/
chemical mechanisms. Of these, activated carbon adsorption process
VII-
-------
Table VIIE-1
Summary of Treatment Investigations
Explosives Industry
Type of
Study
Pi lot
(3 month*,)
Oper.it ionol
Laboratoi y
Labor atoi y
Laboratory
Laboratory
Laboratory
Operat ional
Laboratory
Laboratory
Pi lot
Laboratory
Demonstra-
tion
Lab Unl t
(Pi lot)
Reference
U.S. Army
(PE2<*9)
OperoL ion a 1
Clai k, Oietz
Eng. Rept.
HAAP
Clark. Dietz
Eng. Rept.
HAAP
Clark. Dietz
Eng Rept
HAAP
Clark, Dietz
Eng. Rept.
HAAP
Clark, Dietz
Eng. Rept.
Operational
U.S. Army
PE 2<*9
Phase 1 1
U.S. Army
PE 2W
Phase 1 1
U.S. Army
PE 21*9
Phase 1 1
U.S Army
PE 2**9
Phase 1 1
U 5. Army
PE 2<*9
Phase 1 1
U.S. Army
PE 2^9
Phase 1 1
U.S. Army
PE 2**9
Phase 1 1
Percent Reduction
Treatment BOD COD TOC TKN N03 SOii
Activated 86.7 78.3
SI udge
(NG Waste)
Activated 92.8 ' 71.5 ' 90 2 Increaie 96 2 None
SI udge
(Propel 1 ant
Waste)
(Explosive Failed -(Filamentous Organism)
Waste)
Activated
Sludge
Trickling 83.7 72.9
Filters
Fixed Film 1*1 *» 9**. 9
Deni t rof i cat i on
Dual Media
F i 1 trat ion
A. C. -Note 77-6
Removes al 1
explos i ves
down to 0.0
mg/L
(Propel lant 72.0 ' 78.9 ' 88. 7 2 96.6 2 increase 59. l» '
waste ( Lagoon
Sp. Irr
(NG Waste) (Successful In Decomposing 350 mg/L NG & 130 mg/L DNG)
Decompose
NG & DNG by
Na2S
Using Lime Successful Decomposition
Oxidating
Agent
Ozone NG 20
DNG 1 00
(Propellant Excellent Removal of Dissolved Organics
Wastes)
Activated
Carbon
Inorganic 97.5
SOi,
NC Fines
Separation &
Centrifuge
Reverse 75 99
Osmosi s
Blodenitrlf Ication 70-90
VH-'lB
1.2
75
77.8
99
-------
• ii. ,-r
1 lu.lv
Pilot
Operation
Operation
Pilot and
Laboratory
Commercial
Demonstra-
tion
Laboratory
Laboratory
Pilot
Laboratory
Laboratory
Treatablllty
and Pilot
Laboratory
Tests
Bench
Scale
Pilot Plant*
Refer en^e
Pollution
Abatement
Review Aug.
1973
Pollution
Abatement
Review Aug.
1973
Pollution
Abatement
Review Aug.
1973
Harris, 1973
Pollution
Abatement
Review
Aug. 1973
Pollution
Abatement
Review
Aug. 1973
Harris, 1973
Harris, 1973
Harris, 1973
Harris, 1973
Harris, 1973
U.S. Navy
1972
Table VI IE-1
(Con t i nued)
Percent Reduction
T' c.-iti flit BOD COD TOC TKN NO}
Reverse Osmesis Impractical Due To High Pressure
Treatment of Red.
Water
(Plnkwater) 95 91.5-92.7
Activated
Carbon
(Reduction of TNT
99.5%)
(Plnkwater) -0»ta not atallabla-
Actlvated
Carbon
Blodenltrlfl- 70-97
cation
Ion Exchange 90-99
Reverse 90
Osmosi s
Blodenltrl- 95-99
flcatton
Ion Exchange 98.8
Countercurrant
Reverse 90
Osmosis
Calcium ppt of
sulfate waste
AC adsorption Regeneration of carbon Is feasible
TNT wastes
Activated Sludge Not successful
Aerated Lagoon Not successful
Trickling Filter Not successful
Chemical Precipitation Not Successful
Activated Carbon 98
50|»
None
95. 1*
95
successful
1SS
67
'D.it.i
Survey Data
-------
DRAFT
was recommended. Spent carbon from the adsorption column cannot
be regenerated at the present time and must be incinerated or
landfilled. (E13)
The Army has reached a similar conclusion regarding TNT. In tests
of reverse osmosis, ozonolysis, and activated carbon, only the
latter proved effective, reducing initial concentrations of TNT
in the range of 100 mg/L down to 0.05 mg/L. The Army recommended
development work in the regeneration of carbon, because it is
uneconomical at present. A promising method involves dissolving
the TNT in toluene then crystalling it by a drop in temperature
and filtration to separate the carbon. (E15)
If regeneration of carbon cannot be achieved, the incineration of
the spent carbon is-necessary. However, incineration, though in-
activating TNT and its derivatives, produces a waste high in sul-
fates (from the sel 1 i te purification process resulting in red and
pink water). This ash causes a major solid waste disposal. In
addition, leachate from its storage can cause ground-water con-
tamination. (E5) Reclamation of this ash is being investigated
by the Army. A fluid-bed reduction system is being tested presently
with the focus of regenerating selite.
RDX and HMX
The present removal of RDX and HMX from wastewaters by catch basins
has only partially alleviated the problem. The army has investi-
gated the following treatment methods at Holsten AAP reverse
osmosis, activated carbon adsorption, polymeric column adsorption,
and biological treatment. These treatment techniques are presently
being studied. Hence, a definite statement as to their success
cannot be drawn. However, one conclusion can be drawn; biological
treatment is feasible and will break down as much as 99 percent of
the explosives present. (E15)
End-of-Pipe Treatment
Due to the lack of effective treatment in all but exceptional cases
in the Explosives industry, treatment sytems will be proposed for
all subcategories based on the preceding discussion of laboratory
studies, pilot plant investigations, demonstrated projects, fa-
cilities designed, facilities under construction, and facilities
in operation.
Treatment systems were developed for the Explosives industrial sub-
categories for the following levels of treatment technology:
1. Best Practicable Control Technology Currently Available
(BPCTCA).
VI1-50
-------
DRAFT
2. Best Available Technology Economically Achievable (BATEA).
3. Best Available Demonstrated Control Technology (BADCT).
It should be noted that the treatment systems presented for each level
of technology are not the only systems that are capable of meeting the
effluent limitations prescribed. Moreover, within each subcategory
there may be exceptions to the suggested level of treatment due to
unforeseen complications. The objective of this section is not to
prescribe but to suggest feasible treatment systems that will satisfy
the effluent limitations guidelines developed in this report.
BPCTCA Treatment System
Of the six plants visited during the survey, only one operated a
treatment system other than neutralization and sedimentation. There-
fore, the levels of treatment for BPCTCA will be based on the per-
formance of this existing activated sludge plant. Laboratory and
pilot plant investigations summarized in Table VIIE-1 will be used
to verify these levels of treatment.
The results of nine months of data for this activated sludge treatment
system is shown in the summary tabulation below. It should be noted
that this treatment system was designed for a propellant waste having
typical waste characteristics as indicated in Section V. The BPCTCA
treatment level indicated below includes the survey data as well as
historical data.
BPCTCA Treatment Level
Percent Reduction
Parameter _ of RWL _
BOD5 931
COD 721
TOC 902
TSS
»Based on historical data
-Based on 2^-hour composites from survey
Except average concentration not to exceed 50 mg/L.
VI 1-51
-------
Pretreatment Requirements for
BPCTCA Treatment System
Certain waste flows will have to be pretreated prior to discharging
l.o a central treatment facility = uch as the one proposed for BPCTCA.
The following problem .^astewaterb should be considered in that
category:
1. Discharges high in sulfate
2. Discharges high in TNT (red water, yel low v;at^ r, pink water)
3- Discharges high in NC fines
't. Heavy metals
Since no proof has been shown that pretreatment is absolutely
necessary, design and cost estimates will not be attempted. Instead,
suggested methods of abatement will be explored.
High sulfate concentration can disrupt a biological secondary treat-
ment system. Therefore, the removal of high sulfate concentration
by calcination may be a necessary pretreatment technique. TNT is
suspected of being toxic or an inhibitor of biological processes.
Wastes high in TNT may, therefore, require activated carbon ad-
sorption prior to discharge to a biological system to remove the
dissolved explosive and its isomers. High concentrations of NC
suspended solids could also disrupt a biological system. Removal
by the use of centrifuging has been shown to be economical.
Heavy metals concentration can be toxic to microorganisms and,
subsequently, disrupt the activated sludge process. If heavy metals
are a problem, some means of physical-chemical pretreatment will
necessarily have to be implemented.
BATEA Treatment System
Out of six explosives plants visited, only one had any kind of
treatment that could be considered as exemplary. Hence, oper-
ational performance data from this facility was used to
establish BATEA treatment levels; these levels was verified
by laboratory and pilot studies.
BATEA Treatment Levels
Percent Reduction of
Parameter BPCTCA Waste Effluent
BOD 72
COD5 79,
TSS 78
LxccpL average concentration not to exceed 20 mg/L.
VI I-52
-------
This percent reduction is based on lagooning and spray irrigation
as a treatment system. However, a system specifically designed
to remove dissolved and suspended explosive organics would be pre-
ferable. Therefore, a system using activated carbon has been recom-
mended for BATEA. Laboratory and pilot plant investigations in the
area of activated carbon (indicated in Table VIIE-1) have shown it
to attain comparable percentages of removal.
BADCT Treatment Systems
Not enough information could be gathered to quantify BADCT from
process changes in the Explosive industry. Therefore, any recom-
mendations made must be based on general experience in related
industries. However, new explosive plants initiating production
between now and 1983 should attain a level of treatment somewhere
between BPCTCA and BATEA. It is recommended that dual - media fil-
tration be used as an additional step after BPCTCA to comply with
BADCT.
On the basis of information derived from the contractor's previous
experience and EPA publications, the following percent reductions
are considered reasonable using dual -media filtration:
BADCT Effluent Reductions
Percent Reduction of
Parameter BPCTCA Effluent
BOD 8.0
COD * 13.0
TSS 60.0
VI1-53
-------
DRAFT
F. Carbon Black Industry
In-Plant Pollution Abatement
The elimination or reduction of in-plant pollution sources depends
upon any one or a combination of the following factors:
1. New plant process selection to minimize pollution. Present cor-
porate environmental awareness requires that the new environmental
impact of products and processes be evaluated.
2. The modification of process equipment to improve product recovery
or to minimize pollution.
3. Maintenance and good housekeeping practices to minimize pollution.
The competitive nature of the industry requires that most producers
operate their plants in the most efficient manner possible. This
necessitates good maintenance and housekeeping practices. However,
there are segments of the industry who have minimized maintenance
expenditures and whose management does not adequately fund their
environmental control staff nor support them in their efforts to
enforce rigid housekeeping regulations.
4. The age of the plant and process equipment as it impacts on pol-
lution. Poorly maintained process equipment does not warrant con-
sideration of its age. The real problem is that older equipment
generally pollutes more than new equipment. An example of the
impact of new technology on the Carbon Black industry is the use
of bag filters for carbon black recovery, accepted as state-of-
the-art technology. In the past, cyclones and wet scrubbers were
used, which generate larger quantities of wastewaters.
In addition, older plant layouts do not allow for pollution con-
trol and, in many cases, prohibit segregation of storm and process
waters.
End-of-Pipe Treatment
A summary of the types of treatment technology which were observed
during the field visits are listed in Table VIIF-1. Performance data
for these treatment plants were rather scarce.
V11-
-------
DRAFT
Table VIIF-1
Treatment Technology Survey
Carbon Black Industry
Subcategory Treatment Technology
A Settling/Evaporation
(no discharge)
82 A Settling Basin, Gravity
Fi1tration
83 B Evaporation/Settling Ponds
It is important to note that the treatment technology applied to sub-
category A was not for process contact sources. Rather, the tech-
nology was applied to treatment of stormwater runoff, utility water
and in some instances sanitary wastes (including shower facilities).
Plant 81 collected stormwater runoff from their property and from
adjoining property for use as quench water in their process. Also,
they were implementing a program to include their sanitary wastewater
within this treatment system.
Plant 82 treated miscellaneous utility discharges and stormwater run-
off by gravity settling followed by gravity filtration. At the time
of the plant visit, little discharge was observed. Again, this system
did not treat any process contact water. Plant 83 was a thermal black
plant. All process contact waters (from the dehumidifier system) were
collected in approximately seven acres of evaporation/settling ponds.
No discharge occurred from this system due to the high net evaporation
for the area. The sanitary wastes (including shower water) were also
collected by this system.
Gravity Settling and/or Gravity Filtration
During the plant survey program, historic wastewater treatment plant
performance data were obtained when available. Table VIIF-2 is a
summary of average treatment results attained by the plants surveyed.
The number of data points available were not statistically signifi-
cant. The information in Table VIIF-2 indicates only the relative
effectiveness of the applied treatment technology.
VI1-55
-------
DRAFT
Table VI IF-2
Wastewater Treatment Plant Performance Data
Carbon Black Industry
Plant Number Subcategory Flow Rate, gpm Effluent TSS, mg/L
Average Range Avg. , mg/L Range
82 A 18 12-26 12 6-19
83 B 9001 - 12^*2
iThe reelrculated rate, no discharge occurs from these ponds.
^Represents a single sample taken from the pond effluent-.
It must be emphasized that the data presented above is significant
only in that it illustrates the possible performance of applied treat-
ment technology. Both plants received wastewater from many different
sources, including sanitary wastewater, utilities and stormwater.
These data do not represent the application of these technology to
process contact streams.
BPCTCA Treatment Systems
Historical treatment plant data was reviewed to quantify BPCTCA re-
duction factors, which could then be applied to BPCTCA raw waste
load figures for each subcategory to generate recommended effluent
limitation guidelines. Based on the previous discussions of treat-
ment technologv, it is recommended that the following pollutant re-
duction factors be consistent with BPCTCA treatment technology:
TSS - *»0 percent reduction of RWL
BPCTCA effluent discharge recommendations will be made only for TSS.
A minimum concentration figure would be used when the calculated TSS
concentration was less than the minimum concentration limitation, as
the following example shows:
Min. TSS BPCTCA
Subcategory BPCTCA Effluent Limitations Concentration
(kg TSS/kkg) (SJgTT)
B 0.053 75
VI1-56
-------
DRAFT
In subcategory B, the effluent TSS-BPCTCA effluent limitation is
0.053 kg TSS/kkg product. When applied to actual plant flow RWL
data, the calculated TSS concentration would be 50 mg/L. In this
case, the minimum TSS concentration of 75 mg/L would apply and the
BPCTCA effluent limitation would be recomputed this concentration.
The new TSS effluent limitation would be 0.105 kg/kkg.
BATEA Treatment Systems
Waste reduction factors commensurate with BATEA treatment technology
have been formulated as follows:
Reduction Factors
Applied to BPCTCA Minimum Monthly Average
Parameter Effluent Limitation Effluent Concentration
(percent) (mg/L)
TSS 60 30
BADCT Treatment Systems
Waste reduction factors commensurate with BADCT treatment technology
have been formulated as follows:
Reduction Factors
Applied to BPCTCA Minimum Monthly Average
Pa ramete r Eff1uent Li m itat i on Effluent Concent rat? on
(percent) (mg/L)
TSS 60 30
VII-57
-------
DRAFT
G. Photographic Processing Industry
In-Plant Pollution Abatement
Regeneration and Reuse
Present state-of-the-art techniques can effectively reduce most of the
problems associated with photo-processing effluent loads (G-9). The
most advantageous system, both environmentally and economically, is
the regeneration and reuse of solutions.
Si 1ver Recovery
Basically there are three methods of recovering silver from photographic
processing solutions: metallic replacement, electrolytic plating, and
chemical precipitation. These methods can be used singly or in combina-
tion, depending on which is most suitable for the particular needs of
the user. These three methods are examined in detail.
Metallic Replacement
Metallic replacement occurs when a metal, such as iron, comes in contact
with a solution containing dissolved ions of a less active metal, such
as silver. The dissolved silver, which is present in the form of a
thiosulfate complex, reacts with solid metal (iron); the more active
metal (iron) goes into solution as an ion, and an ion of the less active
metal becomes solid metal (silver).
Silver ions will displace ions of many of the common metals from their
solid state. Zinc or iron can be used to recover silver from fixes.
Because of its economy and convenience, steel wool is the form of
metal used most often. Furthermore, the zinc that would be carried
into the drain is potentially a pollutant. Its use, therefore, is not
generally considered acceptable from an environmental standpoint.
The acidity of the fix is an important factor when using steel wool in
the recovery of silver. Below a pH of k, the dissolution of the steel
wool is too rapid. Above a pH of 6.5. the replacement reaction may be
so slow that an excessive amount of silver may be lost because of the
long reaction time required to recover the silver. Silver loss in
this case will depend on the flow rate through the cartridge.
Silver recovery by metallic replacement is most often carried out using
commercially available cartridges consisting of a sealed plastic bucket
containing steel wool. The fixer that comes out of a steel wool cartridge
will usually contain less than 50 mg/L silver. Common practice is to
replace the cartridge when the silver reaches 1,000 mg/L, as shown on a
silver test paper. With careful maintenance, 90% or more of the silver
in the fixer can be recovered.
VII-58
-------
DRAFT
Electrolytic Recovery
In the electrolytic method of recovery, silver is removed from fixing
baths by passing a controlled, direct electrical current between two
electrodes (cathode and anode) suspended in the fixer solution. Silver
is deposited on the cathode in the form of nearly pure silver plate.
The cathodes are removed periodically, and the silver is stripped off.
Electrolytic systems can be installed in two basic ways. One is to
de-silver the fixer overflow from a processing machine as it flows to
the sewer. The system can be operated for either a batch or a contin-
uous-flow cell. Another method is to remove silver from the fixer in
a continuously recirculating in-line system at approximately the rate
at which silver is being added by processing. The latter procedure has
the advantage of maintaining a low silver concentration in the proces-
sing bath so that the amount of silver carried out with the fixer into
the wash tanks is minimal. A modification of the circulating system
is to collect fixer overflowing from several processing machines, de-
liver it in a separate electrolytic system, and then reconstitute the
de-silvered fixer to supply the processing equipment again where recom-
mended by the manufacturer.
In-line electrolytic silver recovery can maintain the silver concentra-
tion in a recirculated fixer system between 500 mg/L and 1,000 mg/L.
When used as a tailing or terminal treatment, a silver concentration of
10 mg/L to 20 mg/L can be achieved.
Sulfide Precipitation
Silver may be precipitated from fixers and their washes with sodium
sulfide. The precipitation is quantitative in an alkaline solution,
and the resultant silver sulfide is one of the most insoluble substances
known. It has a solubility product of about 10~->0. The physical char-
acteristics are not as favorable as the chemical characteristics. Silver
sulfide tends to form colloidal suspensions. Its very small particle
size makes filtration difficult, and the filter cake produced is extremely
dense. Diatomaceous earth filter aid can be used to improve filtration.
About three grams of filter aid are required for each gram of silver if
a conventional filter press is used.
With sulfide precipitation it is possible to remove virtually all the
silver from both the fixer and the wash following the fixer. Tests on
experimental equipment have given results of less than 0.5 mg/L. The
actual concentration usually depends on the efficiency of the filtering
or settling step. Any silver lost is in the form of insoluble silver
sulfide particles.
There is no commercially available equipment designed to apply to most
processing situations; however, equipment is available for application
to smaller-volume graphic arts applications, and it is within the present
state-of-the-art to produce sulfide precipitation and filtration equip-
ment.
VI 1-59
-------
DRAFT
Regeneration of Perricyanide Bleach
The basis for all the regeneration methods is the use of a sufficiently
strong oxidizing agent that has reaction products compatible with or
used in the process. Since bromide is required in the bleach formula,
bromate, bromite, and elemental bromine have been used. Persulfate can
be used because some sulfate can be tolerated. Ozone, hydrogen peroxide
and electrolytic oxidation have also been used because they leave no
chemical by-products.
Persulfate Regeneration
In actual practice, persulfate is most widely used. This technique has
the advantages of being simple to use, involving no significant capital
expenditure, and requiring only comparatively safe and stable chemicals.
However, regeneration of a bleach with persulfate results in a build-
up of the sulfate ion that slows the rate of bleaching. The build-up
of sulfate is higher in bleaches for reversal products because of the
comparatively large amounts of persulfate used in the regeneration process,
In some processes, especially if squeegees are used to minimize water
carry-in, the sulfate build-up may require the sewering of up to 10
percent of the bleach for each regeneration cycle in order to maintain
adequate bleaching.
Ozone Regeneration
This process is characterized by the following reaction:
2Fe(CN)6~/f + H20 + 0^ —* 2Fe(CN)6"3 + 2(OH)~1 + 02
The pH of the bleach increases as the reaction proceeds; consequently,
it is necessary to add acid. Bromide is required in the bleaching
process; the use of hydrobromic acid, therefore, furnishes both the
bromide and the hydrogen ion. Theoretically, one bromide ion is re-
quired for each ferrocyanide ion that is oxidized to ferricyanide.
The hydrobromic acid avoids all build-up of sulfate and other unwanted
products. If in practice there is a slight build-up of bromide ion,
a small amount of sulfuric acid could be added without danger of high
sulfate build-up. Likewise, slight pH adjustments could be made with
sulfuric acid.
Developer Recovery
Developers become exhausted both by loss of active developing agents and
by increase of reaction products. The limiting factor Is usually the
increased bromide concentration. Two approaches may be taken to reuse
developers: 1) the reaction products can be removed so that the bulk
of the solution may be reused; or 2) specific chemicals can be separated
from the bulk of the solution and reused with or without further purifi-
cation.
VII-60
-------
DRAFT
Ion Exchange
The ion exchange generally can give a greater reduction in chemical
usage. As an example, bromide and developer decomposition products can
be removed by ion exchange from Eastman Color Developers; other constit-
uents are not affected. After passing through the column, the developer
is reconstituted to replenisher strength and is reused. This method
requires additional analytical work for regeneration of the resin.
t
Precipitation and Extraction
The recovery of specific chemicals may not have as great an effect on
reduced chemical usage as the removal of bromide by ion exchange, but
significant cost savings can be realized and certain non-biodegradable
organics can be removed. The most widely practiced application is the
recovery of couplers from the various color developers in the process
for Kodachrome film. The couplers are soluble in an alkaline solution
but precipitate at a neutral or acid pH.
It is common practice to use CCL to adjust the solution to pH 7 and
then remove the precipitated coupler by centrifuging. The coupler is
dried, assayed, and sometimes repurified.
Developing agents can be extracted with organic solvents using conven-
tional liquid-liquid- extraction techniques. One problem is that un-
wanted substances are also extracted, often making the chemical analysis
of the extract difficult. This technique is not in use at the present
time and is being considered only for possible use in the event of
shortages of certain chemicals.
Some of the difficulties with developer reuse are: chemical analysis
is needed; suitably scaled equipment is difficult to find; a higher
degree of operator skill is required; and these operations are not
always economically attractive.
Use of Squeegees
Effluent loads can also be minimized in the photographic process by the
correct use of mechanical aids (such as squeegees), which generally in-
hibit the carry-over from one tank to the next (G-10).
There are four general locations for squeegee action in the photographic
process:
1. After the photographic solution but prior to a wash
2. After a wash but prior to a photographic solution
3. Between two photographic solutions
4. After a wash but prior to drying
VII-61
-------
DRAFT
Generally, a squeegee following a photographic solution will have rela-
tively little effect on the replenishment rate of that solution. An
exception to this would be the first solution in the sequence, such as
a developer or prehardener. The first solution is usually alkaline and
causes a considerable swelling of the gelatin; consequently, large
amounts of chemicals are imbibed in the swollen emulsion. Solution re-
moved in this manner is not replaced by carry-over from any previous solu-
tion. The squeegee action here will retain most of the solution on the
surfaces of the film, thus possibly reducing the replenishment rate. The
advantage of the squeegee in this situation, however, is not only to
reduce the replenishment rate, but rather to increase chemical recovery.
The squeegee prevents the processing solution from being transported by
the film to the wash water which is generally discarded. Instead it
allows more of the solution to overflow where it is collected and ulti-
mately reused or treated to remove unwanted materials.
The squeegee following a wash, like the processing solution discussed,
will have little affect on the wash itself. Again, the water must go
somewhere and if the squeegee removes it from the film, the resulting
build-up of water will simply go out the overflow if the wash rates are
not reduced accordingly. The important effect of the squeegee in this
instance is evident by a reduction in replenishment in the next bath
caused by the reduction in dilution water. The reduction of dilution
water results in higher concentration in the bath, which generally
means both a cost savings to the processor and fewer chemical pollutants
going to the sewer.
Careful study is required when considering a squeegee between two photo-
graphic solutions. There may be some interdependence between the two
chemical baths that was designed into the process. By placing a squeegee
between them, the equilibrium could be upset, thus reducing the effective-
ness of the process.
Use of Holding Tanks
Large-scale processors operate on a continuously replenished system, not
in batches. Normal operations require no dumping of solutions. However,
because of an emergency, periodic shutdown, contamination, or exhaustion
of solutions, occasional disposal of a processing solution may be necessary.
If this is suddenly "dumped", it may shock load or overload wastewater
treatment facilities. This situation can be avoided by a controlled
discharge of the solution. A holding tank large enough to hold the
total volume of solution that might be reasonably expected to be dumped
at any one time is used, and the solution in the holding tank is bled
slowly to the waste water sewer taking advantage of the dilute wastewaters.
VI1-62
-------
DRAFT
End-of-Pipe-Treatment
Biological Treatment
Large-Scale Activated Sludge
An activated-sludge pilot unit is being operated on photographic proc-
essing wastes (G-if). The extended aeration unit has a capacity of
20,000 gpd and was chosen for its high potential for BODj reduction
and its low solids production. The processing wastes fed to the
extended-aeration plant were collected from nine processing machines.
These wastes which varied over a period of years, included effluents from
Ektaprint R, Ektaprint C, Ektaprint3 chemicals, and from the E-4, C-22,
CRI-I, and K-12 processes. The effluents from the machine flows were
collected and pumped to two 1,000-gallon fiberglass holding tanks. These
were used to smooth out surges and to provide a constant source of feed
for the treatment plant and insure a constant flow to the system.
During the first year of operation BOD_ reductions were low, because of
a combination of hydraulic overloading and poor sludge settling charac-
teristics, which caused high suspended solids in the effluent. As a re-
sult, the MLSS content in the aeration tank was low. This was remedied
by the installation of sand filters to increase MLSS by recycling the
backwash wastewater into the aeration tank. After the sand filters were
put into operation, BOD reduction immediately improved. Simultaneously,
the food to microorganisms ratio decreased because of the MLSS increase.
Lagoons
Lagoon ing and ponding are popular methods for treating industrial and
municipal wastes. However, a significant amount of acreage is required
for satisfactory treatment, and the degree of treatment is often unpre-
dictable because the process is very dependent upon the weather. The
use of surface mechanical aeration equipment or of diffused aeration
(i.e. aerated lagoons) has helped lagoons become an economical alterna-
tive in biological waste treatment of industrial wastes.
Several processing laboratories have used lagoons for treating their
photograp
from 30%
aerat ion.
photographic processing effluent. The overall BOD,, reductions ranged
from 30% to 90% depending upon the loading and the use of supplemental
VI I-63
-------
DRAFT
Physical/Chemical Treatment
Ozonation
Biological treatment experiments have shown that the photographic chem-
icals used in the largest quantity (such as thiosulfate, acetate, sulfite,
hydroquinone, and benzyl alcohol) respond well to biological treatment.
However, a small percentage of chemicals (such as color-developing agents
and EDTA) appear to be biodegraded only slowly or not at all. Consequently,
ozonation, a non-biological waste treatment system, has been tested to e-
valuate the treatability of such chemicals.
The results of these experiments are summarized in Table VIIG-I (G-1!).
Only acetate and glyctne were found to be untreatable, and ethylene
glycol, methanol, ferricyanide, and ethylene diamine marginally treatable;
the other chemicals are considered treatable. However, the degree of com-
pletion of the degrading by ozonation is subject to variation and is not
fully substantiated.
The suggested uses of ozone are: 1) as a preliminary treatment for over-
flow color developer solution; 2) as a preliminary treatment for solutions
that may contain substantial amounts of thiocyanate, formate, EDTA, or
black-and-white developing agents (other than hydroquinone); and 3) as a
means of tertiary treatment and disinfection for an overall mixed waste,
after that waste has first been treated biologically.
Activated Carbon Adsorption
The feasibility of treating various photographic processing chemicals and
solutions by activated carbon is summarized in Table VIIG-2.
As with ozonation, more of the photographic processing chemicals are treat-
able than are untreatable, but the group of untreatable or marginally
treatable chemicals is more significant than with ozonation.
VII-6/t
-------
DRAFT
Table VIIG-I
Summation of Ozonation Results (G- 11)
Photographic Processing Industry
Treatable Chemicals Unt rea table Chemicals
HAS Glycine
Benzyl Alcohol Acetate ion
Color Developing Agent
Thiosulfate
Sulfate
Hydroquinone
Kodak Elon Developing Agent
Phenidone
EDTA
Ferric EDTA Marginally Treatable
Formate Ion Chemicals
Fo rma1i n
Maleic Acid Ethylene Glycol
Eastman Color Print Effluent Methanol
Ektaprint 3 Effluent Ferricyanide
Flexicolor Effluent Ethylene Diamine
Synthetic Effluent from Combined Ektachrome ME-4
VI1-65
-------
DRAFT
Table VIIG-2
Feasibility of Treating Photographic Processing Chemicals with Activated Carbon (G- I I)
Photographic Processing Industry
Treatable Solutions
Ektaprint 3 Mixed Efflue'it
Ektaprint R Color Developer
Color Developers
CD-I, CD-2, CD-3, CD-4
Anti-Calcium No. 3
Elon
Phen idone
Citric Acid
Benzyl Alcohol
Hydroquinone
Na^EDTA . 2^0
NH^FeEDTA
Non-Treatable Solutions
Citrizinic Acid
HAS
Na2S2°3
5H2°
Ethylene Glycol
Potassium Oxalate
Ferricyanide
Marginal ly-Trea table
_ Solut ions _
Ethylene Diamine
Fo rm i c Acid
Acetic Acid
Overall Photographic
VI 1-66
-------
DRAFT
Chemical Precipitation
Precipitation can be used effectively for the removal of ferrocyanide
and ferricyanfde from photo processing wastewaters. These complex ions
can be precipitated by using iron salts; ferrous sulfate has proved to
be an economical and effective precipitant.
When employing precipitation for removal of ferri-ferrocyanide, four
items must be considered: equalization, chemical feed system, clari-
fication, and solids handling and disposal. The purpose of equalization
is to minimize the peaks in flow and concentration so that the treatment
system can be designed to provide reliable and consistent results. The
chemical feed system adds the precipitation chemicals in the proper quan
tity at the proper point. (Ferrous sulfate dosage in the range of 250-
500 mg/L with pH of about 8.5 or greater have been reported to give good
results (G-ll). The precipitated materials may be removed in a clar-
i f ier.
The advantages of the precipitation technique for ferri-ferrocyanide over
other forms of destruction or removal are: 1) Precipitation occurs in-
stantaneously, and the system thus requires less reaction tank capacity
per unit volume of wastes; 2) precipitation removes virtually all of the
ferri-ferrocyanide; 3) hour-to-hour fluctuations in concentration of the
waste do not significally change the operating characteristics; and 4)
the process works equally well with a variable influent since only the
ferri-ferrocyanide in the system reacts with iron. Disposal of the
ferrocyanide sludges presents some problems, but the studies to date are
inconclusive as regards the relative hazards of the various disposal
methods.
Reverse Osmosis
The major chemicals used in photo processing have been tested to find
the degree to which they are stopped by a cellulose acetate membrane
under reverse-osmosis conditions (G-ll). Water, hydroquinone, and al-
cohol passed through the membrane easily, but halides and the complex
inorganic ions found in fixing baths and bleaches were easily stopped.
Recent studies have confirmed that fixer wash water is easily separa-
ted into two streams, one containing the concentrated salts and the
other stream nearly pure water. Thus, it is possible to return the
fixer concentrate or the bleach concentrate to the mix area for reuse
in building a new replenisher. The fixer concentrate contains virtually
all of the silver complex that was in the wash water, and it is now prac-
tical to remove electrolytically.
VI I-6?
-------
DRAFT
H. Hospitals
In general, hospital wastes can be readily treated by biological
treatment systems. Although potential does exist for discharge of
biologically inhibiting substances, the industry survey indicates
that the discharge of such substances (such as mercury or silver)
is not general practice. Such substances are usually collected at
the source rather than discharged.
Relatively few hospitals within the United States treat their
own treatment. Most hospitals are located in areas of high
population density, and consequently, it is more convenient for
them to discharge their wastes to municipal treatment systems.
However, the small number of hospitals located in remote areas
must treat their own wastes. Among these hospitals the most
prevalent end-of-pipe wastewater treatment system is the trickling
filter plant; however, some activated sludge systems do exist,
as shown in Table VIIH-1.
In-House Pollution Abatement
During the survey the two most exemplary practiced pollution
control measures observed within hospitals were elimination of
mercury discharge and recovery of silver from spent X-ray
developer. One hospital in particular has gone so far as to
institute a "no mercury discharge" policy. Used chemical compounds
or solutions containing mercury are collected in special containers
rather than discarded in a sink. When a sufficient quantity has
been collected the mercury waste is then disposed of by a private
disposal contractor.
Recovery of silver from spent X-ray developer is practiced at all
hospitals visited during the survey. Larger hospitals processing a
large number of X-rays performed the silver recovery on-site, where-
as smaller hospitals drummed their spent developing solutions and re-
turned them to the manufacturer.
Although many hospitals have active programs aimed at preventing the
discharge of volatile solvents and/or toxic chemicals to sinks and
drains, some are totally unaware of the potential water pollution
problems associated with such practices. In fact, one hospital was
not even aware of the potential fire hazard associated with dis-
carding volatile solvents into sinks. Restrictions on the discharge
of such substances should be an integral part of a hospital's
operating procedure.
End-of-Pipe Control Technology
Table VI IH-1 indicates the types of wastewater treatment technology
observed during the survey and the treatment systems identified but
VI 1-68
-------
DRAFT
not observed. As discussed previously, most hospitals discharge their
wastes to municipal treatment systems. Those hospitals that treat
their wastes generally use trickling filter systems. Activated sludge
systems are in use at several hospitals and aerated lagoons are util-
ized by another hospital.
Table VI IH-1
Treatment Technology Survey
Hospi tals
Number Identified But
Type of Treatment Number Observed Not Observed
Activated Sludge 1 (No. 93) 1
Trickling FiIters 0 11
Aerated Lagoons 0 1
During the survey program, historical wastewater treatment plant per-
formance data were obtained when possible. The historical data were
analyzed statistically, and the performance of individual plants was
evaluated. The results of those analyses are presented in Figures
VI IH-1 through VIIH-8. A summary of the statistical analyses for
two of the hospitals is presented in Table VIIH-2. The amount of
analytical data used in the statistical analyses is indicated in
the "data base" column of Table VIIH-2, and the removal efficiencies
and effluent concentrations shown correspond to 90, 50, and 10 per-
cent probability of occurrence.
During the survey program, 2^-hour composite samples over a two-day
period were collected in order to verify historical performance data
and to provide a more complete wastewater analytical profile. The
performance characteristics which were observed during the survey
are presented in Table VI IH-3- The major purpose for the review of
historical treatment plant performance data was to be able to quantify
BPCTCA reduction factors, which could then be applied to BPCTCA raw
waste load values to develop an end-of-pipe treatment model. Based
on historical data for activated sludge treatment plants, a BODc treat-
ment efficiency of 93 percent was selected as being applicable for the
development of BPCTCA treatment technology.
In addition to BOD, the other major pollutant to be considered is
total suspended solids (TSS). The model BPCTCA treatment system is
an activated sludge system. Such systems generate biological solids
which must be removed before discharge of the effluent. Unless one
is thoroughly familiar with a particular plant's operation, it is
difficult to interpret TSS data. For this reason, recommendation
concerning TSS will be based on effluent concentration.
VII-69
-------
DRAFT
Table VIIH-2
Summary of Historic Treatment Performance
Hospi tals
BOD
Removal E'ff. (%)
Effluent
BODr
TSS
Effluent
Removal Eff. (%) TSS
Hospi tal
93
102
Sk*
95*
96*
97*
98*
99*
1 00*
101*
Type of
Treatment
Act i vated
Sludge
Activated
SI udge
Triekl ing
Fi Iter
Tri ckl i ng
Fi Iter
Triekl ing
Fi Iter
Triekl ing
Fi Iter
Triekl ing
Fi Iter
Triekl ing
Fi Iter
Triekl ing
Fi Iter
Triekl ing
Fi Iter
P90 P50
96 95
93 92
88
92
3k
90
98
96
96
76
mg/L
P10 P90 P50 P10
90 25 14 10
91 20 16 12
27
32
11
2k
k
11
10
56
P90 P50
92 89
95 3k
87
88
95
88
98
95
90
83
mg/L
P10 P90 P50 P10
85 16 12 8
91 15 10 6
12
2k
8
19
3
12
2
33
-•Values based on annual average removal efficiencies
VI 1-70
-------
DR/lFT
Table VI IH-3
Survey Data - Wastewater Treatment Plant
Hospi tals
BOD COD TOC TSS
Effl. Effl. Effl. Effl.
Hospital Type of Removal Cone. Removal Cone. Removal Cone. Removal Cone,
Number Treatment % mg/L % mg/L % mg/L % mg/L
93 Activated 85 3** ^5 325 58 52 neg. 175
Sludge
Since flocculator-clarifiers with polymer addition have been used in
other industries to reduce TSS effluent levels, this process has been
applied to hospital wastewater. On this basis a BPCTCA effluent limi-
tation of 30 mg/L is recommended for TSS.
To assess the economic impact of the proposed effluent standards, a
model activated sludge treatment system was developed. The end-of-
pipe treatment model was designed based on Raw Waste Load (RWL) data
for the Hospitals category. The primary design parameter in BPCTCA,
BADCT and BATEA treatment models is BOD,, removal.
The use of an activated sludge treatment model is done only to facili-
tate the economic analysis and is not to be inferred as the only tech-
nology capable of meeting the effluent limitation guidelines and
standards of performance presented in this report.
VI1-71
-------
DRAFT
SECTION VI I I
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
General
Quantitative cost information for the suggested end-of-pipe treatment
models is presented in the following discussion for the purpose of as-
sessing the economic impact of the proposed effluent limitation guide-
lines on the various Miscellaneous Chemicals industries. A separate eco-
nomic analysis of treatment cost impact on the industry will be prepared
by another contractor and the results will be published in a separate
document.
In order to evaluate the economic impact of treatment on a uniform basis,
end-of-pipe treatment models which will provide the desired level of
treatment were proposed for each industrial subcategory. In-plant control
measures have not been evaluated because the cost, energy, and non-water
quality aspects of in-plant controls are intimately related to the
specific processes for which they are developed. Although there are
general cost and energy requirements for equipment items, these correla-
tions are usually expressed in terms of specific design parameters. Such
parameters are related to the production rate and other specific considera-
tions at a particular production .site.
In the manufacture of a single product there is a wide variety of process
plant sizes and unit operations. Many detailed designs might be required
to develop a meaningful understanding of the economic impact of process
modifications. Such a development is really not necessary, however, be-
cause the end-of-pipe models are capable of attaining the recommended ef-
fluent limitations at the RWL's within the subcategories of each industry.
A series of designs for end-of-pipe treatment models has been provided.
These can be related directly to the range of influent hydraulic and
organic loading within each industry and subcategory, and the costs as-
sociated with these systems can be divided by the production rate for
any given subcategory to show the economic impact of the system in terms
of dollars per pound of product. The combination of in-plant controls
and end-of-pipe treatment used to attain the effluent limitation guide-
lines presented in this document should be a decision made by the indi-
virlu.il plnnt", bnsoH qenorally upon economic considerations.
I In • 11 hi jot I M ji i - w. 11 i • I <|ii, i I i I y (.< in', i >i ••'. . ''>ii
I ro I ini-.isure") i '. llir IIILMMS of u I I iiiMl «-• di'_>pO'jul ol wo'-> 11-'_,. A', (.lie- vo I unu-
of the process RWL is reduced, alternative disposal techniques such as in-
cineration, pyrolysis, evaporation, ocean discharge, and deep-well injection
become more feasible. Recent regulations tend to limit the use of ocean
discharge and deep-well injection because of the potential long-term de-
trimental effects associated with these disposal procedures. Incineration
and evaporation are viable alternatives for concentrated waste streams.
Considerations involving air pollution and auxiliary fuel requirements,
VI I 1-1
-------
DRAFT
•r
depending on the heating value of the waste, must be evaluated individually
for each situation.
Other non-water quality aspects such as noise levels will not be per-
ceptibly affected by the proposed wastewater treatment systems. Most
miscellaneous chemical plants generate fairly high noise levels (85~95
dB (A)) within the battery limits because of equipment such as pumps,
compressors, steam jets, flare stacks, etc. Equipment associated with
in-process and end-of-pipe control systems would not add significantly to
these noise levels.
Extensive annual and capital cost estimates have been prepared for numer-
ous end-of-pipe treatment models for each industry to help EPA evaluate
the economic impact of the proposed effluent limitation guidelines. The
capital costs were generated on a unit process basis (e.g., equalization,
neutralization, etc.) and are reported in the form of cost curves in
Supplement A for all the proposed treatment systems. The following per-
centage figures were added on to the total unit process costs to develop
the total capital cost requirements:
Percent of Unit Process
I tern Capital Cost _
Electrical 1A
Piping 20
Instrumentation 8
Site Work 6
Engineering Design and Construction
Surveillance Fees 15
Construction Contingency 15
Land costs were computed independently and added directly to the total
capital costs.
Annual costs were computed using the following cost basis:
I tern Cost Al location
Capital Recovery
plus Return 10 yrs at 10 percent
Operations and Includes labor and supervision, chemicals,
Maintenance sludge hauling and disposal, insurance and
taxes (computed at 2 percent of the capital
cost), and maintenance (computed at k percent
of the capital cost).
Energy and Power Based on $0.02/kw hr for electrical power and
17C/gal for grade II furnace oil.
-------
DRAFT
The 10 years period used for capital recovery is that which is
presently acceptable under current Internal Revenue Service
Regulations pertaining to industrial pollution control equipment.
The following is a qualitative as well as a quantitative discussion of the
possible effects that variations in treatment technology or design criteria
could have on the total capital costs and annual costs.
Technology or Design Criteria
1. Use aerated lagoons and sludge
dewatering lagoons in place of
the proposed treatment system.
2. Use earthen basins with a
plastic liner in place of re-
inforced concrete construc-
tion, and floating aerators
with permanent-access walkways.
3. Place all treatment tankage
above grade to minimize exca-
vation, especially if a pump-
ing station is required in any
case. Use all-steel tankage
to minimize capital cost.
k. Minimize flows and maximize
concentrations through ex-
tensive in-plant recovery and
water conservation, so that
other treatment technologies,
e.g., incineration, may be eco-
nomically competitive.
3-
k.
Capital
Cost Differential
The cost reduction could be 20
to kO percent of the proposed
figures.
Cost reduction could be 20 to
30 percent of the total cost.
Cost savings would depend on
the individual situation.
Cost differential would depend
on a number of items, e.g., age
of plant, accessibility to
process piping, local air pol-
lution standards, etc.
All cost data were computed in terms of August 1972 dollars, which cor-
responds to an Engineering News Records Index (ENR) value of 1780.
VIH-3
-------
DRAFT
A. Pharmaceutical Industry
This section provides quantitative information relative only to the
suggested end-of-pipe treatment models. Since in-plant modifications
have not been recommended, quantitative information was not developed
for this potential pollution abatement approach.
The design considerations for the model treatment systems (namely,
the influent RWL) were selected so that they represented the average
RWL expected within each subcategory. This generated cost data which
would be representative when applied to most of the RWL data within
a particular subcategory. Activated sludge was proposed in Section
VII as the BPCTCA treatment system for subcategories A, B, C, D and E.
Thermal oxidation is recommended for subcategory C2 for all treatment
levels. The activated sludge plant designs were varied to generate
cost-effectiveness data for each subcategory. Dual-media filtration
was proposed in Section VII as BADCT treatment for subcategories
B, D and E. Activated carbon was proposed for BATEA treatment for
subcategories A and C.
BPCTCA Cost Model
A general flow diagram for the BPCTCA wastewater treatment facilities
for subcategories A, B, C., D and E is shown in Figure VIIIA-1.
Specific unit processes, applicable to each subcategory model treatment
facility, are listed in Table VIIIA-1. A summary of the general design
basis is presented in Table VIIIA-2, and a summary of the treatment
system effluent requirements is presented in Table VIIIA-3.
The recommended BPCTCA treatment facility for subcategory G£ is
thermal oxidation. A general flow diagram is shown in Figure VIIIA-2.
A summary of the general design basis is presented in Table VI I IA-J».
The following is a brief discussion of the treatment technology
available and the rationale for selection of the unit processes
included.
Rationale For Selection of Unit Treatment Processes
Subcategories A, B, Cj, D and E
Equalization facilities are provided in order to minimize short-interval
(e.g. hourly) fluctuations in the organic loading to the treatment plant,
as well as to absorb slug loads from reactor cleanouts and accidental spills,
and to minimize the usage of neutralization chemicals. On the basis of
average flow,two-day detention time is provided for subcategory B, D,
and E flows, compared to one day's detention for subcategories A and C].
VI I 1-
-------
DRAFT
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V I I I-6
-------
DRAFT
Table VI IIA-2
BPCTCA Cost Model Design Summary
Pharmaceutical Industry
Subcategories A,B,Cj,D and E
Treatment System Hydraulic Loading
(average design capacities)
Subcategory Hydraulic Loading
(gpd)(L/day)
A 307,000 1,160,000
B 20,000 76,000
CT 808,000 3,060,000
D 70,000 265,000
E 28,500 108,000
Equalization
For plants with less than 24-hour/day and 7 day/week production, a
minimum holding time of 1.5 days is provided, with continuous dis-
charge from the equalization basin over 2k hours. For plants with
less than 2^-hour/day and 5 days/week production, 2-day equalization
is provided. Discharge from the basin will be continuous over the
seven days. For plants with 2^-hour/day and 7/day week batch pro-
duction processes, one-day holding capacity is provided. For con-
tinuous production processes, no equalization is required except
in special cases. Protective liners are provided, based on the
following criteria:
Influent pH Type of Liner required
Greater than 6 No lining
Between 4.0 and 6.0 Epoxy coating
Between 2.0 and 4.0 Rubber or polypropylene
Below 2.0 Acid brick lining
Neutralization
The two-stage neutralization basin is sized on the basis of an average
detention time of 10 minutes. The size of lime and acid handling fa-
cilities is determined according to acidity/alkalinity data collected
during the survey. Bulk lime-storage facilities (20 tons) or bag
VI I 1-7
-------
DRAFT
Table VII IA-2
(continued)"
storage is provided, depending on plant size. Sulfuric acid storage is
either by 55~gallon drums or in carbon-steel tanks. Lime or acid addi-
tion is controlled by two pH probes, one in each basin. The lime slurry
is added to the neutralization basin from a volumetric feeder. Acid is
supplied by positive displacement metering pumps.
Primary Flocculation ,C1ari f iers _
Primary flocculator clarifiers with surface areas less than
1000 square feet are rectangular units with a length-to-width ratio of
1 to 'f. The side water depth varies from 6 to 8 feet depending on plant
size, and the design overflow rate is 800 gpd/sq ft. Clarifiers
with surface areas greater than 1000 square feet are circular units.
The side water depth varies from 7 to 13 feet depending on plant size
and the design overflow rate is 600 gpd/sq ft. Polymer addition
facilities are provided.
Nutrient Addition
Facilities are provided for the addition of phosphoric acid and anhydrous
ammonia to the biological system in order to maintain the ratio of BOD:N:P
at 100:5:1.
Aeration Basin
The size of aeration basins is based on historic treatability data col-
lected during the survey. Mechanical surface aerators are provided in
the aeration basin.
Aerators were selected on the basis of the following:
Oxygen Utilization: Energy 0.8 Ib 02/lb BOD removed
Oxygen Utilization: Endogenous 6 Ibs Oo/hr/lOOO Ibs MLVSS
-------
DRAFT
Table VI IIA-2
(continued)
Secondary Floccupation Clarifiers
The design basis for secondary flocculation clarifiers is the same as
for primary units except for overflow rate. Secondary clarifiers are
designed for an overflow rate of 600 gpd/sq ft. Feed facilities for
polymer addition are provided.
Sludge Thickener
The thickener provided was designed on the basis of a solids loading of
6 Ibs/sq ft/day.
Aerobic Digester
The size of the aerobic digester is based on a hydraulic detention time of
20 days. The size of the aerator-mixers was based on an oxygen requirement
of 1.6 Ibs 02/lb VSS destroyed and a mixing requirement of 165 HP/mUtlon
gallons of digester volume.
Vacuum FiIt ration
The size of the vacuum filters was based on a cake yield of 2 Ibs/sq ft/hr
for biological sludge, and k Ibs/sq ft/hr for combined primary and biological
sludge. Maximum running times of 16 hours for large plants and 8 hours
for small plants are used. The polymer system was sized to deliver up
to 20 Ibs of polymer per ton of dry solids.
Final Sludge Disposal
For all plants, sludge is disposed of at a sanitary landfill.
Design Philosophy
Individual units within the plant have been sized and arranged so that
they may be taken out of operation for maintenance without seriously
disrupting the operation of the plant.
VII1-9
-------
DRAFT
Subcategory
Table VIIIA-3
BPCTCA End-Of-Pipe Treatment System Requirements
Pharmaceutical Industry
Subcategories A, B, Cj, C~, D and E
Flow SWRL
Flow BOCfc RWL
Effluent BODE
Effluent BOD
kL/kkg Prod.
(gal. /1 00
Ibs product)
A 530
(64,000)
B (67,560)
C1
(19,160)
c2 100
(12,000)
D 15
( 1,750)
E 2
( 285)
kL/day BOD/kkg
(9Pd) Ibs. product
1,200 2,500
(307,000
( 20,076) 144
3,100 302
(808,000)
76
( 20,000)
270 5,200
( 70,000)
(28,108) 0.36
(kg BOD/1000
1 kg product
175
10.1
21.1
52
0.577
0.0252
mg/L
328
18
132
525
39
11
'kg/kkg production is equivalent to lbs/1000 Ibs production
Data for subcategory is expressed in terms of floor area rather than production level
vin-10
-------
DRAFT
V)
5
I
oc
VIII-11
-------
DRAFT
Table VIIIA-4
BPCTCA End-Of-Pipe Treatment System Design Summary
Pharmaceutical Industry
Subcategory 62
Treatment System Hydraulic Loading
The treatment system has been designed for a flow of 20,000 gal/day.
Waste Storage
Storage facilites have-been provided with a capacity to hold waste for
2.5 days.
Thermal Oxidizer
Supplemental fuel requirements for the thermal oxidizers were based on
a heat release of 2.3 x 10& BTU/hr for dilute wastes and 12 x
BTU/hr for concentrated wastes.
VI11-12
-------
DRAFT
The larger detention time is provided to allow for the hydraulic and
organic variability inherent in manufacturing facilities operating less
than 2k hours per day and seven days per week. The added detention time
will provide for continuous seven days per week operation of the waste-
water treatment facilities.
After equalization and depending on the individual plant's product mix, it
may be necessary to neutralize the wastewater to make it more amenable to
biological treatment. Neutralization facilities are provided for subcategory
A and C^ wastes; however, neutralization is not required for wastes in sub-
categories B, D and E.
Primary clarification units are included for subcategory A and C^
however, they are not included in subcategory B, D, and E facilities
because the TSS SRWL data indicated it would not be necessary to remove
TSS before biological treatment.
For all subcategories, a single-stage activated sludge process was
selected because of its demonstrated ability to efficiently treat phar-
maceutical wastes.
Although single-stage activated sludge treatment system has been
selected for the purpose of developing cost models, a multi-stage
activated sludge treatment system merits consideration for sub-
categories A and C-,. The raw waste loads for subcategories A and
Cj are significantly higher than other subcategories, and, although
single-stage processes have provided efficient treatment, use of
a multi-stage system may be desirable for the following reasons:
1. Greater overall removal of BOD.
2. Increased stability and more consistent performance.
3. Greater stability against shock loads.
k. Ability to nitrify in the second stage, resulting in some NH3
removal .
Activated sludge facilities pose a distinct sludge disposal problem.
In the biological process, for every pound of BOD removed from a waste-
water, approximately 0.6 pound of TSS (biological solids) is prpduced
which must be removed from the system.
Subcategory Cp
For subcategory G£ a thermal oxidation process was selected as the model
waste treatment system. This system was selected for the following reasons
VI I 1-13
-------
DRAFT
1. Demonstrated performance
2. High heat release value of the waste
3. High cost of biological treatment of wastes generated by
industries in subcategory G£.
Storage facilities have been provided in order to permit maintenance of
the thermal oxidizers and to insure proper blending and equalizing of
the wastes. A venturi scrubber is also provided to reduce emissions
to the atmosphere. Supplemental fuel is required for the system and use
of fuel will vary depending on the heat release of the waste. Fuel oil
has been selected as the supplemental fuel for the purpose of arriving
at operating costs.
BATEA Cost Model
The BATEA treatment model used for economic evaluation of the proposed limita-
tions includes the BPCTCA treatment model followed by dual media filtration
and activated carbon adsorption. A typical flow diagram for the selected
model treatment facilities is shown in Figure VII 1-3. A summary of the
general design basis is presented in Table VIIA-5. Treatment facilities for
subcategory A and C-| plants include both dual-media gravity filtration and
carbon adsorption. Due to the low COD concentrations obtainable by applica-
tion of BPCTCA technology, carbon adsorption will not be required for sub-
categories B, D and E. The removal efficiencies for dual-media filtration
is established according to the rationale presented in the discussion for
BADCT technology below. No activated carbon treatment systems were observed
during the survey; consequently, to investigate the possibilities of using
activated carbon technology on the effluents from biological treatment plants
treating pharmaceutical wastewaters, a series of carbon isotherms were run
at standard conditions using a contact time of 30 minutes. The results of
the carbon isotherm tests are presented in Tables VIIA-4, VIIA-5, and VIIA-6.
Average performance values for subcategories A and Ci are as follows:
Parameter
COD
BOD,
TOC
Carbon Exhaustion Rate
(Ibs removed/1b carbon)
0.69
0.02
O.A8
Maximum
So 1ub1e Po11utan t Remova1
Cperceht)
80
77
80
VI
-------
DRAFT
Ida
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S ji<
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ui Ho01
3 £u
-------
DRAFT
Table VI IIA-5
BATEA Cost Model Design Summary
Pharmaceutical Industry
Subcategories A,B,Ci,D and E
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of
3 gpm/sq ft. The size of backwash facilities provides rates up to 20
gpm/sq ft and a total backwash cycle of up to 10 minutes in duration.
The filter media are 2k" of coal (1mm effective size) and 12" of sand
(O.i»-0.5 mm effective size).
Backwash Holding Tank
Tankage is provided to hold the backwash water and decant it back to
the treatment plant over a 2^-hour period. This will eliminate hydraulic
surging of the treatment units.
Activated Carbon Columns
The size of the carbon columns is based on a hydraulic loading of
*» gpm/sq ft and a column detention time of 30 minutes. A backwash
rate of 20 gpm/sq ft was assumed for 50% bed expansion at 70°F.
Regeneration Furnace
A carbon exhaustion rate of 0.5 lb COD/lb carbon was used for the
sizing of the regeneration facilities. A multiple-hearth furnace is
employed for regeneration of the carbon and is designed for a carbon
loading of 2.5 Ibs/sq ft/hr and 5 days/week operation.
VI I 1-16
-------
DRAFT
Ideally, pilot-plant continuous column studies should be run in order to
generate design data. However, inspection of the data in Tables VIIIA-1 and
VIIIA-2 indicates carbon adsorption has potential for subcategories A and
Cx, with regard to cost-effective wastewater treatment.
In order to develop BATEA effluent criteria the following treatment efficien-
cies were judged to be reasonable based on the available data, data presented
in process Design Manual for Carbon Adsorption (A-2*0 and the experience of
the contractor.
Pollutant Subcategories A, and Ci
Removal Efficiency!
(percent)
COD 80
BOD 77
TOC 80
Incremental over BADCT filtration effluent
Dual-media filtration is provided since activated carbon typically
requires that the concentration of TSS be 50 mg/L or lower to
maximize carbon adsorption and minimize the filtration function.
High TSS would involve shortened filter runs and increased amounts
of backwash water usage.
Due to the high degree of treatment obtainable by application of
BPCTCA treatment technology, no further treatment is proposed for
subcategory Co.
The BADCT end-of-pipe treatment model used for economic evaluation of the
proposed limitations for subcategories A, B, C^, D and E includes the
BPCTCA treatment model followed by dual media filtration. A typical flow
diagram for the selected model treatment facilities is shown in Figure VIIIA-1
A summary of the design basis is presented in Table VIIIA-6. The BADCT
treatment model for subcategory G£ is the same as the BPCTCA treatment model.
Effluent filtration by use of dual-media filters cannot be considered a
demonstrated technology for the Pharmaceutical industry. During the plant
survey visit use of this technology was not observed. Consequently, his-
torical data needed to quantify the effectiveness of effluent filtration
were not available.
VI I 1-17
-------
DRAFT
ft.
Vlli-18
-------
DRAFT
Table VIIIA-6
BADCT Treatment System Design Summary
Pharmaceutical Industry
Subcategories A,B,Ci,D and E
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of
3 gpm/sq ft. The size of the backwash facilities should provide rates
up to 20 gpm/sq ft and for a total backwash cycle of up to 10 minutes
in duration. The filter media are 2V of coal (1 mm effective size) and
12" of sand (O.k-Q.5 mm effective size).
Backwash Holding Tank
Tankage is provided to hold the backwash water and decant it back to
the treatment plant over a 2^-hour period. This will eliminate hydraulic
surging of the treatment units.
VI I 1-19
-------
DRAFT
In order to quantify the effectiveness of effluent filtration, samples
of biological treatment plant effluents were collected and filtered, using
filter paper, to determine the fraction of effluent BOD, COD and TOC
attributable to suspended solids. Results of these tests are presented
in Table VIIIA-7. Based on this data, the experience of the contractor,
and information contained in the literature, the following suspended pol-
lutant to TSS relationships were selected for the purpose of determining
BODr, COD and TOC removals obtainable by dual-media filtration:
BODr = 0.20; COD = 1.1ft; TOC - O.ftZ
TSS TSS TSS
These valves are based on 1.ft2 Ibs COD, 0.53 Ibs TOC, anc| ySS = 08 TSS
Ib VSS Ib VSS
Cost
Capital and annual cost data were prepared for each of these proposed
treatment systems in accordance with the considerations outlined in
the General part of this section. The cost requirements for imple-
menting the proposed effluent standards are presented in Tables VIIIA-7
through VMIA-12. The detailed breakdown by unit processes are included
in the Supplement A (supporting document).
A discussion of the possible effects that variations in treatment
technology or design criteria could have on capital and annual costs
is presented in the preceding General Section.
Wastes from certain plants within subcategories A and C^ may be amen-
able to sludge incineration because of the large quantities of sludge
produced. For example, sludge incineration would reduce the quanti-
ties of sludge cake by about 90 percent, and is viable alternative
sludge disposal method. However, if additional energy in the form
of auxiliary boiler fuel is required for incineration this alter-
native is strongly discouraged. Sludge incineration costs were
not evaluated for those specific cases in subcategories A and Cj,
because the particular economics depend to a large degree on the
accessibility of a sanitary landfill and the relative associated
haul costs.
Before comparing the variations in costs between each subcategory,
the following discussion is presented to help understand the complexi-
ties involved in evaluating cost effectiveness data. Every treatment
system is composed of units whose design basis is primarily hydrauli-
cally dependent, organically dependent, or a combination of the two.
VI I 1-20
-------
DRAFT
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The following is a list of the unit processes employed, and a break-
down of the design basis:
Hydrauli cal1y
Dependent
Pump station
Equali zation
Neutralizat ion
Nutrient addition
Sludge recycle pump
Clari fier
Organ!cally
Dependent
Thickener
Aerobic digester
Vacuum fi1ter
Hydraulically and
Organically Dependent
Aeration basin
Oxygen transfer equipt,
The annual cost associated with hydraulically dependent unit processes
is not a function of effluent level. On the other hand, the sizing
of the organically dependent units should theoretically vary in
direct proportion to the effluent level: e.g., reducing the BOD re-
moval from 95 to 85 percent should reduce the sizes of the sludge
handling equipment by approximately 10 percent. However, there are
two complicating factors: 1) a relatively few sizes are commercially
available; and 2) capacity ranges are broad. These two factors, es-
pecially in regard to vacuum filters, tend to negate differentials in
capital cost with decreasing treatment levels.
The relationship between design varying contaminant levels and the
design of aeration basins and oxygen transfer equipment is somewhat
more complex. The levels are dependent on the hydraulic flow, organic
concentration, sludge settleabi1ity, and the relationship between
mixing and oxygen requirements. For example, to reach a particular ef-
fluent level, the wastewater's organic removal kinetics will require
a particular detention time at a given mixed-liquor concentration. The
oxygen transfer capacity of the aerators may or may not be sufficient
to keep the mixed liquor suspended solids in suspension within the
aeration basin. Therefore, required horsepower would be increased to
fulfill a solids mixing requirement. On the other hand, the oxygen
requirements may be such that the manufacturer's recommended minimum
spacing and water depth requirements would require that the basin
volume be increased to accommodate oxygen transfer requirements.
Costs abstracted from Tables VIIIA-7 through VIIIA-12are presented in
Table VIMA-13ona per gallon basis. As expected, the estimated total
capital and operation and maintenance costs for subcategory A and C]
are the highest. This reflects the high wastewater flows that charac-
terize these two subcategories. In addition, these wastewaters typi-
cally contain high concentrations of organic material, which require
relatively long aeration times and more extensive sludge handling
faci1i t ies.
VI11-27
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DRAFT
-------
DRAFT
The cost per gallon figures presented in Figure VIIIA-7 decrease with
increasing flows, illustrating treatment system economies of scale.
The annual cost per thousand pounds of product listed in Table VIIIA-1
through VIIIA-6 also indicate that the plants with the higher produc-
tion rates have lower annual costs when seen in terms of dollars per
1,000 pounds of production.
Energy
For the Pharmaceutical industry, the primary energy and power needs
for BPCTCA level treatment for all Subcategories except 62, are pumps,
aerators, and vacuum filters. For Subcategory 62 the need of auxiliary
fuel as estimated could be considerably reduced by mixing primary waste
streams containing high concentration of solvents as normally done in
the industry. Under BADCT, energy is needed for additional pumping
requirements for all Subcategories except €2- Primary energy and power
needs for BATEA include additional pumping and carbon regeneration
furnace fuel requirements. Therefore, the overall impact on energy
for this industry should be minimal.
Tables VI I I A-7 through VI IIA-12present the cost for energy and power
for each treatment models for BPCTCA, BATEA and BADCT. The detailed
energy and power requirements are included in the Supplement A
(supporting document).
Sludge cake quantities from vacuum filtration corresponding to each
treatment system design are presented in Supplement A. The following
table summarizes the sludge quantities generated by the model plants:
Exhausted
Subcategory Cu Yd/Year^ Ibs/day Carbon
A 20,000 6,700 3^0
B 900 15
CT 11,000 3,700 320
D U50 150
E 1,825 ^0
Dry-Weight basis
Non-Water Quality Aspects
The major non-water quality aspects of the proposed effluent limita-
tions guidelines are ultimate sludge disposal, noise and air pollution.
VII 1-29
-------
DRAFT
The BPCTCA treatment models proposes sludge disposal by landfill ing
of the dewatered digested biological sludge for Subcategories A, B,
C, D and E and also landfilling for the residue from the thermal
oxidation in Subcategory ^2- If practised correctly, landfilling
of the digested biological sludge does not create health hazards or
nuisance condition. Sludge incineration is a viable alternative,
but not included in the treatment model due to high fuel require-
ment and high cost. Sludge incineration is practised by some plants
where sludge is incinerated along with other solid waste and strong
waste streams with high fuel value, reducing the auxiliary fuel
requirement to a minimal level.
Noise levels will not be appreciably affected with the implementa-
tion of the proposed treatment models. Most Pharmaceutical plants
in themselves generate relatively high noise levels and the pumps,
aerators, mixers, etc. associated with end-of-pipe treatment plants
will not add significantly to these noise levels.
Provision for air pollution control equipment have been made in
case of thermal oxidation in BPCTCA treatment model for Subcategory
C2 and for carbon regeneration furnaces in BATEA treatment models
for Subcategories A, B, C, D, and E. In case of Subcategory A,
odor is a problem for an activated sludge plant if the plant is
located in the middle of the inhibitory area. Covering of the
aeration basin for odor control is practised in some plant.
VI I 1-30
-------
DRAFT
B. Gum and Wood Chemicals Industry
This section provides quantitative cost information relative to as-
sessing the economic impact of the proposed effluent limitations
guidelines on the Gum and Wood Chemicals industry. A separate
economic analysis of treatment cost impact on the industry will be
prepared by another contractor and the results will be published in
a separate document.
In order to evaluate the economic impact on a uniform treatment basis,
end-of-pipe treatment models were proposed which will provide the de-
sired level of treatment:
End-of-Pipe
Technology Level Treatment Model
BPCTCA Activated Sludge.
BADCT Activated Sludge and Filtration.
BATEA Activated Sludge, Filtration,
and Carbon Adsorption.
The combination of in-plant controls and by end-of-pipe treatment
used to attain the effluent limitations guidelines is left up to
the individual manufacturer to decide on the basis of cost-
effect i veness.
BPCTCA COST MODEL
To evaluate the economic effects of BPCTCA effluent limitations
guidelines on the Gum and Wood Chemicals industry, it was necessary
to formulate a BPCTCA treatment cost model which is activated sludge.
The proposed model is shown on Figure VIIIB-1. A summary of the
general design basis used to size the unit processes is presented
in Table VIIIB-1.
The following is a brief discussion of the treatment technology
available and the rationale for selection of the unit processes to
be included in the BPCTCA waste treatment model.
As shown in Figure VIIIB-1, for critical unit operations, two units,
are proposed in the model. This is to insure operating flexibility
and reliability. Total wastewater flows in the Gum and Wood
Chemicals Industry are characteristically low, generally less than
200,000 gpd. The parallel-train design is not normally used for
treatment plants in the very low flow range because of economic
consideration. However, standby items should be provided for key
process functions.
VI I 1-31
-------
DRAFT
u. _ Ij ace c/> (- u 5
VI11-32
-------
DRAFT
Table VI IIB-1
BPCTCA Treatment System Design Summary
Gum and Wood Chemicals Industry
Subcategory
B
C
D
E
F
Treatment System Hydraul ic Load ing
(capa c i t ie s cove r ed, in gpd)
3,000
130,000
133,000
7,960
2,300
1
Pump Station
Capacity to handle 200 percent of the average daily flow.
capability included, with minimum pump motor of 1A hp.
Stand-by
Equalization
One day detention time is provided for subcategories B,C and F. Two
days are provided for subcategory E. Three days are provided for sub-
category D. The basins are not provided with mixers to prevent oil
and grease emulsification.
Neutralization
The two-stage neutralization basin is sized on the basis of a minimum
detention time of 30 minutes. The lime-handling facilities are sized
to provide 1,000 Ibs of hydrated lime per MGD of wastewater for pH
adjustment as needed in subcategories B, D, E, and F. Subcategory C
requires no adjustment. Bag storage is provided for all plants. Lime
addition is controlled by two pH probes, one in each basin. The lime
slurry is added to the neutralization basin from a lime slurry recir-
culation loop. The lime-handling facilities are enclosed tn a build-
ing.
Air Flotation
The air flotation units recommended for subcategories B, C, D and F
are designed for oil and grease removal. They are sized on a rise rate
of 1.5 gpm/ft2 including recycle of 75 percent with a minimum ^0 minute
detention time. Air is provided for the units at a rate of 1.5 scf per
100 gallon recycle at 50 psig.
Equalized flow is 5,680 gpd.
VIII-33
-------
DRAFT
Table VI I IBH
(cont i nuedT
Nutrient Addi.tion
Facilities are provided for the addition of phosphoric acid and aqua
ammonia to the biological system in order to maintain the ratio of
BOD:N:P at 100:5:1.
Aeration Basin
Platform-mounted mechanical aerators are provided in the aeration basin.
In addition, walkways are provided to all aerators for access and main-
tenance. The following data were used in sizing the aerators:
Energy oxygen 0.8 Ib 02/lb BOD removal
Endogenous oxygen 6 Ib 02/hr 1,000 Ib MLVSS
Field Oxygen Transfer 2.0 Ib 02/hp-hr
Oxygen is monitored in the basins using D.O. probes. All aeration
basins are sized using kinetics developed from treatability data for
plants 2, A, B (see Table VIIB-2).
Secondary Clarifiers
All secondary clarifiers are rectangular units with a length-to width
ratio of 4 to 1. The overflow rate varies between 40 and 400 gpd/sq.
ft. depending on plant size. Sludge recycle pumps are sized to deliver
100 percent of the average flow.
Aerobic Digester
The aerobic digester is sized on the basis of a hydraulic detention
time of 20 days. The sizing of the aerator-mixers is based on 165 hp/MG
of digester volume.
Sludge Holding Tank - Thickener
A sludge-holding tank is provided for all plants, with sufficient ca-
pacity to hold 7 days flow from the aerobic digester. Facilities are
included for discharge to tank trucks for hauling and disposal.
VI I 1-34
-------
DRAFT
The topography of a particular plant site will dictate whether pumping
is required. Equalization facilities are provided to minimize short-
interval (e.g., hourly) fluctuations in the organic loading to the
treatment plant to absorb loads from reactor cleanouts, accidental
spills and other heavy loads, and to minimize the usage of neutrali-
zation chemicals. Equalization will provide for continuous (seven
days per week) operation of the wastewater treatment facilities even
though the manufacturing facilities operate only five days a week.
Since many of the gum and wood chemical waste streams are of low pH,
neutralization may be necessary. Alkaline neutralization is provided
in the form of hydrated lime storage and feed facilities. Since some
of the subcategories have high oil RWL concentrations, dissolved air
flotation was recommended.
An activated sludge process was selected for the biological treatment portion
of the system. However, many of the gum and wood chemical plants are located
in the southeastern United States, where aerated lagoons could provide a viable
treatment alternative. However, to make the subsequent cost estimates
universally applicable, activated sludge was selected.
The sludge handling scheme proposed in Figure VII IB-l was developed to handle
anticipated small quantities of sludge. The aerobic digester will produce
a nonputrescible sludge which can be thickened and stored before being trucked
for either land spreading or to a regional treatment facility for dewatering.
BATEA Cost Model
For the purpose of the economic evaluation of BATEA on the Gum and Wood
Chemicals industry, it was necessary to formulate a BATEA waste treatment
model, which is presented in Figure VII IB-2. The model includes dual media
filtration followed by carbon adsorption of the BPCTCA biological treat-
ment plant effluent. A summary of the general design basis used to size
the unit processes is presented in Table VIIIB-2.
Dual media filtration was selected for the BATEA treatment model to minimize
plugging of the carbon column during biological treatment plant upsets. The
pulsed bed upflow carbon system was selected to minimize capital investment
for a system with a relatively high carbon exhaustion rate compared to the
carbon column inventory.
The BATEA waste treatment model in Figure VI I I B-2 shows the exhausted carbon
being hauled to a sanitary landfill. This is because the amount of carbon
exhausted per day is generally substantially less than 500 pounds/day, which
is generally considered below the break-even point for on-site carbon re-
gene rat ion.
VI I 1-35
-------
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DRAFT
Table VI I IB-2
BATEA End-of-Pipe Treatment System Design Summary
Subcategory Treatment System Hydraulic Loading
(capacities covered, "in'gpd")
B 3,000
C 130,000
D 133,000
E 7.9601
F 2,300
Dual-Media Filtration
The filters are sized on the basis of an average hydraulic loading of
2 gpm/sq. ft. Backwash facilities are sized to provide rates up to
20 gpm/sq. ft. and for a total backwash cycle of up to 20 minutes in
duration. The filter media are 2V of coal (1mm effective size) and 12"
of sand (Q.k-Q.5 mm effective size).
Granular Carbon Columns
The carbon columns are sized on a hydraulic loading of k gpm/sq. ft.
and a column detention time of ^fO minutes. A backwash rate of 20 gpm/
sq. ft. was assumed for kQ percent bed expansion at 70°F.
Backwash Holding Tank
Tankage is provided to hold the backwash water and decant it back to
the treatment plant over a 2^-hour period. This will eliminate hydraulic
surging to the treatment units.
Virgin/Exhausted Carbon Storage
Tankage is provided to handle the virgin and exhausted carbon. A
carbon exhaustion capacity of 0.6 Ibs. COD/lb. carbon was used for
design. The quantities of carbon exhausted based on the previous ex-
haustion capacity are not sufficiently large enough to warrant the in-
vestment in a regeneration furnace. For this reason the exhausted
carbon is disposed of in a sanitary landfill as indicated in Figure
VI IB-2.
Equalized flow is 5,680 gpd.
VI 11-37
-------
DRAFT
BADCT Cost Model
The evaluation of the economic effects of the BADCT effluent limitations
guidelines on the Gum and Wood Chemicals industry necessitated the
formulation of a treatment model using a dual media filtration treatment
system. A summary of the general design basis and proposed model is
presented in the previous discussion on BATEA treatment systems.
COST
Capital and annual cost estimates were prepared for these
end-of-pipe treatment models for five of the six subcategories.
Subcategory A has a no discharge and therefore end-of-pipe
treatment was not applicable. The prepared cost estimates are
presented in Tables VIIIB-3 through VI I IB-?. The detailed cost
breakdown by unit processes are included in the Supplement A
(supporting document).
The costs presented in these tables are incremental costs for
achieving each technology level. For example, in Table VIMB-1»,
the total capital cost for biological treatment to attain BPCTCA
effluent limitations is shown to be $1,390,000 for a plant pro-
ducing 11^,000 Ibs/day of wood turpentine and rosin. The BPCTCA
effluent limitations in Table VIIIB-4 were determined using the
reduction factors presented in Section VII. The incremental
capital costs for achieving the recommended BADCT effluent
limitation is shown in Table VIIIB-^ to be $135,000. This cost
would be in addition to the capital investment made to achieve
the BPCTCA effluent limitation. In contrast the incremental
cost for achieving the BATEA COD effluent limitation would be
$^03,000.
A discussion of the possible effects that variations in treatment
technology or design criteria could have on capital and annual costs
is presented in the General section.
ENERGY
The size ranges of the BPCTCA and BATEA treatment models preclude
the application of some high energy-using unit processes such as
sludge incineration and carbon regeneration. Therefore, the over-
all impact on energy should be minimal. Tables VIIIB-3 through
VIIIB-7 present the cost for energy and power, for each treatment
model for BPCTCA, BATEA and BADCT. The details for energy and
power requirements are included in the Supplement A (supporting
document).
VI I 1-38
-------
DRAFT
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-------
DRAFT
Liquid waste incineration is a viable industry alternative for
concentrated waste streams. The heating value of the particular
waste dictates the auxiliary fuel requirement and thus these energy
considerations must be evaluated on an individual basis.
NON-WATER QUAUTYrASPECTS
The major non-water quality aspects of the proposed effluent limita-
tions guidelines are ultimate sludge disposal, noise and air pollution.
The BPCTCA treatment model proposes land spreading of the digested
biological sludge. If practiced correctly, this disposal method will
not create health hazards or nuisance conditions. However, there is
a widespread diversity of opinion over the effects of heavy metals on
crop toxicity and in the food chain, and the possible nitrate con-
tamination of the ground water. Carefully controlled sludge applica-
tion should minimize these problems. The following are summaries of
the biological sludge and exhausted carbon residue from the proposed
BPCTCA and BATEA treatment facilities:
Exhausted
Subcategory Biological Sludge Quantity Carbon Residue
(gal Ions/day)1 (cu yd/year)2
B 430 54
C 1,910 249
D 1,820 28
E 140 16
F 760 97
iBased on a 2 percent solids concentration,
2Dry weight basis.
Noise levels will not be appreciably affected with the implementation
of the proposed treatment models. Air pollution should only be a
consideration if liquid incineration were selected as the waste dis-
posal alternative.
VI I I-M
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-------
DRAFT
Pesticides and Agricultural Chemistry Industry
BPCTCA COST MODEL
General flow diagram's for the BPCTCA wastewater treatment facilities
are shown in Figures VI I IC-1 through VI I IC-5. A summary of the general
design basis is presented in Table VI MC-1-
The following is a brief discussion of the treatment technology ap-
plicable to the individual subcategories and the rationale for
selection of the unit processes included.
Model treatment systems for all subcategories include a biological
treatment system preceded by various types of pretreatment, depend-
ing on the particuliar subcategory. Extensive pretreatment systems
are required due to the toxic nature of many pesticide wastewaters.
Pretreatment Required
The type and arrangement of pretreatment processes varies from sub--
category to subcategory; however, in general facilities include
neutralization, alkaline hydrolysis, oil and solids separation,
and metals removal.
The pH of raw process wastewaters flowing into the model biological
treatment systems will potentially deviate from neutral conditions.
In order to make the wastewater more amenable to biological treat-
ment, neutralization facilities are provided for all subcategories.
Subcategory B (organo-phosphorous) wastes frequently contain con-
taminants that are slow to biodegrade and also exhibit toxic or
inhibitory characteristics for biological treatment. Accordingly,
detoxification of these species is required. Lime slurry is added
to the waste in a rapid mix tank and the pH is raised to approxi-
mately 10. The waste passes from the mix tank to a settling tank
where the lime solids settle out and are removed. The overflow
proceeds to the detoxification unit.
The detoxification of organo-phosphorus wastes is based on extended
heat treatment in an alkaline medium. The unit consists of a flow-
through basin providing 8 to 24 hours of detention. The optimal
pH range is usually 10 to 11, and caustic soda addition is fre-
quently required to raise the pH above that produced by the lime
precipitation process. Steam is injected into the detoxifier basin
to maintain a temperature of approximately 100 F, and plastic bubbles
should be kept on the water surface to reduce sensible and evaporative
heat losses. Since subcategory E wastes may contain organo-
phosphorus contaminates, provisions for detoxification by alkaline
hydrolysis have been provided.
-------
DRAFT
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VI11-50
-------
DRAFT
Table VI IIC-1
BPCTCA Treatment System Design Summary
Pesticides and Agricultural Chemicals Industry
Treatment System Hydraulic Loading
(Design Capacities)
Subcateqory
A
A
B
B
C
C
D
El
Small Plant
Large Plant
Small Plant
Large Plant
Small Plant
Large Plant
Typi cal
Typical
Hydraul ic Load! nq
(gpd)
66,000
350,000
76,000
812,000
88,300
1 ,080,000
120,000
16,000
(L/day)
250,000
1 ,320,000
288,000
3,070,000
33^,000
k ,090 ,000
^5^,000
60,600
API Separators
The API type seperators are sized based on the following:
Temperate = 40°F
Rise rate of oil globules = 0.16 ft/min
Maximum allowable mean horizontal velocity = 2.k ft/min
Detoxification Unit
Alkaline hydrolysis units for the purpose of detoxifying pesticide wastes are
designed for a detention time of 12 hours and a length to width ratio of 5 to 1
VI I 1-51
-------
DRAFT
Table VI IIC-1
(Continued)
Inci nerators
The design of incinerator is based strictly on flow as the heat release
values of the waste are neglibible. Fuel requirements are based on a
heat requirement of 1,000 BTU's/lb of waste.
Neutralizat ion
The two-stage neutralization basin is sized on the basis of an average
detention time of 10 minutes. The size of lime and acid handling facilities
is determined according to acidity/alkalinity data collected during the survey,
Bulk lime-storage facilities (20 tons) or bag storage is provided, depending
on plant size. Sulfuric acid storage is either by 55-gallon drums or in
carbon-steel tanks. Lime or acid addition is controlled by two pH probes, one
in each basin. The lime slurry is added to the neutralization basin from a
volumetric feeder. Acid is supplied by positive displacement metering pumps.
Equali zat ion
Equalization basins for all plants are sized for a holding time of 36 hours.
Primary Flocculation Clarifiers
Primary flocculator clarifiers with surface areas less than 1,000 square
feet are rectangular units with a length-to-width ration of 1 to k. The
VI I I-52
-------
DRAFT
Table VI IIC-1
(Continued)
side water depth varies from 6 to 8 feet, depending on plant size, and the
design overflow rate is kOO gpd/sq ft. Clarifiers with surface areas greater
than 1,000 square feet are circular units. The side water depth varies from
7 to 13 feet, depending on plant size and the design overflow rate is ^00 gpd/
sq ft. Polymer addition facilities are provided.
Nutrient Addi tion
Facilities are provided for the addition of phosphoric acid and anhydrous
ammonia to the biological system in order to maintain the ration of BOD:N:P
at 100:5:1.
Aeration Basin
The size of aeration basins is based on detention times and food to micro-
organism ratios commonly used within the industry. Mechanical surface aerators
are provided in the aeration basin.
Aerators were selected on the basis of the following:
Oxygen Utilization: Energy 0.8 Ib 02/lb BOD removed
Oxygen Utilization: Endogenous 6 Ibs 02/hr/1,000 Ibs MLVSS
Oxygen Transfer 3-5 Ibs 02/hr/shaft HP at 20°C
and D.0. in tap water •
Motor Efficiency 85 percent
Minimum Basin D.O. 2 mg/L
Minimum Number of Aerators 2
Oxygen is monitored in the basins using D.O. probes.
VIII-53
-------
DRAFT
Table VI IIC-1
(Continued)
S1 udqe Th i ckene.r
The thickener provided was designed on the basis of a solids loading of 6
Ibs/sq ft/day.
Aerobic Digester
The size of the aerobic digester is based on a hydraulic detention time of
20 days. The size of the aerator-mixers was based on an oxygen requirement
of 1.6 Ibs 02/lb VSS destroyed and a mixing requirement of 165 HP/mg of
digester volume.
Vacuum Filtration
The size of the vacuum filters was based on a cake yield of 2 Ibs/sq ft/hr
for biological sludge, and k Ibs/sq ft/hr for combined primary and biological
sludge. Maximum running times of 16 hours for large plants and 8 hours for
small plants are used. The polymer system was sized to deliver up to 20
Ibs of polymer per ton of dry solids.
£inal Sludge Disposal
For all plants, sludge is disposed of at a sanitary landfill.
Des i gn Ph i1osophy
Individual units within the plant have been sized and arranged so that they
may be taken out of operation for maintenance without seriously disrupting
the operation of the plant.
-------
Since subcategory A and B wastewaters can contain seperable organics
which would interfere with downstream treatment processes, oils re-
moval in an API type separator is needed. The separator can be
rectangular or circular depending on land availability, flow, and
other design considerations.' The skimmed organics cannot be re-
claimed in most cases and should be incinerated or containerized
for disposal. Subcategory C wastes contain high suspended solids
loadings in addition to oil and grease. Removal of both pollutants
can be accomplished in a combination oil and solids separation.
Skimmed oils, or organics, should be incinerated or containerized
for disposal. Settled solids are held in a holding tank prior to
dewatering with biological solids.
Subcategory D production facilities generate wastewaters containing
metal, particularly heavy-metal components. The removal of the
heavy metals is best accomplished on the undiluted metals-laden
wastes prior to combination with general process wastewaters. The
most common method for removing heavy metals is lime precipitation.
The metals-laden wastewaters first pass through a rapid mix tank
where lime and flocculating aids are added. The treated wastewater
then proceeds to a flocculator where the metal/lime solids are
flocculated to improve their settleabi1ity. The waste finally
flows into a settling basin where the metal/lime precipitate is
removed.
In addition to the pretreatment systems mentioned above for less
concentrated process wastes, waste streams which are not compatible
with biological treatment, such as distillation tower bottoms or
tars, will be generated by all subcategories except E. The most
applicable treatment for such wastes is incineration. The incin-
erator will burn principally liquid wastes, but it is possible
that provisions will be necessary to incinerate toxic or polluting
components from off-gases and vessel vents. The incinerator should
be equipped with air pollution control devices, and the wastewater
effluent from these units should be discharged to the wastewater
treatment plant, potentially to the neutralization stage.
Biological Treatment
After pretreatment the plant wastewaters require equalization prior
to biological treatment to equalize flow, organics, and toxic ma-
terial surges. Equalization is best carried out in a mixed-concrete
or concrete-1ined basin. The size of the basin is dependent on the
flow and contaminant loading patterns which, of course, are closely
related to the production processes with particular consideration
given to the batch-type operations.
For all subcategories except E], biological treatment consists of
an activated sludge system. The overall activated sludge process
includes aeration basins, final flocculator-clarifiers, and sludge
handling facilities. Aerated lagoons were selected as the model
treatment system for subcategory E] plants formulating water-based
pesticides due to the relatively low and intermittant wastewater flows,
VI I 1-55
-------
Sludge handling facilities for subcategory A and C plants consist
of sludge thickening, aerobic digestion, and vacuum filtration.
For subcategories B, E, and D aerobic digestion will not be required,
as the sludge produced will contain a large amount of lime and should
be relatively stable without digestion.
No model waste treatment facilities are provided for subcategory
E£ wastes since no discharge of process wastewater pollutants
is recommended.
BATEA COST MODEL
In order to recommend further treatment technologies as candidates
for BATEA, it is necessary to evaluate the residual characteristics
of the effluents potentially produced by the proceeding technologies.
In all cases, the significant characteristics remaining after ap-
plication of the respective BPCTCA technologies are COD and TSS.
The use of dual media filtration and activated carbon adsorption
to treat biological treatment effluent has been shown to be an ef-
fective method for removing TSS and COD in other industries. There-
fore, it is recommended that such technology be applied to the treat-
ment of pesticide wastes. A generalized wastewater flow diagram for
dual media filtration and activated carbon adsorption is shown in
Figure VlllC-6. A summary of the general design basis is presented
in Table VI I IC-2.
In order to develop BATEA COD effluent criteria, a removal efficiency
of 75 percent was judged to be reasonable. In addition, an effluent
TSS concentration of 20 mg/L was judged to be obtainable by dual media
filtration, based on inspection of data contained in Upgrading Existing
Wastewater Treatment Plants (EPA 1974).
BADCT COST MODEL
The BADCT end-of-pipe treatment model used for economic evaluation
of the proposed limitations includes the BPCTCA treatment model fol
lowed by dual media filtration. A typical flow diagram for the
selected model treatment facilities is shown in Figure VIIIC-7 and
a summary of the design basis is presented in Table VI I 1-3.
As discussed previously, the recommended effluent TSS value for
dual media filtration is 20 mg/L.
VI I 1-56
-------
DRAFT
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VI11-57
-------
Table VI I IC-2
BATEA Treatment System Design Summary
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of 3 gpm/sq ft.
The size of backwash facilities provides rates up to 20 gpm/sq ft and a total
backwash cycle of up to 10 minutes in duration. The filter media are 2V of
anthrafelt (No. 1-1/2) and 12" of sand (Q.k - 0.5 rim Muscatine sand).
Filter-Column Decant Sump
Tankage is provided to hold the backwash water and decant it back to the
treatment plant over a 2^-hour period. This will eliminate hydraulic
surging of the treatment units.
Granular Carbon Columns
The size of the carbon columns is based on a hydraulic loading of k gpm/sq ft
and a column detention time of 30 minutes. A backwash rate of 20 gpm/sq ft
was assumed for 50% bed expansion at 70°F.
Regeneration Furnace
A carbon exhaustion rate of 0.5 lb COD/lb carbon was used for the sizing of
the regeneration facilities. A multiple-hearth furnace is employed for re-
generation of the carbon and is designed for a carbon loading of 2.5 Ibs/ft/hr
and 5 days/week operation.
VI I 1-58
-------
DRAFT
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VI11-59
-------
Table VI IIC-3
BADCT Treatment System Design Summary
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of 3 gpm/sq ft,
The size of the backwash facilities should provide rates up to 20 gpm/sq ft
and for a total backwash cycle of up to 10 minutes in duration. The filter
media are 2k" of anthrafelt (No. 1-1/2) and 12" of sand (0.4 - 0.5 mm Muscatine
sand).
Fi Itex~Cpl_umn Decant Sump
Tankage is provided to hold the backwash water and decant it back to the
treatment plant over a 24-hour period. This will eliminate hydraulic
surging of the treatment units.
VI I 1-60
-------
DRAFT
COST
The development of the cost for various treatment levels follows
the procedure used for the other industries. For some categories,
costs of treatment are presented for two plant sizes to indicate,
where necessary, the effect of plant size on treatment cost.
Tables VIIIC-^ through VIMC-11 present the cost data for each sub-
category. The detailed cost breakdown by unit processes are in-
cluded in the Supplement A (supporting document).
ENERGY
For the Pesticides and Agricultural Chemicals Industry, the
primary energy and power needs for BPCTCA level treatment are
pumps, aerators, mixers and incineration fuel. Under BADCT,
energy is needed for additional pumping requirements. Primary
energy and power needs for BATEA include additional pumping
and carbon regeneration furnace requirements. Tables VIIIC-4
through VIMC-11 present the cost for energy and power, for
each treatment models for BPCTCA, BATEA and BADCT. The de-
tails for energy and power requirements are included in the
Supplement A (supporting document).
NON-WATER QUALITY ASPECTS
The major non-water quality considerations of the proposed
treatment systems involve the use of alternative means of
waste streams. The off-gases from incineration can be
adequately scrubbed and controlled and the effluent dis-
charged to the treatment system. Accordingly, the proposed
treatment facilities do not have significant air quality
impact.
Primarily, lime and biological sludges are all compatible
with ultimate disposal in a sanitary landfill. Where
necessary, biological solids can be adequately stabilized
by digestion prior to landfill. The following table summarizes
the sludge quantities generated by the model plants.
VIII-61
-------
DRAFT
Plant Size, gpd Ibs/day
Subcategory A (66,000) 1,200
(350,000)
B (76,000) 2,400
(812,000) 24,000
C (88,300) 2,160
(1,090,000) 14,900
D (120,000) 5,140
E (16,000) 200
'Dry weight basis
Other non-water quality aspects, such as noise levels, will not be
perceptibly affected. Most pesticide plants in themselves generate
relatively high noise levels, and the pumps, aerators, mixers, in-
cineration equipment, etc., associated with in-plant or end-of-pipe
wastewater control and treatment systems will not add significantly
to these levels.
VII1-62
-------
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DRAFT
D. Adhesives and Sealants Industry
This section provides quantitative cost information relative to as-
sessing the economic impact of the proposed effluent limitations on
the Adhesive and Sealants industry. A separate economic analysis
of treatment cost impact on the industry will be prepared by another
contractor and the results will be published in a separate document.
In order to evaluate the economic impact on a uniform treatment basis,
end-of-pipe treatment models were proposed which will provide the de-
sired level of treatment:
(Subcategory)
End-Of-Pipe
Technology Level Treatment Model
BPCTCA (A) Activated Sludge
(B&C) Double Effect Liquid
Evaporation
BATEA (A) Two Stage Activated Sludge
and Filtration
(B&C) Double Effect Liquid
Evaporation
BADCT (A) Activated Sludge
and Filtration
(B&C) Double Effect Liquid Evap-
oration
BPCTCA Treatment Systems
Subcategory A
A genera) flow diagram for the BPCTCA wastewater treatment facilities
for Subcategory A is shown in Figure V MID-1.
A summary of the general design basis for this system is presented
in Table VI I ID-1.
The following is a brief discussion of the treatment technology
available and the rationale for selection of the unit processes
included in the described BPCTCA treatment system.
VI I 1-71
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VIII-72
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DRAFT
Table VI IID^]
BPCTCA Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A
Treatment System Hydraulic Loading: k mqc!
Equalization
Two days of detention time are provided. Floating mixers are pro-
vided to keep the contents completely mixed.
P r i ma ry C]a r i f i e r
The primary clarifier is a circular reinforced concrete unit. The
side water depth is ten feet and the overflow rate is 800 gpd/sq ft
Sludge recycle pumps are sized to withdraw sludge at 1.5 percent.
Neutralizat ion
The size of the two-stage neutralization basin is based on an
average detention time of twenty minutes. The sulfuric acid
handling facilities are designed to add 9,700 Ibs of sulfuric acid
per mgd of wastewater, to adjust the pH. Bulk-storage facilities
(based on 15 days usage) are provided. Sulfuric acid addition is
controlled by two pH probes, one in each basin.
Nutrient Addition
Facilities are provided for the addition of phosphoric acid to the
biological system in order to maintain the ratio of BOD:P at 100:1.
There should be sufficient nitrogen concentrations in the waste-
water to maintain the desired ratio of BOD:N of 100:5-
Aeration Basin
Platform-mounted mechanical surface aerators are provided in the
aeration basins. Concrete walkways are provided to all aerators
for access and maintenance. The following data were used in
determining the size of the aerators.
Energy Oxygen 0.8 Ibs 02/lb BOD removed
Endogenous Oxygen 6 Ibs 0_/hr/1000 Ibs MLVSS under aeration
Minimum Basin D...O. 2 mg/L
Oxygen is monitored in the basins using D.O. probes.
VIII-73
-------
DRAFT
Table VI IID-1
(cont inued)
Secondary Clarifiers
The secondary clarifiers are circular units with flocculator mech-
anisms. A flocculation time of 20 minutes is provided. The side
water depth is 10 ft, and the overflow rate is 600 gpd/sq ft. Sludge
recycle pumps are sized to deliver 50 percent of the'average flow.
Sludge Holding Tank-Thickener
The thickener provided for this plant was designed on the basis of
6 Ibs/sq ft/day and a side water depth of 10 ft.
Aerobic Diqestor
The size of the aerobic digester is based on a hydraulic detention
time of 20 days. The size of the aerator-mixers was based on an
oxygen requirement of 1.6 Ibs 02/'b VSS destroyed and mixing require-
ment of 165 HP/million gallons of digester volume.
Vacuum F i1trat ion
The size of the vacuum filters was based on a cake yield of 2 Ibs/sq
ft/hr and an average running time of 16 hrs/day. The polymer system
was sized to deliver up to 20 Ibs of polymer/ton dry solids.
Final Sludge Disposal
Sludge is disposed of at a sanitary landfill assumed to be 10 miles
from the wastewater treatment facility.
Desi gn Philosophy
The process units of the treatment model are designed for series
flow except for the final clarifiers which are designed for parallel
flow.
VI I I-Ik
-------
DRAFT
Equalization facilities are provided in order to minimize short-
interval (e.g. hourly) fluctuations in the organic loading to the
treatment plant, as well as to absorb slug loads from reactor
cleanouts, accidental spills, and other high-level sources, and to
minimize the usage of neutralization chemicals. A two-day detention
time is provided, based on average flow. This detention time is
provided to allow for the hydraulic and organic variability inherent
in batch chemical production wastes. Also, this detention time will
provide for continuous operation of the wastewater treatment facilities,
After equalization, it will be necessary to remove the suspended
solids and chromium from the wastewater to make it mqre amenable to
biological treatment. A primary clarifier will be used to remove
the primary sludge, which will be pumped directly to the sludge
conditioning tank prior to vacuum filtration. The sludge is a high
lime content sludge and contains lime solids, lime soaps, grease,
dirt, and hair. Past analyses have shown the chromium to be tri-
valent chromium, which can be precipitated at the high pH values of
the raw wastewater (pH 11 to 12). The trivalent chromium will be
removed with the primary sludge and go directly to the sludge de-
watering system.
Neutralization will also be necessary to make the wastewater more
amenable to biological treatment. Acid neutralization is provided
in the form of sulfuric acid storage and feed facilities.
An activated sludge process was selected for the biological treat-
ment portion of the system. This process was selected over aerated
lagoons because of the nature and concentrations of pollutants
in the wastewater to be treated. Both aerated lagoons and acti-
vated sludge processes involve aeration basins, but aerated
lagoons normally discharge directly without a clarification step.
This results in a much lower concentration of microorganisms in the
aerated lagoon than in an activated sludge basin because the micro-
organism mass is not recirculated back to the aeration lagoon.
Therefore, for comparable organic loadings, a much larger aerated
lagoon would be required to provide treatment equivalent to that of
an activated sludge plant. Also, the influent 8005 (approximately
kOOO mg/L) to the treatment plant is high in protein content and
thus high in organic-nitrogen.
In the biological process, for every pound of BODr removed from a
wastewater, approximately 0.6 pounds of TSS (biological solids)
are produced which must be removed from the system. In the areas
where aerated lagoons are applicable, settling lagoons are often
used to separate these biological solids. In the activated sludge
process, sludge wasting is done daily to dewatering facilities.
Sludge removal is accomplished by allowing the solids to settle in
flocculation clarifiers.
VI11-75
-------
DRAFT
Sludge thickening is provided to concentrate the waste activated
sludge before digestion. The sludge will be aerobically digested
and removed by vacuum filtration. The sludge cake would then be
acceptable for sanitary landfill or incineration. Filtrate from
the vacuum filtration process will be returned to the aeration
basins along with the thickener overflow.
Subcategories B and C
A general flow diagram for the BPCTCA wastewater treatment
facilities for Subcategories B and C is shown in Figure VIIID-2.
A summary of the general design basis for these subcategories is
presented in Table VIIID-2, and a summary of the treatment system
effluent requirements is presented in Table VIIID-3.
BATEA Treatment Systems
The BATEA treatment system recommended for subcategory A is a two-
stage biological activated sludge treatment system followed by
dual-media filtration. A general flow diagram for the BATEA treat-
ment system for subcategory A is shown in Figure VIIID-3. A summary
of the general design basis is presented in Table VIIID-4, and a
summary of the treatment system effluent requirements is presented
in Table VIIID-5. Possibilities of in-plant measures and recircula-
tion of part of the treated effluent should be explored as a possible
means of reducing the pollution loads.
The technology and effluent limitations guidelines applied for
BPCTCA treatment systems in subcategories B and C are also applied
for BATEA treatment systems.
BADCT Treatment Systems
The BADCT treatment system recommended for subcategory A is
activated sludge followed by dual-media filtration. A general
flow diagram for the BADCT treatment system for subcategory A is
shown in Figure VI I ID-'*. A summary of the general design basis is
presented in Table VIIID-6, and a summary of the treatment system
effluent requirements is presented in Table VIIID-7.
The technology and effluent limitations guidelines applied for
BPCTCA treatment systems in subcategories B and C are also applied
for BADCT treatment systems.
VI I 1-76
-------
DRAFT
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51
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VIM-77
-------
DRAFT
Table VIIIB-2
BPCTCA Treatment System Design Summary
Adhesive and Sealants Industry
Subcategories B and C
Treatment System Hydraulic Loadings
0.01 mgd - Subcategory B
0.006 mgd - Subcategory C
Equali zat ion
Two days of detention time are provided. Floating mixers are pro-
vided to keep the contents completely mixed.
Evaporation System
The selection of evaporative equipment depends on the job require-
ment. In selecting the optimum number of effects, a balance has to
be made between equipment costs and operating costs. Due to waste-
water characteristics and operating conditions, double effect liquid
evaporation was used. Heat-transfer area, operating conditions of
each unit, and steam consumption were estimated.
Sludge Disposal
Sludge is disposed of at a sanitary landfill assumed to be 10 miles
from the wastewater treatment facility.
Pus i gn Philosophy
Equalization of the wastewater for continuous flow to the evaporation
system is required because of the intermittent discharges. The
wastewater is pumped from the equalization basin to the fluidizing
tank where it is mixed with recycle oil before it proceeds to the
vapor chambers.
VI I 1-78
-------
DRAFT
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DRAFT
V I I I-80
-------
DRAFT
Table VI1ID-A
BATEA Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A
Second Stage Aeration Basin
Platform-mounted mechanical surface aerators are provided in the
aeration basin. Concrete walkways are provided to all aerators
for access and maintenance. The following data were used in
sizing the aerators.
Energy Oxygen 0.8 Ibs 02/lb BOD
Endogenous Oxygen 6 Ibs 02/hr/1000 Ibs
MLVSS under aeration
Minimum Basin D.O. 2 mg/L
Oxygen is monitored in the basins using D.O. probes.
Secondary Clarifiers
The secondary clarifiers are circular units with flocculator mechanisms,
A flocculation time of 20 minutes is provided. The side water depth is
10 ft, and the overflow rate is 600 gpd/sq ft. Sludge recycle pumps
are designed to deliver 50 percent of the average flow.
Sludge Holding Tank-Thickener
The thickener provided for this plant was designed on the basis of
6 Ibs/sq ft/day and a side water depth of 10 ft.
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of
three gpm/ft^. Backwash facilities are designed to provide rates up
to 20 gpm/ft^ and for a total backwash cycle of up to 10 minutes in
duration. The backwash water holding tanks are designed to hold two
backwashes.
VI I 1-81
-------
DRAFT
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VI I 1-83
-------
DRAFT
Table VI IID-6
BADCT Treatment System Design Summary
Adhesives and Sealants Industry
Subcategory A
Dual-Media Filtration
The size of the filters is based on an average hydraulic loading of
three gpm/ft^. Backwash facilities are sized to provide rates up to
20 gpm/ft and for a total backwash cycle of up to 10 minutes in
duration. The backwash water holding tanks are designed to hold two
backwashes.
-------
DRAFT
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Capital and annual cost estimates were prepared for these end-of-pipe
treatment models for three of the six subcategories. The prepared cost
estimates are presented in Tables VIIID-8 through VIIID-10. The de-
tailed breakdown by unit processes are included in the supplement A
(Supporting Document).
The costs presented in these tables are incremental costs for achiev-
ing each technology level. For example, In Table VIIID-1, the total
capital cost for biological treatment to attain BPCTCA effluent limi-
tations i-3 $10,600,000 for a plant producing 99,000 pounds per day of
animal glue and gelatin. The BPCTCA effluent limitations in Table
VIIID-1 were determined using the reduction factors presented in
Section IX. The capital costs for achieving the recommended BATEA and
BADCT effluent limitations for the plant producing 99,000 Ibs/day of
animal glue and gelatin are $1,600,000 and $^80,000, to be added to
the cost of BPCTCA treatment.
A discussion of the possible effects that variations in treatment
technology or design criteria could have on capital and annual costs
is presented in the General section.
Energy
The size of the BPCTCA and BATEA treatment models for subcategory A
preclude the application of some high energy-using unit processes
such as incineration and carbon regeneration. Therefore, the over-
all impact on energy for subcategory A should be minimal.
Each type of evaporator is suited to particular areas of performance.
The selection of evaporative equipment depends on the job require-
ments. The amount of power required depends on the evaporative situa-
tion. In selecting the optimum number of effects, a balance has to
be made between equipment costs and operating costs. If the addition
of an effect will not pay for itself in lower steam costs within a
certain period of time, the effect probably should not be added. Inter-
relationships between number of effects, capital cost, and steam usage
can be developed.
Tables VIIID-8 through VIIID-10 present the cost for energy and power,
for each of the treatment models for BPCTCA, BATEA and BADCT. The
details for energy and power requirements are included in the Supplement
A (supporting document).
VI
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DRAFT
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DRAFT
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V I I I-89
-------
DRAFT
Non-Water Qua 1ity Aspects
The major non-water quality aspects of the proposed effluent limitations
are ultimate sludge disposal, noise and air pollution.
The BPCTCA treatment models propose disposal of sludge to sanitary
landfills. If practiced correctly, this disposal method will not
create health hazards or nuisance conditions.
The following table summarizes the sludge quantities generated by the
model plants :
Subcategory Pounds per Year
A 58,^00,000
B 125,000
C 1,250
Dry-Weight Basis
Noise levels will not be appreciably affected with the implementation
of the proposed treatment models. Air pollution should only be a con-
sideration if liquid incineration is selected as the waste disposal
alternative.
VI I 1-90
-------
DRAFT
E. Explosives Industry
This section provides quantitative cost information relative to as-
sessing the economic impact of the proposed effluent limitations on
the Explosives industry.
In order to evaluate the economic impact on a uniform treatment basis,
end-of-pipe treatment modeis were proposed based on design criteria
that provide the desired level of treatment. A summary of the treat-
ment models follow:
End-of-P i pe
Technology Level Treatment Model
BPCTCA Activated Sludge
BADCT Activated Sludge and Filtration
BATEA Activated Sludge, Filtration,
and Carbon Adsorption.
The treatment technology shown above is intended to attain the
effluent limitations guidelines proposed. Individual plants may
attain effluent limitations guidelines through in-plant controls or
by different end-of-pipe treatment than is shown. The decision
is left up to the manufacturer as to which is the most cost-
effect! ve.
BPCTCA Cost Model
To evaluate the economic effects of BPCTCA on the Explosives industry,
a BPCTCA treatment model was developed. The treatment model is de-
scribed in Table VIII-E1. As shown in Figure VIII-E1, there are two
parallel treatment trains in the proposed system. This is to ensure
operating flexibility and reliability. Treatment systems involving
very low flow may not be able to use this parallel mode.
The following is a brief discussion of the treatment technology
available and the rationale for the selection of the unit processes
included in the described BPCTCA treatment system.
The topography of a particular plant site will dictate the type of
pumping equipment required. Equalization facilities are provided
in order to minimize short interval (e.g.,hour 1y) fluctuations in
the hydraulic loading to the treatment plant and to absorb organic sludge
VI I 1-91
-------
DRAFT
Table VIIIE-1
BPCTCA Treatment System Design Summary
Explosives Industry
Equali zat ion
For plants with less than 2k hour/day and 7 day/week production,
a minimum holding time of 1.5 days is provided with continuous
discharge from the equalization basin over 2k hours.
For plants with less than 2k hour/day and 5 days/week production,
two day equalization is provided. Discharge from the basin will
be continuous over the seven days. For plants with 2k hour/day
and 7 day/week batch production, one day holding capacity is pro-
vided. For continuous processes (2k hours/day, 7 days/week) no
equalization is required except under special cases.
Protective liners are provided, based on the following criteria:
Influent pH Type of Liner Required
Greater than 6 No Lining
Between *t.O and 6.0 Epoxy Coating
Between 2.0 and k.O Rubber or Polypropylene
Below 2.0 Acid Brick Lining
Neutralization
The size of the two-stage neutralization basin is based on an average
detention time of 10 minutes. Lime and acid handling facilities are
sized according to acidity/alkalinity data collected during the sur-
vey. Bulk lime-storage facilities (20 tons) or bag storage is pro-
vided, depending on plant size. Sulfuric acid storage is either
by 55-gallon drums or in carbon-steel tanks. Lime or acid addition
is controlled by two pH probes, one in each basin. The lime slurry
is added to the neutralization basin from a volumetric feeder. Acid
is supplied by positive displacement metering pumps.
Primary Flocculation Clarifiers
Primary flocculator clarifiers with surface areas less than 1,000
square feet are rectangular units with a length-to-width ratio of
1 to k. The side water depth varies from 6 to 8 feet and the over-
flow rate varies between 600 and 800 gpd/sq ft depending on plant
size. Clarifiers with surface areas greater than 1,000 square feet
are circular units. The side water depth varies from 7 to 13 feet
and the overflow rate varies between 600 and 800 gpd/sq ft, de-
pending on plant size. Polymer addition facilities are provided.
VI I I-92
-------
DRAFT
Table VI I IE-1
(continued)
Nutrient Addition
Facilities are provided for the addition of phosphoric acid to the
biological system to maintain the ratio of BOD:N:P at 100:5:1.
Aeration Basin/Aerated Lagoons
The size of the aeration basins is based on historical treatability
data collected during the survey. Mechanical surface aerators are
provided.
The necessary design criteria for the aeration basins are:
Oxygen Utilization: Energy Q.8 Ibs O./lb BOD removed
Oxygen Utilization: Endogenous 6 Ibs 09/Rr/1,000 Ibs MLVSS
-------
DRAFT
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DRAFT
loads from reactor cleanouts and accidental spills and minimize
the usage of neutralization chemicals. Equalization will provide
continuous (seven days per week) operation of the wastewater treat-
ment facilities even though the manufacturing facilities operate
only five days a week.
Since many of the explosive waste streams have, extreme values of
pH, neutralization is necessary. Alkaline neutralization is
provided in the model system in the form of hydrated lime storage
and feed faci1ities.
An activated sludge process was selected for the biological treat-
ment portion of the system. However, for plants located in the
area with available land space, aerated lagoons with clarification
could provide a viable treatment alternative. However, for the
purpose of cost estimates, activated sludge was selected.
The sludge, handling scheme is shown in Figure VII{-1. The aerobic
digester will produce a nonputrescible sludge which can be thickened
and stored before being trucked to a certified landfill.
It should be noted that the activated sludge process cannot be justi-
fied for the dilute waste streams of subcategory B. However, since
most load and pack operations are part of larger plant operations
which include manufacturing activities in the other subcategories,
the same percentage removals were applied.
BATEA Cost Model
For the purpose of the economic evaluation of BATEA, it was neces-
sary to formulate a BATEA waste treatment model (Table VI I 1-2). The
model, composed of dual media filters and activated carbon adsorption, is
presented in Figure VIIIE-2. It is intended that this model be
added on to the BPCTCA treatment system.
Dual media filtration is intended to remove the suspended solids
to avoid clogging of the activated carbon column. The down-flow
fixed bed system was selected. Regeneration of activated carbon
has been a problem in TNT waste streams, but no studies have shown
it to be a problem in composite waste streams.
BADCT Cost Model
For the purpose of the economic evaluation of BADCT, a cost model
(Table VI I 1-2) was formulated consisting of dual media filtration
added on to the BPCTCA treatment system.
VI I 1-95
-------
DRAFT
Backwash
Table VII1-2
BATEA and BADCT Treatment System
Design Summary
Explosives Industry
Multimedia Filtration
Filters were sized using the criteria of 3 gpm/sq ft.
rates used were 20 gpm/sq ft for 10 minute duration.
Carbon Adsorption
The unit is designed as a downflow fixed bed. Pretreatment for
removal of suspended solids is provided so as to thwart clogging
of the carbon column. Carbon contact time was set at 30 minutes.
Hydraulic loading rates used were k gpm/sq ft. The spent carbon
to be regenerated was calculated on a 0.5 1b of COD/lb carbon
The regeneration furnace itself was designed for 2.5 Ibs/sq
ft/hr.
V I I I-96
-------
DRAFT
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VI11-97
-------
DRAFT
Cost
Capital and annual cost estimates were prepared for the previous end-
of-pipe treatment models for all subcategories. The prepared cost
estimates are presented in Tables VIIIE-1 through VIIIE-^f. The costs
presented in these tables are incremental costs for acheiving each
technology level. The detailed cost breakdown by unit processes are
included in the Supplement A (supporting document).
For example, in Table VIIIE-1, the total capital cost for subcategory A
to attain BPCTCA effluent limitations is $192,000 for a plant pro-
ducing an average of 112,000 pounds of explosive per day. The BPCTCA
effluent limitations in Table VIIIE-1 were determined using the re-
duction factors presented in Section VII.
The incremental capital costs for achieving the recommended BADCT ef-
fluent limitation in Table VIIIE-1 would be in addition to the capital
investment made to achieve the BPCTCA effluent limitation. Similarly,
the incremental cost for achieving the BATEA effluent limitation for
subcategory A would be $1,180,000.
A discussion of the possible effects that variations in treatment tech-
nology or design criteria could have on capital and annual costs is
presented in the General section.
Energy
The size ranges-of the BPCTCA and BATEA treatment models preclude the
application of some high energy-using unit processes such as sludge
incineration. Carbon regeneration will require significant amounts
of energy; however, the overall impact on energy consumption should
be minimal. Tables V I I IE-3 through V I I I E-6 present the cost for
energy and power, for each treatment model for BPCTCA, BATEA and
BADCT. The details for energy and power requirements are included
in Supplement A (supporting document).
Non-Water Quality Aspects
The major non-water quality aspects of the proposed effluent limita-
tions encompass ultimate sludge disposal, noise and air pollution.
The BPCTCA treatment model proposes land spreading of the digested
biological sludge. If practiced correctly, this disposal method will
not create health hazards or nuisance conditions. The possibility
of trace explosives leaching into groundwater reservoirs can be
minimized by carefully controlled sludge application. The following
are summaries of the biological sludge from proposed BPCTCA and
BATEA treatment facilities:
VI I 1-98
-------
DRAFT
Subcategory Biological Sludge Quantity
Ibs/day1
A1 17,600
A2 33,000
B 5,360
C 480
on solids concentration (dry weight basis)
Noise levels will not be appreciably affected with the implementation
of the proposed treatment models. Air pollution should only be a
consideration if liquid incineration were selected as the waste dis-
posal alternative.
V I I I-99
-------
DRAFT
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VI I 1-103
-------
DRAFT
F. Carbon Black Industry
This section provides quantitative cost information relative to as-
sessing the economic impact of the proposed effluent limitations
guidelines on the Carbon Black industry. Since no discharge of
pollutants is proposed for subcategory A, to be achieved through
housekeeping measures, no treatment models were developed for this
subcategory. End-of-pipe treatment models were only considered
for subcategory B. In order to evaluate the economic impact on a
uniform treatment basis, end-of-pipe treatment models were pro-
posed which will provide the desired level of treatment. These
treatment models are summarized below;
End-of-Pipe
Technology Level Treatment Model
BPCTCA Gravity Settling Pond
BADCT Gravity Settling and Filtration
BATEA Gravity Settling and Filtration
The choice of whether to use in-plant controls or end-of-pipe treat-
ment to attain effluent limitations is left up to the individual
manufacturer.
BPCTCA Cost Model
To evaluate the economic effects of the BPCTCA effluent limitations
on the Carbon Black industry, it was necessary to formulate a 8PCTCA
treatment model. The model selected was gravity settling ponds, as
shown in Figure VI I I-1.
BATEA Cost Model
The BATEA treatment model used for economic evaluation of the pro-
posed limitations includes dual media filtration in addition to
BPCTCA treatment model. A typical diagram of the system is shown
in Figure VI I 1-2.
BADCT Cost Model
The BADfT treatment model used for economic evaluation of the proposed
limitations includes the BPCTCA treatment model, followed by dual
media filtration, as shown in Figure VI I 1-3.
VI I 1-104
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DRAFT
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VIII-107
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DRAFT
Cost
Annual and capita] cost estimates have been prepared for the above
end-of-pipe models for each technology level. These costs are pre-
sented in Table VIIIF-1. The costs presented in this table are in-
cremental costs for achieving each technology level. The detailed
cost breakdown by unit processes are included in the Supplement A.
(supporting document).
A discussion of the possible effects that variations in treatment
technology or design criteria could have on capital and annual costs
is presented in the General section.
Energy
Since the BPCTCA treatment models were designed to use landfill ing of
gravity compacted sludge, the only possible consumers of energy could
be low-horsepower pumps and the energy required to dredge the ponds.
BATEA and BADCT models add gravity filtration. The energy impact of
these would be very small; only small-horsepower pumps. Table VIIIF-1
presents the cost for energy and power, for the treatment models for
PPCTCA, BATEA, and 3ADCT. The details for energy and power require-
ments are included in the Supplement A (supporting document).
Non-Water Quality Aspects
The non-water quality considerations for the Carbon Black industry in
achieving the proposed effluent limitations are minimal. The major
consideration will be disposal of the settled carbon black, which will
be done primarily by landfilling.
Other non-water quality aspects will not be perceptibly affected.
Equipment associated with in-process or end-of-pipe control systems
would not add significantly to these.
VI I 1-108
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DRAFT
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VI I 1-109
-------
DRAFT
G. Photographic Processing Industry
This section provides quantitative cost information relative to as-
sess irg the economic impact of the proposed effluent limitations on
the Photographic Processing industry. A separate economic analysis
of treatment cost impact on the industry will be prepared by another
contractor and the results will be published in a separate document.
In order to evaluate the economic impact on a uniform treatment basis,
end-of-pipe treatment models were proposed which will provide the de-
sired level of treatment:
End-of-Pi pe
Technology LeveJ Treatment Model
BPCTCA Extended aeration activated sludge.
BADCT BPCTCA plus Filtration.
BATEA BPCTCA plus Filtration.
The combination of in-plant controls and end-of-pipe treatment used
to attain effluent limitations is left up to the individual manu-
facturer to decide on the basis of cost-effectiveness.
BPCTCA COST MODEL
Activated sludge treatment process has been selected as the BPCTCA
treatment system. The 20,000 gpd activated sludge facility was
chosen as the model for Level I treatment. Performance data on
other end-of-pipe treatment systems presently on line were insuf-
ficient. Furthermore, a survey of the Photographic Industry in-
dicated that there are no full plant scale end-of-pipe wastewater
treatment systems.
The application of the activated sludge treatment scheme in the Photo-
graphic Processing industry was made because of the success encountered
by the system in reducing BOD. Average BOD removals from this process
were 70%. Higher BOD removals (perhaps as much ac 85%) are possible,
however, by increasing the size of the equalization tank used in the
model plant (G-4). This slight design change will allow the treaitment
process to accomodate variable incoming flows without adversely affec-
ting performance. Also, allowances were made in the proposed BPCTCA
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VIII-111
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DRAFT
Table VI I IG-I
BPCTCA Treatment System Design Summary
Photographic Processing Industry
Treatment System Hydraulic Loading: 20,000 qpd (G-l)
Equalizat ion
For plants with less than 2^-hour/day and 7 day/week production
(as is the case for most photoprocessors), a minimum holding time
of 1.5 days is provided, with continuous discharge from the equal-
ization basin over 2k hours. Given the design flow of 20,000 gpd,
the basin size becomes 30,000 gallons.
Aeration Basin
Aeration Basins are sized on the basis of historic treatability
data collected during the survey. The aeration tank has a voluhe
of 20,000 gallons. Mechanical turbine blowers will be provided
to supply the air. There are sufficient phosphates and nitrates
in the wastewaters to satisfy the nutrient requirement of the
system.
Secondary Flocculator Clarifiers
Secondary flocculator-clarifiers are designed for an overflow rate
of 300 gpd/sq ft. The required surface area of the clarifier is
then 70 square feet.
SIudqe Thickener
The thickener was designed on the basis of a solids loading of
6 Ibs/sq ft/day.
Final Sludge Disposal
Excess biological sludge is disposed of to a sanitary landfill by
a contract hauler.
VI I 1-112
-------
DRAFT
Specific in-plant modifications aimed to reduce both the silver and
ferrocyanide concentrations in the wastewater flow should be incor-
porated into end-of-pipe treatment. These in-plant changes are con-
sidered part of good housekeeping practice, and modifications include
electrolytic silver recovery from the fix or bleach-fix baths; re-
generation of the ferricyanide bleach by ozone; using ferric EDTA
bleach in some processes, after evaluating the respective effectiveness;
using squeegees; and collecting the spent concentrated solutions in a
holding tank for controlled bleed-off to a dilute wastewater stream.
Pollutants of special significance such as silver (in the form of silver
thiosulfate) can be tolerated in the influent in concentrations as high
as 10 mg/L (G-3). Ferrocyanide passes through the biological system
unchanged and does not exhibit an inhibitory action on the treatment
system. However, ferrocyanide may convert to free cyanide in the
presence of sunlight, and therefore, an effluent limitation of 1.35
mg/L Fe (CN)g4 (equivalent to 1 mg/L CN~) should be imposed, based on
cyanide toxicity studies (G-8).
Additional study into the fate of ferrocyanide may turn up evidence
correlating excessive levels of free cyanide found in the receiving
waters from the degeneration of the complex ferrocyanide ion. In that
event, pretreatment of the ferrocyanide by precipition techniques
should be imposed on the industry.
BATEA COST MODEL
The filtration of the effluent from the biological system, using dual-
media filters, was selected as BATEA treatment system. Filtration of
the effluent from the biological treatment process would provide in-
cremental BOD reduction of 33 percent. Silver measured in the effluent
from the model plant was 1 mg/L, which represents an 80 percent reduc-
tion from the influent to the biological system (G-3). Figure VIIIG-2.
illustrates the unit processes involved in the treatment system. A
summary of the general design basis for the system is presented in
Table VI IIG-2.
Table VI MG-2
BATEA Treatment System Design Summary
Photographic Processing Industry
Dual-Media Filter
The filters are sized on the basis of an average hydraulic loading
of 3 gpm/sq ft. Backwash facilities are sized to provide rates up
to 20 gpm/sq ft and for a total backwash cycle of up to 10 min. in
duration. The filter media are 18" of anthracite (O.^5m) 6" of
sand (0.15m) and a drainage bed of 12" (0.3m) of graded gravel.
VI11-113
-------
FIGURE VIIIG-2
DRAFT
PHOTOGRAPHIC PROCESSING INDUSTRY
BATEA COST MODEL
CLARIFIED
EFFLUENT
INFLUENT
WET
WELL
r—C*}-
DUAL MEDIA FILTERS
-exh
TO SLUDGE
THICKENER
BACKWASH
SUMP
-00
BACKWASH
HOLDING
TANK
VIII-114
-------
DRAFT
BADCT COST MODEL
For new plant sources, the in-plant modifications available for re-
ducing the raw waste loads should be applied wherever possible. In
addition, a minimum of end-of-pipe treatment as described in the BATEA
Treatment System subsection should be applied; this consists of the
BPCTCA system plus dual-media filtration.
COST
Capital and annual cost estimates were prepared for the treatment
models described above. Average process water consumption (2,960
gal/1,000 sq ft) for the industry was based on the average of the
three plants visited. Costs were developed for an average flow
rate of 20,000 gpd, as explained earlier in Section VII under
"Size of Facility." The costs presented for BATEA and BADCT in
these tables are incremental costs over the cost for BPCTCA. For
example, in Table VIIIG-1 the total capital cost for the average
size photoprocessing plant to attain BPCTCA effluent limitation is
$207,000. (This cost includes in-plant modifications.) The incre-
mental capital costs for achieving the recommended BADCT in Table
VIIIG-1 would be $43,900. This cost would be in addition to the
capital investment made to achieve the BPCTCA effluent limitation.
The detailed cost breakdown by unit processes are included in the
Supplement A (supporting document).
Table VIIIG-1 also illustrates RWL, and effluent limitations based on
the production for a model plant. Percent removals for BOD and COD
are based on past operating experience of the large-scale activated
sludge treatment process. Applying the 85 percent reduction factor
to the BOD RWL, BPCTCA effluent limitations are determined. Applying
the 90 percent reduction factor to BOD RWL, BADCT effluent limitations
result. The respective COD reduction for BPCTCA and BADCT treatment
systems factors are 50 percent and 60 percent. There are no incre-
mental pollutant reductions for BATEA'treatment.
These cost estimates were prepared based on the recommended design
basis. Variations in the design basis or selection of alternative
treatment process cnn hnve nppreri.ihlo effort', on tin- reported
i .11) i I .1 I ( o1, I ', , . r, (I i •,( ii',',c(J in I In- lii-iii-1 ,i I MM I i on
11-115
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VI I 1-116
-------
DRAFT
ENERGY
The sizes ranges of the BPCTCA and BATEA treatment models preclude
the application of high energy-using units such as sludge incinerators,
Therefore, the overall impact on energy should be minimal. Estimated
energy consumption per year for BPCTCA and BATEA treatment models are
32,570 kwh and 9,700 kwh, respectively. Table VI IIG-1 presents the
cost for energy and power for the treatment models for BPCTCA, BATEA
and BADCT. The details for energy and power requirements are included
in the supplement A (supporting document).
NON-WATER DUALITY ASPECTS
The major non-water quality aspects of the proposed effluent limita-
tions encompass are sludge disposal, noise and air pollution.
The BPCTCA treatment model proposes landfill ing of biological sludge.
If practiced correctly, this disposal method will not create health
hazards or nuisance conditions. However, there is a widespread
diversity of opinion over the effects of silver leaching into ground
water supplies. Carefully controlled sludge application should mini-
mize these problems.
Noise levels will not be appreciably affected with the implementation
of the proposed treatment models. Air pollution should only be a con-
sideration if sludge incineration is selected as the waste disposal
alternative.
VI I 1-117
-------
DRAFT
H. Hospitals
Ilii1. '-uclion provide'!) quonl i lal i vc cosl i nf onikil ion tclolive lu
assessing the economic impact of the proposed effluent limitations
guidelines on hospitals. A separate economic analysis of treatment
cost impact on the industry will be prepared by another contractor
and the results will be published in a separate document.
In order to evaluate the economic impact on a uniform treatment
basis, an end-of-pipe treatment model which will provide the
desired levels of treatment was proposed.
End-of-Pipe
Technology Level Treatment Model
BPCTCA Activated Sludge
BATEA Activated Sludge and
FiItration
BADCT Activated Sludge and
Fi1tration
BPCTCA Cost Model
A flow diagram for the BPCTCA wastewater treatment facility for
hospitals is shown in Figure VMIH-1. A summary of the general
design basis is presented in Table VIIIH-1, and the treatment
system effluent requirements are as follows:
Influent (RWL) Effluent
Flow BOD. BOD,-
gal/1,000 lbs/1,000 lbs/1,000
occupied beds occupied beds occupied beds mg/L
(gpd)
319,000 587 4i.i 18
172,000
Occupied beds on average annual basis.
The following is a brief discussion of the rationale for selection
of the unit processes included in the model wastewater treatment
system.
VI I 1-118
-------
DRAFT
-I P HI
s 35
if!
VIII-119
-------
UKAFT
Table VI IIH-1
BPCTCA Treatment Systems Design Summary
Hospitals
Hydraulic Loading
The model plant was designed for a flow of 191,000 gpd.
Aeration Basin
The size of the aeration basin is based on data collected during the
survey. Mechanical surface aerators are provided on the following
bas is:
Minimum Number of Aerators 2
Oxygen Utilization: Energy 0.8 Ibs 02/lb BOD removed
Oxygen Utilization: Endogenous 6 lbs/hr/1,000 Ibs MLVSS
0< 0.75
6 0.90
Oxygen Transfer (Standard) 3-5 Ibs 02/hr/shaft HP at 20°C
and zero D.O. in tap water
Motor Efficiency 85 percent
Minimum Basin D.O. 2 mg/L
Secondary Flocculator/Clari fiers
Secondary flocculator clarifiers are rectangular units with a length
to-width ratio of 1 to A and a side water depth of 8 feet. The over-
flow rate is approximately ^50 gpd/sq ft. Polymer addition facilities
are provided.
Chlorination Facilities
Chlorine contact basins have been designed to provide 30 minutes
detention time, based on average flow.
Sludge Thickener
The thickener provided was designed on the basis of a solids loading
of 6 Ibs/sq ft/day.
Aerobic Digester
The aerobic digester was designed on the basis of a hydraulic deten-
tion time of 20 days. The size of the aeration-mixers was based on
an oxygen requirement of 1.6 Ibs 02/lb VSS destroyed and a mixing re-
quirement of 165 HP/mg of digester volume.
Vacuum Fi1tration
The size of the vacuum filters was based on a cake yield of 2 Ibs/
sq ft/hr and a maximum running time of 8 hours per day. The polymer
system was designed to deliver up to 20 Ibs of polymer per ton of dry
sol ids.
VI I 1-120
-------
DRAFT
BATEA Cost Model
The BATEA model treatment system used for economic evaluation of the
proposed limitations includes the BPCTCA treatment model followed by
dual-media filtration. A typical flow diagram for the selected model
treatment facilities is shown in Figure VlllH-2. A summary of the
general design basis is presented in Table VlllH-2.
Based on effluent filtration data presented in Process Design Manual
for Upgrading Existing Wastewater Treatment Plants, U.S. EPA, 197^,
BATEA effluent limitations of 10 mg/L (22.6 lbs/1,000 occupied beds)
for both BOD and TSS are recommended. Selection of these values
actual field data, since no effluent filtration facilities were ob-
served during the survey.
BADCT Cost Model
The BADCT model treatment system is identical to the proposed BATEA
treatment system.
An activated sludge process was selected because of its demonstrated
ability to efficiently treat hospital wastes. Because of the relatively
low suspended solids concentrations, primary clarifiers are not included
in the model facilities. The activated sludge system produces biological
solids which must be removed from the system and returned to the aeration
basin or wasted in order to maintain the proper load to microorganism
ratio. To serve this purpose, secondary flocculator-clarifiers have been
provided. Sludge handling facilities consisting of thickening, aerobic
digestion and vacuum filtration have been provided to facilitate ultimate
disposal of sludge to a sanitary landfill.
Cost
Capital and annual costs estimates were prepared for an end-of-pipe
treatment model. The prepared cost estimates are presented in Table
VIIIH-3. The costs presented in this table are incremental costs for
achieving each technology level. The total capital cost for biological
treatment to attain BPCTCA effluent limitations is $830,000 for a hospital
with 600 beds. The BPCTCA effluent limitations were determined using the
reduction factors presented in Section IX. The incremental capital cost
for achieving the recommended BATEA and BADCT effluent limitations for a
hospital with 600 beds, over the cost for BPCTCA, is $169,000. The
detailed cost breakdown by unit processes are included in the Supplement A
(supporting document).
VIII-121
-------
DRAFT
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VI I 1-122
-------
DRAFT
Table VIIIH-2
BADCT Treatment System Design Summary
Hospitals
Dual-Media Filtration
The size of the filters is based on average hydraulic loading of 3
gpm/sq ft. Backwash facilities are designed to provide rates up
to 20 gpm/sq ft and for a total backwash cycle of up to 10 minutes
in duration. The filter media are 2k" of coal (1mm effective size)
12" of sand (0.4-0.5 mm effective size).
Backwash Holding Tank
Tankage is provided to hold the backwash water and decant it back
to the treatment plant over a 24-hour period. This will eliminate
hydraulic surging of the treatment units.
\MlM23
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VI II-1
-------
DRAFT
The previous cost estimates were prepared based on the recommended de-
sign basis. Variations in the design basis or selection of alterna-
tive treatment processes can have appreciable effects on the reported
capital costs, as discussed in the General section.
Energy
Due to the characteristics of wastewater generated from hospitals and the
high degree of pollutant removal obtainable by use of activated sludge
treatment systems, application of high energy-consuming processes was not
considered. Therefore, the overall impact on energy for hospitals should
be minimal. Table VIIIH-1 presents the cost for energy and power for the
treatment model for BPCTCA, BATEA and BADCT. The details for energy and
power requirements are included in the Supplement A (supporting document).
Non-Water Quality Aspects
The major non-water quality aspects of the proposed effluent limitations
guidelines are ultimate sludge disposal, noise and air pollution.
The ultimate sludge disposal by landfill ing for the digested biological
sludge has been proposed. Is practiced correctly, landfill ing of the di-
gested biological sludge does not create health hazards or nuisance con-
dition. Sludge incineration is a viable alternative, but is not included
in the treatment model due to high cost and high fuel requirement.
The sludge quantities generated by the treatment model plants are estimated
to be 33,000 Ibs/year on dry solids weight basis.
Noise levels increase by the implementation of the proposed treatment model
needs a consideration in Hospital.
However in the installations observed, noise levels due to the treatment
plants were not a problem.
As incineration is not proposed in the treatment model, air pollution is not
of concern.
VI I 1-125
-------
DRAFT
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE (BPCTCA)
General
The effluent limitations that must be achieved by all plants by 1 July
1977 through the application of the best practicable control technology
currently available (BPCTCA) are based upon an average of the best per-
formance achievements of existing exemplary plants. In those industrial
categories where an exemplary treatment plant does not exist, the effluent
limitations have been based upon levels of technology which are
currently practiced in other industries with similar wastewater character-
istics and which can be practicably implemented by 1 July 1977.
The development of best practicable control technology currently avail-
able has been based on both in-plant and end-of-pipe technology for each
industrial subcategory. The effluent limitations commensurate with the
best practicable control technology currently available have been estab-
lished for each industrial subcategory on the basis of information in
Sections III through VIM of this report, and are presented in the
following sections. It has been shown that these limitations can be
attained through the application of BPCTCA pollution control technology.
The approach taken by each industry in developing BPCTCA effluent limita-
tions is described in the following text.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-1
-------
DRAFT
A. Pharmaceutical Industry
Based on the information contained in Sections III through VIII of this
report, effluent limitations guidelines commensurate with the Best
Practicable Control Technology Currently Available, which explicitly
set numerical values for the allowable pollutant discharges within each
subcategory are presented in Table IXA-1. The effluent limitations
guidelines specify allowable discharge of BODc and COD, based on re-
movals attainable through the application of BPCTCA pollution control
technology described in Section VII of this report. It should be empha-
sized that the removal efficiencies selected for determining BPCTCA ef-
fluent limitations guidelines represent average historical values of
exemplary waste treatment facilities within the Pharmaceutical industry.
For subcategories A, B, C^, D, and E, model BPCTCA waste treatment
technology includes equalization, neutralization, a biological treat-
ment system with sludge digestion, vacuum filtration and ultimate dis-
posal via landfill. For subcategory G£ the model waste treatment system
is thermal oxidation.
As previously discussed in Section VII, promulgation of effluent TSS
limitations based on historical TSS removal efficiencies is not feasible.
Since flocculator-clarifiers with polymer addition have been used in
other industries to reduce effluent TSS, it is reasonably assumed that
they can also be applied in the Pharmaceutical industry. On the basis
of this information, a TSS effluent limitations guideline of 50 mg/L
has been recommended for subcategories A and C-| , and 20 mg/L for sub-
categories B, Cp, D, and E. It is recommended that if more severe re-
strictions for total suspended solids are desired, these should be
established on the basis of water quality objectives. The objective of
these effluent limitations is to provide inducement for in-plant re-
duction of both flow and contaminant loadings, prior to end-of-pipe
treatment. However, it is not the Intent of these effluent limitations
guidelines to specify either the unit wastewater flow which must be
achieved, or the wastewater treatment practices which must be employed,
at the individual pharmaceutical plants.
As indicated in Section VII, the following treatment efficiencies,
based on historical treatment plant data (except for subcategory
were selected as being applicable for the determination of BPCTCA
effluent limitations guidelines. The treatment efficiencies for sub-
category Co are based on the performance of a thermal oxidation system.
Treatment Efficiency
(percent)
Subcategory BOD^ COD,
A, B, Clt D, E 93 89
C2 99 99
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-2
-------
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IN THIS REPORT AW ARE SOJJfCT TO CMAKGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-3
-------
DRAFT
The BPCTCA effluent limitations guidelines shown in Table IXA-1 were
developed by applying these treatment efficiencies to the RWL's shown
in Table VA-1 . *
It should be understood that the effluent limitations guidelines are
to be applied to individual subcategories. The information required
to do thi s is :
*•
1. The identity of the manufacturing process, so that it can be *"
subcategorized.
2. The production rate so that the specific limitation can be
calculated.
The actual effluent limitations guidelines would be applied directly
only to a plant whose manufacturing processes fall within a single
subcategory. In the case of multi-subcategory plants the effluent
limitations guidelines to be placed upon a plant would be the sum
of the individual effluent limitations guidelines applied to each of
its subcategory operations. This building-block approach allows the
system to be applied to any facility regardless of its unique set of *
processes.
Since separate limitations are specified for BODr, COD, and TSS, there
may be cases where compliance with one of the limitations would require
treating to levels below the active limitations for the other parameter,,
In such cases, compliance with BODc and TSS limitations will be factors
used to determine if a plant is in compliance with effluent limitations
gui deli nes.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-4
-------
DRAFT
B. Gum and Wood Chemicals Industry
Strategy for Development of BPCTCA
Effluent Limitations Guidelines
The effluent limitations guidelines for BPCTCA for the Gum and
Wood Chemicals Industry were developed by steps, starting from
the process raw waste loads (RWL).
As previously discussed in Section IV, subcategory A (production
of char and charcoal briquets via carbonization of hardwood and
softwood) is a net water consumer and discharges no process waste-
waters. Raw materials, intermediate char and charcoal briquets are
handled in a dry form. The char is brittle and disintegrates with
excessive handling, thus generating excessive fines and creating
fugitive dust problems in the production area. This problem can be
mitigated by utilizing buggies for material transport. Any off-
specification materials in the production can be reworked or dis-
posed of in dry form. Therefore, no discharge of process waste-
water pollutants Is consistent with BPCTCA for this subcategory
For the other five subcategories, the process RWL is a production-
based ratio relating specific pollutants to production quantities.
During the field sampling program, process RWL's were developed
for the five subcategories by sampling contact process wastewaters
wherever possible. Where it was not feasible to sample a segre-
gated, process wa:tewater stream (e.g., subcategory D), the total
process discharge was sampled but the RWL-flow was determined by
subtracting the uncontaminated cooling water and steam condensate
contribution from the total process discharge.
There were also instances where the data obtained for RWL-flow was
not considered representative of the process. For example, in
subcategory F, Plant No. 57 has the operating practice of venting an
aqueous waste stream to the atmosphere in a vapbr phase. It was
determined that normal industry practice is to condense such steam
vapor; therefore, this stream was included in the RWL-flow for that
plant, since the stream contacted small quantities of entrained
material and noncondensible hydrocarbons.
Single RWL values were established in each category for all pertinent
pollutants, historic data on raw waste loads was only available at
Plant No. 55, subcategory B, and Plant No. 55, subcategory F. All other
data was derived from the field sampling survey conducted by the con-
tractor. These data are indicative of the variations in raw waste
load which may exist for a single process at a particular plant or
between different manufacturers operating the same process. For
example, this variation in RWL's was observed between Plants No. 55
and No, 52 in subcategory B and is discussed in Section V.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-5
-------
DRAFT
The single set of values assigned to each process was designated as
the RWL which can be obtained through the application of in-process
pollution control practices which are commensurate with BPCTCA.
Briefly, the process modifications considered consistent with
BPCTCA include the following:
1. The recycle of still condensate for raw material washing water
as illustrated in Plant No. 55, subcategory B.
2. The on-site treatment and recycle of raw material wash water as
demonstrated in subcategory C.
3. The direct recycle of immiscible solvents as an absorbent of
noncondensible hydrocarbons as demonstrated in Plant No. 55,
subcategory F.
k. The recycle of water used in barometric condensers as demon-
strated in subcategory D.
End-of-pipe treatment technologies commensurate with BPCTCA are
based on the utilization of biological treatment, including activated
sludge or aerated lagoon with clarification of the lagoon effluent.
These end-of-pipe systems may include additional treatment operations
such as equalization, neutralization, dissolved air flotation for the
separation of insoluble hydrocarbons, or nutrient addition.
Although biological systems are considered as most generally appli-
cable to the wide variety of waste generated by this industry, it
should be noted that only two such systems were observed during
the study. The performance data for these two systems are presented
in Table VMB-2. The effluent from Plant No. 55, while producing a
high quality effluent, was considered atypical because the plant
was operating at low levels of production for approximately two weeks
prior to the plant survey. Plant No. 55 employed a trickling filter
which was inoperative during the survey period due to flooding of
the filter media. Therefore, the data could not be used to develop
adequate treatment models.
The design criteria for the proposed biological treatment models
were developed from bench scale biological treatability studies on
wastewaters from a wood naval stores production operation and two
tall oil by-product production facilities, as discussed in Section
VI IB of this document. It should be noted that metal catalyst may
in some cases be used in the production of rosin based derivative;.,
and that the process wastewaters may contain sufficient levels of
metal to be toxic or inhibitory to a biological system. However,
if specific manufacturing processes employing such catalyst discharge
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-6
-------
DRAFT
wastewaters are combined with wastewaters from processes not employ-
ing metal catalysts, the resulting toxicity of the total wastewater
may be reduced to non-inhibitory levels for biological treatment.
If this is not the case, BPCTCA does not preclude the use of in-
process pretreatmept for discharge to biological facilities, or
physical chemical processes to remove the toxic metals from the
process wastewaters.
Effluent Reduction Obtainable
Through Application of BPCTCA
Based on the information contained in Sections IV and VII of this
document, a determination has been made of degree of effluent re-
duction obtainable via BPCTCA, which is presented in Table IXB-1.
Although the effluent limitations guidelines for BPCTCA may be
obtained by whatever combination of in-process and end-of-pipe
means is best suited to the individual manufacturer, the numerical
values for the guidelines were calculated through application of
waste reduction factors based on the use of end-of-pipe biological
treatment systems. The waste reduction factors used for calculating
the BPCTCA effluent limitation guidelines for BOD and COD parameters are:
6005 - 95 percent
COD - 73 percent
These factors are based on the performance of biological treatment
systems described in Section VII -.Control and Treatment Technol-
ogies.
It should be noted that BODc should be used as the controlling
parameter for BPCTCA effluent limitations guidelines. The value specified for
COD would be used in those cases where the process waste (even after
dilution with other waste from plant operations) cannot be effec-
tively reduced in a biological system. In such cases, it is antici-
pated that some combination of in-process control coupled with
end-of-process system (e.g., physical-chemical processes) can achieve
the recommended effluent COD limitation. It should also be noted
that compliance with both BOD^ and COD effluent limitations guidelines
is not required.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-7
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
MO FURTHER INTERNAL REVIEW BY EPA.
IX-8
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
Based on the information contained in Sections III through VIM of
this report, effluent limitations guidelines commensurate with the
best practicable control technology currently available, which
explicitly set numerical values for the allowable pollutant dis-
charges within each subcategory, are presented in Table IIC-1.
The effluent limitations specify allowable discharge of BOD,- based
on removals attainable through the application of BPCTCA Pollution
Control Technology, described in Section VII of this report.
BPCTCA waste treatment technology includes various types of pre-
treatment, depending on the particular subcategory, a biological
oxidation system and sludge handling facilities. In addition, the
recommended technology includes incineration of highly concentrated
toxic wastes.
With few exceptions, untreated raw wastes generated by the
Pesticides and Agricultural Chemicals industry as a whole exhibit
some degree of toxicity to biological treatment and biological
analytical procedures. This phenomenon is illustrated by the high
COD to BODr, ratios indicated in Tables VC-6 to VC-10. Accordingly,
it would not be reasonable to drive limitations for biological treat-
ment effluents using removal efficiencies as a basis.
By contrast, effluent waste load data (refer to Bable VIIC-2) do
not exhibit the same degree of biological toxicity as raw waste load
data. This can be attributed to the fact that effluents discharged
from biological treatment systems, where residence times are commonly
high, have lower concentrations of toxic components. In other words,
effluent BODr data is more reliable and usable than raw waste load
data.
Since all of the recommended BPCTCA treatment models for the Pesti-
cides and Agricultural Chemicals industry feature biological treat-
ment, BODr limitations are the only direct measure of the treatment
effectiveness and the only reasonable parameter for developing ef-
fluent standards and limitations.
Based on the above arguments, it was decided to derive limitations
on effluent qualities and treatment performances being attained and
proven in the industry, and, in addition, these limitations should be
in terms of BODj-.
The BPCTCA limitations for the industry were developed in a stepwise
manner. First, based on industry data and observations, it was as-
certained that wel1-designed and operated treatment facilities could
achieve 30 mg/L BODr and *»0 mg/L TSS. These levels agree favorably
with the effluent data reported in Table VIIC-2.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-9
-------
DRAFT
Flow data of the industry were compiled for each subcategory,
as shown in Table IXC-1. From this data reasonable flow allo-
cations based on production rates were established for each sub-
category.
Subcategory A: Halogenated Organ!cs
Since Plant 70 does not utilize good water management practices,
it therefore cannot be considered as exemplary; the wastewater
flow from this plant is higher than the industry's in general.
In addition, the flow data for Plant 70 presented in Table IXC-1
includes non-process effluents, such as cooling water. Accordingly,
1,750 gal/1,000 Ib flow from Plant 6k was used as the flow allocation
value for the halogenated organics subcategory.
Subcategory B: Organo-Phosphorus
The flow allocation for this subcategory was derived from the
average of the data presented in Table IXC-1, and is equivalent
to 3,000 gal/1000 Ib.
Subcategory C: Organo-Nitrogen
The flow allocation for the organo-nitrogen subcategory was
developed from the data presented in Table IXC-1 by utilizing
the average flow value of 3,700 gal/1,000 Ib of product.
Subcategory D: Metallo Organic
The flow allocation for this subcategory is based on the data for
Plant 71 (Table IXC-1) and was set at 8,000 gal/1,000 Ib.
Subcategory E-l: Water-based Formulators/Packagers
The flow data presented in Table IXC-1 for this subcategory is not
considered representative of the industry as a whole, since Plant
66's is extremely good from a water and effluent management point
of view; on the other hand, Plant 69's is very poor. Therefore,
the data presented in Table VC-10 was used to develop a more
reasonable and realistic flow allocation. Since Plant 69 is quite
definitely non-exemplary, its flow data was not used. Using the
data from the other three plants, a flow allocation of 160 gal/1,000
Ib was establi shed.
Subcategory E-2: Solvent-based and "Dry" Formulator/Packagers
Since this subcategory is considered capable of attaining no dis-
charge of process wastewater pollutants, a flow allocation is not
appropriate or necessary.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-10
-------
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NOTICE THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-ll
-------
DRAFT
Using these flow values and the BODr (30 mg/L) and SS (kO mg/L)
concentrations, effluent limitations guidelines, in terms of
pound of pollutants per 1,000 pounds of product, were calculated.
These effluent limitation guidelines loadings agree well with
the observed loading attained by the existing wastewater treatment
plants in the industry (refer to Table VIIC-2).
The objective of these effluent limitations guidelines is to
provide inducement for in-plant reduction of both flow and
contaminant loadings, prior to end-of-pipe treatment. However,
it is not the intention of these effluent limitations guidelines
to specify the unit wastewater flow which must be achieved, or
the wastewater treatment practices which must be employed, at the
individual plants.
It should be understood that the effluent limitations guidelines
are to be applied to individual subcategories. To do this the
following information is required:
1. Identify of the manufacturing process (for subcategorization).
2. Production rate (for calculation of specific limitation).
The actual effluent limitations would be applied directly only to a
plant whose manufacturing processes fall within a single subcategory.
In the case of multi-subcategory plants, the effluent limitations
guidelines to be placed upon a plant would be the sum of the in-
dividual effluent limitations guidelines applied to each of its
subcategory operations. This building-block approach allows the
system to be applied to any facility, regardless of its unique set
of processes.
Since separate limitations are specified for various pollutants,
there may be cases where compliance with one of the limitations
would require treating to levels below the active limitations for
the other parameter. In such cases, compliance with BODr and TSS
limitations will be factors used to determine if a plant is in
compliance with effluent limitations guidelines.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-12
-------
DRAFT
D. Adhesives and Sealants Industry
Based on the information contained in Sections III through VIM of
this report, effluent limitations guidelines commensurate with the
best practicable control technology currently available have been
established for each subcategory of the Adhesives and Sealants
industry. These limitations may be attained through the application
of BPCTCA pollution control technology. BPCTCA in-process technology
includes the segregation of non-contact wastewaters from contaminated
process wastewater. The batch process wastewaters include mainly
cleaning and washing water.
As discussed in Section VII, BPCTCA end-of-pipe technology for
subcategory A is equivalent to the application of equalization,
primary clarification, a biological treatment, sludge digestion,
vacuum filtration, and off-site landfill for sludge cakes. BPCTCA
end-of-pipe technology for subcategories B and C is equivalent to
the application of evaporation systems. In subcategories D, E and
F, there is no discharge of process wastewater pollutants.
The recommended BPCTCA treatment systems are not the only ones which
may be applicable to a given subcategory. Specific treatability
studies may be required to determine effluent limitations guidelines
for some processes whose RWL's were not specifically defined by
sampling during this study.
It should be understood that the eff1uent 1imitations guidelines
are to be applied to individual processes as they are defined within
the five industrial subcategories. The actual effluent limitations
guidelines would only be applied directly to a plant whose manu-
facturing processes fall within a single subcategory; many adhesive
plants, however, are involved in multi-product manufacturing. In
this case, the effluent limitations guidelines placed upon a plant
would be the sum of the individual effluent limitations guidelines
applied to each of its subcategories. This additive approach allows
the system to be applied to any facility regardless of its unique
set of processes.
For the case of the biological treatment system, in absence of any
existing exemplary treatment facilities in the industry, the treat-
ment efficiencies considered to be attainable are based on pilot
studies with similar wastewaters. For the case of the liquid
evaporation system, since there are no data available for the
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-13
-------
DRAFT
treatment efficiencies, it is assumed that at least the same removal
efficiencies attainable by biological treatment for subcategory A
could be achieved by the liquid evaporation treatment system. In
reality, higher removal efficiencies will be attainable with the
application of liquid evaporation systems.
The treatment efficiencies selected as being applicable to subcate-
gories A, B, and C for the determination of BPCTCA effluent limitations
guidelines are as follows:
Parameter Treatment Efficiency
percent
BODr 33
COD 93
These treatment efficiencies were applied to the RWL for each
subcategory to attain BPCTCA effluent limitations guidelines
as shown in Table IXD-1.
It should also be noted that, since separate limitations are
specified for BOD, COD, and TSS, there may be cases where compliance
with one of the limitations will require treating to levels below the
actual limitations for the other. In such cases, it will be necessary
to ascertain the particular character of the waste and to determine
whether compliance with all these limitations is reasonable. This
discussion should be based on actual treatability studies of the
specific wastes or combination of wastes in question.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
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NOTICE THESE ABE TENTATIVE BE COMMENDATIONS BASED UPON INFORBATION
IN THIS REPORT AND ARE SUBJECT TO CHANCE BASED UPON COMMENTS RECEIVED
AW FURTHER INTERNAL REVIEW BY EPA.
IX-15
-------
DRAFT
E. Explosives Industry
The effluent limitations guidelines for BPCTCA for the Explosives
industry were developed from the information contained in Sections
IV to VIM of this document. The limitations are expressed in terms
of allowable pounds of pollutant per 1,000 pounds of products produced.
The guidelines are based on pollutant reductions being achieved in the
industry at the present time.
For all subcategories, the treatment system is the same: equalization,
neutralization, primary sedimentation, aeration basin, final clarifi-
cation, and sludge handling facilities. Subcategory B and C, however,
may choose to limit their effluent by other means. Subcategory B,
with a low flow of 6,800 gallons per day and moderate strength concen-
tration, could eliminate all wastewater flow in many cases. Averaging
only 2,520 gallons per day, Subcategory C with its concentrated waste
may find liquid incineration the most cost-effective solution. Sub--
category C could, by employing dry clean-up and more careful operations,
reduce its waste load to a level where it would be feasible to drum
all wastes and ship them to a regional treatment center.
It is recognized that the waste flow from Subcategory B is very dilute.
Hence, a biological process would not work well on this waste. However,
since load and pack operations are almost always combined with the manu-
facturing of explosives or propellants in a plant, it was concluded that
the same level of treatment be required for Subcategory B wastes. Hence,
no separate treatment system has been devised.
As indicated in Section VII, the following treatment levels, based on
historical data, were selected for the determination of BPCTCA effluent
limitations guidelines for all subcategories.
Average Concentrations
Parameter Percent Removal of RWL Limitation
BODr 93
COD 72
TSS -- 50 mg/L
TSS has a concentration limitation because, as previously discussed,
removal rates using activated sludge that produces an effluent TSS
concentration of less than 50 mg/L are unrealistic.
Note that although NO?-N can be in certain instances a significant
problem in this industry, np_ effluent limitation has been prescribed,
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-16
-------
DRAFT
The only reason to put an effluent limitation on NOo-N is if there
is a public water supply a short distance downstream. Since there
is no way of assuring that a munitions plant is significantly close
to a water supply intake, it is recommended that this be governed
in local conditions.
Application of these removal rates to the RWL produces the BPCTCA
effluent limitations guidelines shown in Table IXE-1.
It should be understood that the effluent limitations guidelines
are to be applied to individual subcategories. The information
required to do this are:
1. The identity of the manufacturing process, so that it can be
subcategorized.
2. The production rate, so that the specific limitation can be
calculated.
The actual effluent limitations guidelines would be applied
directly only to a plant whose manufacturing processes fall within
a single subcategory. In the case of multi-subcategory plants, the
effluent limitations guidelines to be placed upon a plant would re-
present a production-weighted sum of the individual effluent limitations
guidelines applied to each of its subcategory operations. This building-
block approach allows the guidelines to be applied to any facility
regardless of its products because of the different water bodies dis-
charged to.
It is anticipated that local conditions will control discharges of
nitrates and sulfates. Because of this, nitrates and sulfates are
not addressed in BPCTCA.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-17
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-18
-------
DRAFT
F. Carbon Black Industry
Based on the information contained in Sectjons Ml through VIM of
this report, effluent limitations guidelines commensurate with the
best practicable control technology currently available, which
explicitly set numerical values for the allowable pollutant dis-
charges within each subcategory, are presented in Table IXF-1.
The effluent limitations guidelines specify allowable discharges of
TSS based on removals attainable through the application of BPCTCA
Pollution Control Technology described in Section VII of this report.
The removal efficiencies selected for determining BPCTCA effluent
limitations guidelines represent average historical values of existing
waste treatment facilities within the Carbon Black industry. For
subcategory B, model BPCTCA waste treatment technology includes either
pond settling or more conventional clarifiers.
Based on a dehumidifier/quench water flow rate of 8,6^0 gallons per
thousand pounds of carbon black produced (72,100 L/kkg) in a closed
loop system, a blowdown of 100 gallons per thousand pounds of carbon
black produced (835 L/kkg) was considered reasonable. This is the
waste stream to which BPCTCA was applied. On the basis of these
data, an average TSS effluent limitation guideline of 0.053 kg/kkg
is recommended. Since variability data were unavailable, no daily
maximum values are presented. These should be developed through
experience in the industry.
Survey findings indicate that the furnace process is a net user of
water, i.e., no process contact wastewater is discharged from the
process. Based on this fact, no discharge of process wastewater
pollutants is recommended for subcategory A.
The objective of these effluent limitations guidelines is to provide
inducement for in-plant reduction of both flow and contaminant loadings,
prior to end-of-pipe treatment. However, it is not the intent of these
effluent limitations guidelines to specify either the unit wastewater
flow which must be achieved, or the wastewater treatment practices which
must be employed, at the individual carbon black plants.
It should be understood that the effluent limitations guidelines
are to be applied to individual subcategories. The information
required to do this is:
1. The identity of the manufacturing process, so that it can be
subcategori zed.
2. The production rate so that the specific limitation can be
calculated.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-19
-------
3 u
NOTJ_CE_. THESE ARE TENTATIVE RECOMMENDATIONS 8ASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA
-------
UKMr I
The actual effluent limitations guidelines would be applied directly
only to a plant whose manufacturing processes fall within a single
subcategory. In the case of multi-subcategory plants the effluent
limitations guidelines to be placed upon a plant would represent the
sum of the individual effluent limitations applied to each of its
subcategory operations. This building-block approach allows the
system to be applied to any facility regardless of its unique set
of processes.
It should be noted that BPCTCA treatment technology, as discussed
in Section VII, has been designed with TSS removal as the primary
design consideration.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-21
-------
[1RAFT
G. Photographic Processing Industry
Effluent limitations guidelines for the entire Photographic
Processing industry were developed by applying the in-plant
measures and end-of-pipe treatment model presented in Section VII.
The in-plant measures include silver recovery, bleach regeneration,
and squeegee installation. The raw waste loads developed from the
three processing plants visited were subject to percentage removal?'
commensurate with these controls. The variability in this system
is discussed in Section XIII.
The design data from the large-scale activated sludge unit was the
basis of the BODc, COD, and silver thiosulfate reduction obtainable
through BPCTCA presented in Table IXG-1. Although the effluent
limitation guidelines for BPCTCA may be attained by a number of
combinations of in-process and end-of-process means, the numerical
values for these guidelines were calculated by the application of
waste reduction factors in the BPCTCA treatment model for BOD, COD,
and silver thiosulfate parameters. The reduction factors are as
follows:
6005 - 85 percent reduction (effluent is 15 percent of RWL)
COD - 50 percent reduction (effluent is 50 percent of RWL)
Silver thiosulfate - 80 percent reduction (effluent is 20
percent of RWL)
The concentration limitatin placed on ferrocyanide was based on
studies which indicated that cyanide in levels greater than 1 mg/L
inhibited biological systems. Insufficient data on TSS removal
rates by the biological system prevents a direct determination of
an effluent limitation for the industry; however, based on tech-
nology transfer from other industries, a daily average concentration
of 20 mg/L of suspended solids has been set.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-22
-------
O 0
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DRAFT
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o o o -
— O (M
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
IX-23
-------
DRAFT
H. Hospi tals
Based on the information contained in Sections III through VIM of
this report, effluent limitations guidelines commensurate with the
best practicable control technology currently available have been
established for hospitals. The limitations which explicitly set
numerical values for allowable pollutant discharges are presented
in Table IXH-1. The effluent limitations guidelines specify allow-
able discharges of BOD^ and TSS based on removals attainable through
application of BPCTCA pollution control technology described in
Section VII of this report. Model BPCTCA waste treatment technology
includes biological treatment with sludge handling facilities con-
sisting of digestion, dewatering, and ultimate disposal via a
sanitary landfill.
As indicated in Section VI I, a BODr removal efficiency of 93
percent, based on historical treatment plant data, was selected
as being applicable for the determination of BPCTCA effluent
limitations guidelines. Promulgation of effluent TSS limitations
based on historical TSS removal efficiencies is not feasible in
that activated sludge treatment systems generate biological solids.
The BPCTCA model treatment plant has been designed to include a
flocculatoi—clarifier with polymer addition. Such systems have
been shown to be capable of achieving extremely efficient TSS
removal. On this basis, a TSS effluent limitation guidelines of
20 mg/L is recommended. If a more severe restrictions for total
suspended solids is desired, it should be established on the basis
of water quality objectives.
The objective of these effluent limitations guidelines is to pro-
vide inducement for reduction of both flow and contaminant loading
prior to end-of-pipe treatment. However, it is not the intent of
these effluent limitations guidelines to specify either the unit
wastewater flow which must be achieved, or the wastewater treatment
practices which must be employed at individual hospitals.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
\X-2k '
-------
•o TJ
ja ja
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NOTICE THESE ARE TENTATIVE RECOMMCNDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COHMtHTS RECEIVED
AND FURTHER INTERNAL REVIEW BV EPA.
IX-25
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
Gene ra 1
The effluent limitations guidelines to be achieved by all plants by
July 1, 1983 through the application of the best available technology
economically achievable (BATEA) are based upon the very best control and
treatment technology employed by the existing exemplary plants in each
industrial subcategory. In those industrial subcategories where this
level of control and treatment technology was found inadequate for the
purpose of defining BATEA, control and treatment technologies trans-
ferrable from other industries or technology demonstrated in pilot
plant studies were employed.
BATEA in-plant technology and end-of-pipe systems for the individual
industrial categories are discussed in the following text.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-l
-------
A. Pharmaceutical Industry
L,,.u^,.l. ..VJ,.,^,,-. v,u.v.^..,.^^ v^ v....,u. u..,, ..,,.,, ,.,,v- ^JU uvaiiaui^
technology economically achievable are presented in Table XA-1. BATEA
effluent limitations guidelines were developed by evaluating those end-
of-pipe modifications which seemed applicable for achieving better
effluent quality. The BATEA effluent limitations guidelines presented
in this section can be attained with the end-of-pipe treatment technology
outlined in Section VII, which consists of the addition of dual-media
filtration and activated carbon adsorption to the proposed BPCTCA
technology for sub-categories A and Cj. BATEA effluent limitations
guidelines for subcategories B, D and E are based on the addition of
dual-media gravity filtration to the proposed BPCTCA technology. For
subcategory C2, BATEA effluent limitations guidelines are the same
as BPCTCA effluent limitations guidelines.
BATEA effluent limitations guidelines were developed by the following
procedure:
1. Based on the contractor's experience with application of dual-media
filtration in other industries, filtration information contained
in Process Design Manual for Upgrading Existing Wastewater Treat-
ment Plants (EPA 197*0, and information contained in other liter-
ature, the following effluent TSS concentrations were selected as
being achievable by dual-media filtration of biologically treated
wastes.
Subcategory Effluent TSS. mq/L
A, C1 20
B, D, E 10
2. As discussed in Section VII, samples of biological treatment plant
effluents were filtered to determine the BODq and COD concentrations
associated with TSS. Based on those tests, the following relation-
ships were developed:
BOD q _ . COD . ..
TSS 5 ~ °'2° TSS ~ ]']k
The amount of BOD^ and COD that could be removed by filtration
was then calculated by multiplying the expected TSS removal by
the above relationships. For example: BODc due to filtration =
0.20 (BPCTCA TSS effluent limitation - BATEA TSS effluent limi-
tation) .
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-2
-------
UKAh
Effluent limitations guidelines for dual-media filter effluents
w were then calculated by subtracting from the BPCTCA effluent limitations
guidelines the BQDr and COD removed by filtration. 'n the cdse <>T
subcategories B, D? and E these values have been used as the BATEA
effluent limitations guidelines.
3. For subcategories A and Cj, the values obtained by the procedure
discussed above were further reduced by applying the following
removal efficiencies, which are achievable by the use of activated
carbon adsorption.
Parameter Activated Carbon Treatment Efficiencies
(percent)
BOD5 77
COD 80
As discussed in Section VII, these treatment efficiencies were
based on results of laboratory carbon isotherm tests. As actual
full-scale performance data become available, effluent limitations
guidelines based on these performance standards will be re-evaluated.
In cases where compliance with one of the effluent 1imitationsguidelineS
would require treating to levels below the - limitations for
the remaining parameters, determination of compliance should be
based on the following controlling parameters:
Subcategory Controlling Limitations
A, Cr C2 COD, TSS
B, D, E BOD5, TSS
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-3
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MOT ICI: THESE ARE TENTATIVE MCONHENOATIONS BASED UPON INFOMMTION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW IV EPA.
»-*
-------
DRAFT
B. Gum and Wood Chemicals Industry
Treatment commensurate with BATEA for Gum and Wood Chemicals industry
requires the application of activated carbon adsorption to filtered
effluent from the biological treatment system described for BPCTCA,
or the use of second stage biological treatment in series with the
BPCTCA. The specific choice of waste treatment systems should depend
on the specific process, or group of processes, in operation at any
gi ven faci1i ty.
The performance of these systems has been discussed in Section VII -
Control and Treatment Technologies. Incremental waste reduction
associated with these technologies for BOD and COO parameters are:
BOD - 70 percent reduction (BATEA effluent is 30 percent of a
5 BPCTCA.effluent)
COD - 70 percent reduction (BATEA effluent is 30 percent of a
BPCTCA effluent)
Effluent 1imitat ions guide!ines for BATEA were calculated by applying
the above reduction factors to average effluent for BPCTCA shown in
Table IXB-1.
The effluent limitations guidelines for BATEA are presented in Table
XB-1. Again, it must be understood that the BOD and COD values as
presented are average daily effluent limitations guidelines for BATEA
and should not be directly applied before adjustment for variation in
treatment plant performance, as presented in Section XIII.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-5
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NOTICE: THESE ARE TENTATIVE KECONMENDATIONS BASED UPON IHfOdMATIOK
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON CONNECTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
Best available technology economically achievable (BATEA) for the pesti-
cides segment of the miscellaneous chemicals pojnt source category is
based upon end-of-process treatment technologies. The wide diversity of
the Pesticides and Agriculture Chemicals industry prevents describing a
concise list of in-plant control techniques applicable to the industry
as a whole under BATEA. This problem is aggravated by the fact that the
industry zealously guards information relating to the nature of a specific
manufacturing process. This secrecy may or may not be warranted in order
to maintain a competitive position. However, it makes the development of
effluent limitations guidelines utilizing considerable in-plant control
impossible. Therefore, although the use of in-plant techniques may
represent a viable alternative for specific manufacturers, general
effluent limitations guidelines for BATEA have been developed based
upon the application of additional end-of-pipe treatment technologies.
Treatment commensurate with BATEA requires the application of multi-media
filtration and activated carbon adsorption to the effluent from the
activated sludge treatment proposed under BPCTCA.
Effluent limitations guidelines for each subcategory of pesticides
manufactured are presented in Table MC-2.
BATEA COD effluent limitations guidelines are based on achievement of
75 percent COD removal by the activated carbon system. TSS limitations
are based on filtration information contained in Process Design Manual
for Upgrading Existing Wastewater Treatment Plants, EPA, 197**, and in"-'
formation contained in other literature.
The application of BATEA treatment technology will not have a significant
effect on other pollutant parameters limited by BPCTCA quidelines. Con-
sequent, ly, the recommended BATEA effluent 1i in iLa I ions guidelines for
these parameters are identical to those specified under BPCTCA effluent
1imi tat ions.
NOT ICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASFO UPON COMMENTS RFPFIVFD
AND FURTHER INTFRNAl RFVIFW RY FPA.
X-7
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-------
DRAFT
D. Adhesive and Sealants Industry
Effluent limitations guidelines commensurate with the best available
technology economically achievable and with new-source performance
standards are identical for subcategories B and C. It must be recog-
nized that, in most cases, in-process modifications to existing plants
are equivalent to those which can be designed for new ones. Although
there are specific systems which can effectively reduce the RWL from
particular processes to zero, these "zero discharge" systems may or
may not be uniformly applicable throughout each subcategory. Investi-
gations should be conducted for all types of adhesive wastewaters to
see if the wastewaters can be totally recycled or to see if the waste-
water discharges can be eliminated altogether. The specific systems
and associated processes are identified in Section IV of this report.
None of the plants sampled during the data collection program had
end-of-pipe treatment systems, and therefore, information collected
was inadequate for establishing effluent limitations commensurate
with the best available technology economically achievable or with
new-source performance standards. A thorough investigation of avail-
able literature, treatability studies for similar wastewaters, and
the contractor's experience in this area were utilized to supplement
existing data in the development of the treatment systems and effluent
limitations guidelines.
The BATEA treatment system for subcategory A included BPCTCA plus ad-
ditional biological treatment followed by dual-media filtration. The
end-of-pipe treatment system proposed for BATEA and BADCT for sub-
categories B and C is identical to BPCTCA, i.e., double effect evapo-
ration preceded by an equalization basin or surge tank.
Each of the BATEA and BADCT affluent limitations guidelines is attain-
able with the treatment systems indicated. However, each plant should
use those treatment processes which are applicable to its own waste-
water.
The BATEA limitations proposed represent a combination of in-process
and end-of-pipe control measures. The specific nature of this com-
bination depends on the contact process wastewater flow to which the
control measures are applied. This is not meant to imply that reduc-
tion in water usage is an acceptable substitute for reduction of pol-
lutant loads. However, practical technical considerations dictate
that most in-plant modifications for decreasing contact process water
flow do not reduce he accompanying pollutant loadings in the same
proportion.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-9
-------
IJKAFI"
BATEA effluent limitations guidelines are based upon the following re-
movals from BPCTCA:
Percent Removal of
Parameter BPCTCA Effluent
BOD Removal
COD Removal
The BATEA effluent limitations guidelines were developed by applying
these treatment efficiencies to BPCTCA effluent as shown in Table XD-1
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-10
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NOTICE THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANCE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA
-------
DRAFT
E. Explosives Industry
The BATEA effluent limitation guidelines for the Explosives industry
presented below have been developed from the best available technology
presently operating in the field. Historical data was used to develop
effluent limitations guidelines. For all subcategories, the BATEA
treatment focuses on filtration and carbon adsorption. Published
findings generally support the biodegradation of most explosives.
Those explosives that are resistant to biodegration will be removed
by carbon adsorption.
BATEA Effluent Limitation Guidelines
Explosives Industry
Percent Removal of
Parameter BPCTCA Effluent
BOD5 12%
COD 79%
TSS
Application of these removal rates to BPCTCA effluent waste loads is
shown in Table XE-1 .
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-12
-------
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NOTICE: THESE ARE TENTATIVE KECOMHENDATIONS lASED UPON INFOKMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE USED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-U
-------
DRAFT
F. Carbon Black Industry ^^
Effluent limitations guidelines commensurate with the best available
technology economically achievable are presented in Table XF-1. BATEA
effluent limitations guidelines were developed by evaluating those end-
of-pipe modifications which seemed applicable for achieving better ef-
fluent quality. The BATEA effluent limitations guidelines presented in
this section are attainable with the end-of-pipe treatment technology Q
outlined in Section VII, which consists of the addition of dual-media
gravity filtration to the treatment system proposed for subcategory B
as BPCTCA technology. BATEA effluent limitations guidelines for sub-
category A wi 11 remain at no discharge of process wastewater pollutants.
As indicated in Section VII, the following treatment efficiencies in £
cremental over BPCTCA were considered to be applicable for determi-
nation of BATEA effluent limitations.
Subcategory Effluent TSS
A No discharge of process £
wastewater pollutants
B 60 percent
BATEA effluent limitations guidelines were developed by applying these
treatment efficiencies to the BPCTCA effluent limitations guidelines
shown in Table IXF-1.
The treatment efficiency for subcategory B was based on performance
data for filtration processes used in other applications. As actual
full-scale performance data become available, effluent limitations
guidelines based on these removal efficiencies may require revision.
Although the thermal black plant visited discharged no wastewater,
this fact cannot be uniformly applied to the entire industry to develop
no discharge of process wastewater. This is due to the location of the
facilities in question. As discussed in Section VII, it was not possible
during the survey to gain sufficient access to individual manufacturing
processes to quantitatively ascertain the effectiveness of in-plant con-
trol measures. Consequently, recommendations for specific in-plant
process modifications for achieving better effluent quality have not
been made.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-14
-------
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MOT ICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW IV [PA.
X-15
-------
DRAFT
G. Photographic Processing Industry
Treatment commensurate with BATEA for the Photographic Processing in-
dustry requires the application of filtration to the effluent from
BPCTCA biological treatment.
The performance of these systems has been discussed in Section VII.
Incremental waste reduction possible with these technologies is:
BODr - 33 percent reduction (BATEA effluent is 6? percent
of BPCTCA effluent)
COD - 20 percent reduction (BATEA effluent is 80 percent
of BPCTCA effluent)
Silver thiosulfate = 0 percent
Effluent limitations guidelines for BATEA were calculated by applying
the above reduction factors to the BPCTCA effluent limitations guide-
lines as shown in Table IXG-1. Insufficient data on TSS removal rates
prevented an effluent limitations guidelines determination for the in-
dustry, but, based on technology from other industries, a daily average
concentration of 10 mg/L was set.
The effluent limitations guidelines for BATEA are presented in Table XG-1
Again, it must be understood that the BOD and COD values as presented
are average daily effluent limitations guidelines for BATEA and should
not be directly applied before compensating for variation in treatment
plant performance in the manner described in Section XIII.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-16
-------
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUWECT TO CHANCE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-17
-------
DRAFT
H. Hospi tals
Effluent limitations guidelines commensurate with the best available
techonology economically achievable are presented in Table XH-1. BATEA
effluent limitations guidelines were developed by evaluating those end-
of-pipe modifications which indicated applicability for achieving better
effluent quality. The BATEA effluent limitations guidelines are attain-
able with the end-of-pipe treatment technology outlined in Section VII,
which consists of the addition of dual-media filtration to the treatment
system proposed as BPCTCA technology.
In absence of any performance data for dual-media filtration on the
biological treatment effluent for Hospitals, the performance of the
dual-media filters as contained in Process Design Manual for Upgrading
Existing Wastewater Treatment Plantl; by EPA 197** is considered appli-
cable to the Hospitals wastewaters. The BATEA effluent limitations
guidelines are based on this performance data. As additional plant
performance data becomes available, it may be used to verify the initial
judgements.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-18
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
X-19
-------
DRAFT
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
Genera 1
The term "new source" is defined in the Environmental Protection Act to
mean "any source, the construction of which is commenced after the publi
cation of proposed regulations prescribing a standard of performance".
Technology applicable to new sources shall be the Best Available Demon-
strated Control Technology, defined by a determination of what higher
levels of pollution control can be attained through the use of improved
production process and/or treatment techniques. Thus, in addition to
considering the best in-plant and end-of-process control technology,
BADCT technology is to be based upon an analysis of how the level
of effluent may be reduced by changing the production process itself.
BADCT fn-plant technology and end-of-plpe systems for individual
industrial categories are discussed in the following text.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-1
-------
DRAFT
A. Pharmaceutical Industry
New source performance standards commensurate with BADCT for the
Pharmaceutical industry are presented in Table XIA-1. These per-
formance standards are attainable with the end-of-pipe treatment
technology outlined in Section VII, which consists of the addition
of filtration to the treatment system proposed as BPCTCA technology
for subcategories A, B, C, D and E. New source performance standards
for subcategory C are identical to BPCTCA limitations.
The wastewater treatment technology recommended for new source pel—
formance standards does not include the use of activated carbon adsorp-
tion, as this advanced wastewater treatment technology has not been
sufficiently demonstrated in the Pharmaceutical industry to establish
operating performance, reliability, and economics.
For subcategories B, D, and E, new source performance standards are
identical to BATEA effluent limitations guidelines. The performance
standards for subcategories A and C^ were developed according to the
rationale presented in Section X for determining pollutant removals
obtainable by filtration. It is conceivable that in certain cases
compliance with one of the specific performance standards presented
in such cases determination of compliance should be based on BODr
and TSS performance standards.
With the construction of new pharmaceutical plants, potential exists
for substitution of processes which produce lower raw waste loads for
others with higher raw waste loads. However, no recommendations are
made with regard to such process substitutions, since in most cases
during the survey the access to individual manufacturing processes
needed to develop such recommendations were not permitted. In addi-
tion, major changes in pharmaceutical manufacturing processes are
subject to the approval of FDA and often require extensive research
programs. Consequently, process modifications are not as readily
expedited in the Pharmaceutical industry as within other industries.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-2
-------
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-------
DRAFT
B. Gum and Wood Chemicals [industry
Best Available Demonstrated Control Technology (BADCT) for the Gum
and Wood Chemicals industry is based upon the utilization of both
in-process controls and end-of-pipe process treatment technologies,
which include biological treatment as proposed for BPCTCA and removal
of additional total suspended solids via effluent filtration. The
reduction in BOO and COD parameters via the filtration of BPCTCA
effluent is as follows:
BOD - 8 percent reduction of BPCTCA effluent
COD - 13 percent reduction of BPCTCA effluent
As with BATEA, suspended solids limitation is 20 mg/L, which will be
applied to the effluent from the entire treatment facility.
Table XIB-1 indicates BADCT effluent limitations guidelines for the
Gum and Wood Chemicals industry for subcategories B through F. As
with BPCTCA and BATEA, the values shown for the average BADCT ef-
fluent should not be directly applied until they are adjusted, as
presented in Table XIB-1, for variation in treatment plant perform-
ance as provided in Section XIII, Performance Factors in Treatment
Plant Operations.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-It
-------
DRAFT
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-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
New source performance standards commensurate with BADCT for the
Pesticides and Agricultural Chemicals industry are presented in
Table XIC-1.
Best Available Demonstrated Technology Control Technology proposed
consits. of addition of filtration to BPCTCA treatment model, as a
means of further suspended solids removal. The recommended perform-
ance standards are identical to the BPCTCA values with the exception
of TSS. The recommended TSS standards is 20 mg/L for all subcategories.
With the construction of new pesticides production facilities, potential
exists for the application of in-plant pollution control measures which
could reduce raw waste loads. However, no specific recommendations
are made with regard to in-plant measures since sufficient data was
not available to develop such recommendations in detail.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-6
-------
Hew Source Performance Standards
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NOTICE: THESE AM TENTATIVE KCOMMENDATIONS IASED UPON INFORMATION
Ik THIS «EPO«T AND AM SIWJECT TO CHANCI IASED UPON COMMENTS MCEIVED
AND FURTHER INTERNAL MVIIW IT IPA.
XI-7
-------
DRAFT
D . Adhesive and Sealants Industry
Best Available Demonstrated Control Technology (BADCT) for the Adhesive
and Sealants industry js based upon the utilization of both in-plant
controls and end-of-pipe process treatment technologies. The end-of-
pipe treatment technology for subcategory A includes biological treat-
ment as proposed for BPCTCA and removal of additional total suspended
solids via effluent filtration. New source performance standards
were obtained by applying the following reduction in the BPCTCA ef-
fluents :
TSS removal = 60 percent
BODc removal = 0.2 x TSS removed
COD removal = 1.1^ x TSS removed
The end-of-pipe treatment technology for subcategories B and C are
identical to those for BPCTCA which is a double effect evaporation
preceded by an equalization basin or surge tank. The new source
performance standards commensurate with BADCT are identical with
BPCTCA for subcategories B and C.
*.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-8
-------
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MOT ICE THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ABE SUUECT TO CHANCE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW IV EPA.
-------
E xp1os i ves Industry
BADCT is based upon the utilization of in-house controls and filtration
as an addition to BPCTCA end-of-pipe processes. The BADCT limitations
presented in Section VII were developed on the basis of the contractor's
previous experience and EPA publications on the efficiency of a filter.
The waste load reductions are presented below. Application of these
removal rates to BPCTCA effluent production loads is shown in Table XIE-1
New Source Performance Standards
Wasteload Reductions
Percent Reduction of
Parameter BPCTCA Effluent
BOD5 8.0
COD 13.0
TSS 60.0
It was anticipated that, for this level of treatment, significant
reduction of hydraulic loading will be implemented by application
of good water management practices.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-10
-------
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IN VHIS REDOUT AMD AM SUtJECT TO CHANCE IASEO UMN COMMENTS RECtlVEO
AND FURTHEK INTERNAL REVIEW IY EPA.
-------
DRAFT
F. Carbon Black Industry
New source performance standards commensurate with BADCT for the Carbon *
Black industry are presented in Table XIF-1. These performance stand-
ards are attainable wi|;h the end-of-pipe treatment technology outlined
in Section VII, which consists of the addition of filtration to the
treatment system proposed as BPCTCA technology.
As indicated in Section VII, the following treatment efficiencies were *
selected as being applicable for determination of new source perform-
ance standards:
Subcateqory TSS Removal Efficiency
(Incremental over BPCTCA)
A No dicharge of process waste-
water pollutants
B 60%
These removal efficiencies were selected on the basis of a review of
the application of filtration to the other industries.
New source performance standards were developed by applying these
treatment efficiencies to the BPCTCA effluent limitations shown in
Table XIF-1 .
A
No recommendations have been made regarding the substitution of pro- ^^
cesses which produce a lower raw waste load for others with higher
raw waste load. In most instances, the access to individual manu-
facturing processes needed to develop such recommendations was not
permitted.
Table XIF-1 *
New Source Performance Standards
Carbon Black Industry
Average *
Subcateqory Daily TSS
kg/kkg
A No discharge of process waste-
water pollutants _
B 0.021
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-12
-------
DRAFT
G. PhotographI c Process i nq Industry
Best Available Demonstrated Control Technology (BADCT) for the
Photographic Processing Industry is based upon the utilization of
both in-process controls and end-of-pipe process treatment tech-
nologies which include biological treatment as proposed for BATEA.
Performance standards for BODr and COD parameters are identical
with the BATEA effluent limitations guidelines. Table XIG-1 presents
BADCT performance standards for the Photographic Processing industry.
As with BPCTCA and BATEA, the values shown for the average BADCT ef-
fluent should not be directly applied until they are adjusted for
variation in treatment plant performance as provided in Section XIII-
Performance Factors In Treatment Plant Operations.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-13
-------
DRAFT
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-14
-------
DRAFT
H. Hospitals
The performance standards commensurate with the Best Available Tech-
nology Economically Achievable are also recommended as new source
performance standards. These performance standards are presented in
Table XIH-1.
It must be recognized that, in most cases, in-house modifications to
existing hospitals are interchangeable with those which can be de-
signed for new ones. Investigations should be conducted for all types
of hospital wastewater sources to see if the wastewaters can be elimin-
ated or reduced in quantities.
NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-15
-------
DRAFT
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NOTICE: THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
IN THIS REPORT AND ARE SUBJECT TO CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER INTERNAL REVIEW BY EPA.
XI-16
-------
DRAFT
SECTION XI I
PRETREATMENT GUIDELINES
General
Pollutants from specific processes within the Miscellaneous Chemicals
industry may interfere with, pass through, or otherwise be incompatible
with publicly owned treatment works (municipal system) The following
sections examine the general wastewater characteristics of the various
industries and the pretreatment unit operations which may be applicable,
XI 1-1
-------
DRAFT
A. Pharmaceutical Industry
The majority of the manufacturing plants in the Pharmaceutical industry
discharge their wastewaters into municipal sewage collection systems.
The major sources of wastewaters in the Pharmaceutical industry are
product washings, extraction and concentration procedures, and equipment
washdown. Wastewaters generated by this industry have high concentra-
tions of 8005, COD, TSS, and volatile organics. Wastewaters from some
chemical synthesis and fermentation operations may contain metals
(Fe, Cu, Ni, Ag, etc.) or cyanide and have anti-bacterial constituents,
which may exert a toxic effect on biological waste treatment processes.
For example, one class of pharmaceutical chemicals produced is bacterio-
stats, disinfectants, and compounds used for sterilizing public facilities,
hospitals, etc. Certain formulations containing phenolics have been
effective in this area. Since these products are, by nature, disinfectant,
a biological treatment system could be deactivated if the raw effluent
from such a manufacturing process was directly charged to the treatment
system at too high a concentration. It may be necessary to equalize or
chemically treat process effluents. This pretreated effluent, in certain
circumstances, shoud then be acceptable for treatment in a conventional
municipal system.
Considerations significant to the design of a pretreatment plant which
will receive pharmaceutical plant effluent are the highly variable 8005
loadings, high chlorine demand, presence of surface-active agents, and
the lack of required nutrients which may characterize the wastewater.
In view of the wastev^ater characteristics discussed above, it was con-
cluded that certain production techniques could be grouped together on
the basis of pollutants requiring pretreatment. Accordingly, the pre-
viously determined five technology subcategories for the pharmaceutical
industry were divided into two pretreatment sub-groups as follows:
Sub-Group 1 Sub-Group 2
Subcategory A Subcategory B
Subcategory C Subcategory D
Subcategory E
The principle difference in the general characteristics of the process
wastewaters generated by the process techniques in these two Sub-Groups
is that the wastewaters of Sub-Group 1 are more likely to include signi-
ficant amounts of metals, cyanide, and spent solvents. The waste-
waters generated by the two process subcategories in Sub-Group 1 are
also generally much higher-strength wastes than those from the Sub-Group 2
process subcategories.
XI I-2
-------
DRAFT
The types and amounts of metals and spent solvents in the wastewater
from a pharmaceutical manufacturing process depend primarily on the
manufacturing process and on the amounts and types of catalysts and
solvents lost from the process. Most catalysts and solvents are
expensive and therefore, are recovered for reuse. Only unrecoverable
catalysts (metals), generally in small concentrations, and spent
solvents appear in the wastewater.
Pharmaceutical industries generate wastewaters on an intermittent basis
and equalization may be needed as pretreatment. When solvents are used
for extraction, solvent removal can be accomplished by using gravity
separation and skimming. Neutralization may be required to neutralize
acidic or alkaline wastewaters generated from the production of specific
pharmaceutical products. The metals present in some pharmaceutical
wastes are in many cases so low in concentration that the removal of
metals is not required from the standpoint of treatability characteristics.
However the effluent limitations for metals and toxic pollutants may
require additional pretreatment (chemical precipitation) for removal of
these materials.
The pretreatment unit operations which may be necessary for various types
of joint treatment facilities are shown in Table XIIA-1. The pretreat-
ment unit operations which may be required for a Sub-Group 1 consist of
equalization, neutralization, solvent separation, cyanide removal and
spill protection for chemical storage areas. For Sub-Group 2 the general
requirements are equalization and neutralization.
XI 1-3
-------
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DRAFT
B. Gum and Wood Chemlca1s Industry
A review of the wastewater characteristics in the Gum and Wood Chemicals
industry reveals that the process wastewaters contain high concentrations
of soluble oxygen demanding materials, and are generally acidic and
deficient in the nutrients phosphorous and nitrogen. Significant con-
centrations of zinc were noted during the survey in subcategories B and
F. The zinc metal in subcategory F was attributed to losses of process
catalyst. Contamination of gum distillation wastewaters with process
wastewaters from subcategory F process is the suspected source of zinc
in subcategory B wastewaters.
Oil and grease (from vegetable sources) was found in wastewaters from
subcategories B, D and F. These oils are not hazardous and generally
considered more biodegradable than oils from petroleum sources. However,
separable oils should be removed from the process wastewaters by pre-
treatment prior to discharge to public sewers in order to minimize
fouling problems in the sewer.
The scope of this study did not allow for a specific toxicity evaluation
of individual product wastewaters. However, the completeness of the
RWL analytical data did provide a wastewater profile which could be used
to evaluate possible biological inhibition. Such evaluations must bring
into account the dilution effect of domestic wastewaters when considering
concentrations of possible inhibiting materials. Domestic wastewaters
should also provide sufficient nitrogen and phosphorous to improve the
treatability characteristics of the process wastes. Because this indus-
try's wastewaters contain high levels of soluble oxygen demand in
relatively small discharge flow, it will be necessary that the sewage
treatment facility have sufficient oxygen transfer and solids handling
and disposal capacity to adequately treat wastewaters from the Gum and
Wood Chemicals industry. If such capacity cannot be made available at
the public system, biological pretreatment facilities must be provided
by industry to reduce the oxygen demand content of the process wastewaters
to acceptable levels before discharge to the public sewers. In all cases,
the industry should provide sufficient equalization and neutralization
of wastewaters to prevent discharge loadings which could cause adverse
impact on the performance of the municipal system. Table XIIB-1 shows
possible unit operations which may be required for pretreatment of gum
and wood chemicals wastewaters.
Xll-5
-------
DRAFT
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XI 1-6
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
Pollutants from specific processes within the pesticide industry may
pass through inadequately treated, interfere with, or otherwise be
incompatible with a publicly-owned treatment works.
Strong wastes and toxic wastes should not be discharged to municipal
treatment systems. Wherever possible, such wastes should be incinerated
or disposed of in an approved manner by a certified contractor.
General process wastewaters will require neutralization to protect
sewer collection lines from corrosion damage. Removal of separable
organics should be performed by means of an API-type separator, and
solids which could potentially block municipal sewer systems require
removal. Equalization is recommended to avoid shock loads of flow,
basic organic contaminants and toxic components. In addition to
these general pretreatment requirements, the individual pesticide
subcategories generally require specific pretreatment steps.
Halogenated Organic Pesticides
The wastewaters from this category require no specific pretreatment
other than those mentioned above.
Organo-Phosphorus Pesticides
In addition to the general pretreatment guidelines outlined above,
process wastewaters from facilities in tlvs subcategory may require
detoxification. Detoxification is best accomplished by extended heat
treatment in alkaline conditions. Without detoxification, the wastes
would have an inhibitory affect on biological treatment. In addition,
alkaline precipitation of phosphate-type naterials may be necessary
in seme cases.
Organo-Nitrogen Pesticides
The general discussions on pretreatment are applicable to the Organo-
Ni trogen subcategory. In addition, some method of cyanide removal may
be necessary to bring cyanide concentrations down to acceptable levels
for municipal treatment.
Metallo-Organic Pesticides
Recommended pretreatment of process wastewaters includes the general
guidelines, plus the removal of heavy metals by lime precipitation.
Formulators/Packagers
Since formulators and packagers can potentially process the products
from all subcategories of active ingredients, pretreatment may consist of
a combination of the preceding recommendations.
XI 1-7
-------
DRAFT
Adhesive, and Sealants Industry
Pollutants from specific processes within the Adhesive and Sealants
industry may interfere with, pass through, or otherwise be incompatible
with a publicly-owned treatment works. Compatible pollutants are
biochemical oxygen demand, suspended solids, pH, and fecal coliform
bacteria, and any additional pollutants identified in the NPDES permit
if the publicly-owned treatment works was designed to treat such pollu-
tants and in fact does remove such pollutants to a substantial degree.
The term "substantial degree" is not subject to precise definition, but
is taken here to mean 80 percent or greater removal. Examples of the
additional pollutants which may be considered compatible include:
1. Chemical oxygen demand
2. Total organic carbon
3. Phosphorus and phosphorus compounds
k. Nitrogen and nitrogen compounds
5. Fats, oils, and greases of animal or vegetable origin
(except as prohibited where these materials would interfere
with the operation of the publicly-owned treatment works).
In-plant measures to reduce the quantity and strength of industrial
wastewater flows can be beneficial to joint treatment, and should be
encouraged. Pretreatment for the removal of the compatible pollutants
is not required by the Federal pretreatment standards. Pretreatment of
wastewaters containing compatible pollutants may be necessary in the
form of spill protection or flow equalization in order to ensure com-
pliance with the pretreatment standards. To allow for the broad spectrum
of industries, waste constituents, and treatment plants, pretreatment
requirements should be based on an individual analysis of the permitted
effluent limitations placed on a publicly-owned treatment works and on
the potential for adverse effects on such works.
The characteristics of wastewaters from animal glue manufacturing plants
vary according to the type of raw material being processed. The process
wastewaters from animal glue plants contain BOD5, COD, TOC, suspended and
dissolved solids, alkalinity, organic-nitrogen, chromium, and oil and
grease as major constituents. Since oil and grease occur in large
quantities, they are recovered in the plant for sale as a non-edible
by-product. Tankage may also be reclaimed as a by-product for the manu-
facture of fertilizer. The alkaline wastewater, which is high in lime
solids, can be used to advantage for precipitation of the trivalent
chromium. The trivalent chromium in the waste stream will be removed
with the lime solids during clarification. In general, animal glue
XI I-8
-------
DRAFT
wastewaters are amenable to joint treatment by conventional methods,
if the industrial wastewater is adequately pretreated. The pretreat-
ment unit operations which may be necessary for various types of joint
treatment processes are shown in Table XIID-1. Screening to remove
debris, equalization to provide uniformity of effluent, chemical pre-
cipitation to reduce the amount of chromium and neutralization to
prevent excessively high pH values are generally necessary prior to
discharge to a municipal collection system. The considerations In
Table XIID-1 assume that fat and grease will be recovered as a by-product.
Where this is not practiced, grease removal facilities may also be needed.
The characteristics of wastewaters from water- and solvent-based adhesive
manufacturing plants vary according to the type of adhesives being pro-
duced. The wastewaters contain 6005, COD, TOC, suspended and dissolved
solids, and usually alkalinity as major constituents. Wastewater dis-
charges from plants producing certain types of adhesives may also contain
organic-nitrogen, oil and grease, and phenol as major constituents. The
diversity and complexity of the adhesive products produced, as well as
the proprietary nature of many of the process chemicals, may require that
the pretreatment be established on a case-by-case basis after thorough
investigation. The pre-treatment unit operations which may be necessary
for various types of joint treatment processes are shown in Table XIID-1.
The survey data collected during the sampling program were examined for
specific pollutants which may inhibit biological treatment. Since most
adhesive plants discharge directly to municipal treatment facilities,
pretreatment requirements for these wasteweter discharges are very
important. The pollutants of major concerr; in the Adhesive and Sealants
industry are chromium and phenol. Chromium has been shown to be toxic
to activated sludge and trickling filter processes above certain concen-
trations. Trivalent chromium will precipitate from alkaline solutions,
while hexavalent chromium will not precipitate. Therefore, the first
step in treating wastewaters containing hexavalent chromium is to reduce
it from the hexavalent to the trivalent form. Chromium reduction pro-
ceeds most rapidly in acid solution. When the chromium has been reduced,
the pH of the wastewater is increased to precipitate not only the tri-
valent chromium, but other heavy metals as well.
Phenol is biologically degradable in an acclimated system. It has been
reported that concentrations of mixed phenolics as high as 2,000 to
3,000 mg/L are degradable in a properly designed system. However, con-
centrations as low as 50 mg/L can inhibit biological treatment if the
organisms are not properly acclimated.
In recent years, the activated sludge process has been adapted to indus-
trial wastes similar in composition to that of effluents from the adhesive
and sealants industry. Similarly, reductions greater than 90 percent of
both BODg and phenols from these types of wastewaters by the activated
sludge process have been reported.
XII-9
-------
DRAFT
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Explosives Industry
A review of the wastewater characteristics of the explosives
industry indicates that the process wastewaters contain high
concentrations of soluble oxygen-demanding materials, varied
ranges of suspended solids, nitrates, sulfates, organic
nitrogen and carbon, metals and trace quantities of explo-
si ves.
The scope of this study did not allow for a specific toxicity
evaluation of explosive wastewaters. However, all but the
last two parameters appear to be amenable to secondary treat-
ment.
Metals such as lead and mercury have been shown to be
discharged in quantities sufficient to disrupt biological
activity. In one ffeld investigation in subcategory C,
lead discharges were found in concentrations of 200 mg/L.
This makes physical/chemical precipitation mandatory as a
pretreatment step.
Trace quantities of explosives may present a significant
problem for a municipal sewage treatment system because of
their toxicity and hazardous nature. However, a pretreatment
system can be designed to ensure that toxicity and safety
hazards are eliminated. The system would have to ensure that
a slug of explosive material from an emergency discharge could
never enter the municipal system. Such a system would consist
of the following unit operations: equalization, chemical *
precipitation of metals, and neutralization.
XI1-11
-------
DRAFT
Carbon Black Industry
Pollutants from specific processes within the Carbon Black industry
will not interfere with, pass through inadequately treated, or otherwise
be incompatible with a publicly-owned treatment works.
Subcategory A should have no process contact discharges. The only
wastewater from this subcategory would be sanitary wastewater and utility
blowdowns. All discharges of these types would be governed by local
ordi nances.
Subcategory B will have a single process contact wastewater, in addition
to those non-contact sanitary and utility sources: i.e., the blowdown
from the dehumidifier loop. The only significant contaminant in this
source is TSS, which is compatible with a publicly-owned treatment works.
Therefore, the discharges from subcategory B would also be governed by
local ordinances.
XII-12
-------
DRAFT
G. Photographic Process|nq Industry
Approximately 5 percent of all major photoprocessing plants are
classified as existing point sources and, therefore, are subject
to the effluent limitations contained herein. The remaining 95
percent of the plants discharge their effluent to municipal treat-
ment systems and are regulated by the pretreatment guidelines for
those systems. These guidelines are designed to prevent plants
from discharging industrial wastewaters which would upset the
treatment processes used by the municipal system and industrial
wastewaters which would pass through the works without adequate
treatment (G-12).
Information presently available indicates that ferrocyanide should
not exceed 1 mg/L expressed as free cyanide, since concentrations
above this level have been shown to inhibit biological systems (G-5)
Pretreatment of silver thiosulfate should be practiced to attain
levels not to exceed 10 mg/L in the municipal treatment plant
influent (G-3).
XII-13
-------
DRAFT
H. Hospitals
•
Pollutants from hospitals may interfere with, pass through,
or otherwise be incompatible with a publicly-owned treatment
works. Bio-chemical oxygen demand, suspended solids, pH,
and fecal coliform bacteria are defined as compatible pollu-
tants, along with any other pollutants which publicly-owned
treatment works are designed to remove. 41
In-process measures to reduce the quantity and strength of in-
compatible pollutants in the wastewater flow can be beneficial
to joint treatment, and should be encouraged, Pretreatment for
the removal of the compatible pollutants is not required by the
Federal pretreatment standards. Pretreatment requirements should ^
be based on an individual analysis of the permitted effluent
limitations placed on a publicly-owned treatment works and on
the potential for adverse effects on such works.
The most practicable and economical pretreatment of incompatible
pollutants in hospitals involves in-process modifications or *
changes in operating and maintenance procedures to completely
eliminate the pollutants from the wastewater, rather than end-
of-pipe treatment for removal of these pollutants. Economic
advantages can be realized from in-process removals (for example,
silver recovery), especially in large hospitals. M^L
The following in-house controls have been recommended as methods
of dealing with the pollution problems of hospitals:
1. All X-ray processing units should utilize the boron-
free fixer which is now available from most manufacturers.
2. Wherever possible, stand-by control units should be in-
stalled on all X-ray processing units to decrease the usage
of water by the processor. In the event that stand-by
controls are not adaptable to the processing unit, it is
recommended that the water flow be reduced to the minimum
input possible without distracting from the final radiograph. ^
3. All barium should be encased in a plastic bag container and
this container should be disposed of through solid waste
procedures.
4. The discharge of silver from X-ray processing units should ^
be controlled by utilization of a silver recovery system or
by containing the spent developer and returning it to the
manufacturer for silver recovery. If an in-house silver
recovery system is utilized, it is recommended that recovery
units for heavily-used X-ray processing equipment be placed ^
in tandem.
-------
DRAFT
5. Because the sources of potential mercury pollution
are varied and complex, the administration should be-
come familiar with the total mercury problem and
establish staff responsibilities with appropriate
duties.
Since most hospitals discharge directly to municipal treatment
facilities, pretreatment requirements for their wastewater dis-
charges are very important. If in-process modifications and
operating procedures are not incorporated to reduce silver,
mercury, barium, and boron from the waste stream, end-of-pipe
pretreatment methods will have to be implemented to remove or
reduce these incompatible pollutants from the hospital discharge
before going to municipal treatment plants. The pretreatment
unit operations which may be necessary for various types of joint
treatment processes are shown in Table XII H-1.
TABLE XII H-1
Pretreatment Unit Operations
Hospitals
Suspended
Biological
System
Fixed
Biological
System
Independent
Physical
Chemical
System
Chem i ca1
Precipitation
(Metals)
+ Solids
Separation
Chemical
Preci pitation
(Metals)
+ Sol ids
Separation
Chem i ca1
Precipi tation
(Metals)
+ Sol ids
Separation
X I I -1 5
-------
DRAFT
SECTION XI I I
PERFORMANCE FACTORS FOR
TREATMENT PLANT OPERATIONS
General
As referenced in the discussion of End-of-Pipe Treatment Systems in
Section VII, the historic treatment plant data were analyzed on the
basis of 50 percent occurrence value based upon long-term data, where
possible.
In the past, effluent requirements have been issued by regulatory agencies
without stated concern for uniform expression. Some agencies have issued
regulations without definition of time interval or without stipulation of
the type of the sample (grab or composite). This has caused difficulties
in determining whether a particular plant was in violation. To overcome
that situation, daily historic data (when available) from several bio-
logical treatment plants were reviewed, monthly averages were calculated,
and then the data were analyzed statistically by each industrial category.
The results of these analyses are discussed separately for each industrial
category.
The significance of the data is that although a biological treatment plant
is producing an effluent with a certain BOD^ concentration 50 percent of
the' time or less, it will also produce an effluent with a greater 6005
concentration 50 percent of the time.
Variations in the performance of wastewater treatment plants are attrib-
utable to one or more of the following:
1. Severe ambient air temperature changes which are
uncontrollable in conventional designs.
2. Variations in sampling techniques.
3. Variations in analytical methods.
k. Variations in one or more operational parameters, e.g.,
the organic removal rate by the biological mass,
settling rate changes of biological sludge.
5. Controllable changes in the treatability characteristics
of the process wastewaters even after adequate equali-
zation.
XI Il-l
-------
DRAFT
These variations are purely a function of the wastewater treatment
plant performance. They will still occur even if the wastewater
treatment plant has provisions for equalization of fluctuation in
the influent raw waste load which it receives.
XI I 1-2
-------
DRAFT
A. Pharmaceutical Industry
Variability in historic effluent data from exemplary biological treat-
ment plants treating pharmaceutical wastes were statistically analyzed,
The results of these analyses are shown in Table XIIIA-1. Ratios of
the 99 percent probability of occurrence to the 50 percent probability
of occurrence, the 95 percent to the 50 percent value, and the 90
percent to the 50 percent value were computed for each plant. The
average of the ratios are presented in Table XIIIA-2.
The 50 percent probability of occurrence values shown in Table XIIIA-1
are based upon long-term daily data. The 99 percent, 95 percent and
90 percent probability of occurrence values for the monthly average
were based on "normalized data"; that is data values were assumed to
follow a normal distribution. However, is should be emphasized that
no data points were discarded. The maximum daily values were not
normalized, because adequate long-term data were available to form
definite distribution patterns. The occurrence of these abnormally
high values, causing the skewing in the data distribution, is indica-
tive of unusually poor treatment performance, probably attributable
10 some sort of process upset. Because of this phenomenon, selection
of 99 percent probability of occurrence values as a basis for
establishing daily variability is not recommended, since the 99/50
ratios of probability would be abnormally high. Use of 95 percent
probability of occurrence values results in 95/50 ratios of proba-
bility more within a range typically observed in the past as being
reasonable in the context of statistical analysis of treatment plant
dates. Use of 95 percent probability of occurrence values for
establishing monthly variability is also recommended since use of
95 percent probability suggests that a plant would be in violation
less than one month/year.
The following effluent adjustment factors are proposed for the follow-
ing parameters and time intervals:
Performance Factor Performance Factor
for Maximum Daily for Maximum Monthly
Parameter Effluent Value1 Effluent Value^
BOD5 *K1 2.3
COD 2.9 2.1
TSS 5.0 2.6
95/50 ratio of probability
XI I I-3
-------
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-------
DRAFT
Table XIIIA-2
Pharmaceutical Industry
Average Ratios of Probabilities of Occurrence
Ratio Of
Probabi1ity Dai1y Monthly
BOD5
99/50 10.9 3.0
95/50 4.1 2.3
90/50 3.1 2.0
COD
99/50 4.3 2.5
95/50 2.9 2.1
90/50 2.2 1.9
TOC
99/50 5.3 1.8
95/50 3.0 1.6
90/50 2.0 1.5
TSS
99/50 8.0 3.0
95/50 5.0 2.6
90/50 3-2 2.3
Xlll-5
-------
DRAFT
The following is an illustration of how the EPA Regional Offices would
employ the monthly effluent adjustment factors:
BODc; COD TSS
kg/kkg kg/kkg kg/kkg
product product product
Average BPCTCA Effluent
Limitations 8 15 1
Daily Effluent Performance
Factor k.\ 2.9 5.0
Monthly Effluent Performance
Factor 2.3 2.1 2.6
Acceptable Maximum for Any
One Day 32.8 k3.S 5.0
Average of Daily Values for
30 Consecutive Days Shall
Not Exceed 18.4 31.5 2.6
There is not enough performance data available from physica1/chemical
treatment systems at this time to determine variability for BATEA and
BADCT effluent limitations; consequently, the ratios established for
BPCTCA have been used. As performance data become available, their
ratios should be reevaluated.
The performance factors in this section were applied to the average
daily effluent limitations to develop the effluent limitations guide-
lines presented in Sections II, IX, X, and XI.
XIII-6
-------
DRAFT
B. Gum and Wood Chemicals Industry
Biological Wastewater Treatment
Only two wastewater treatment plants which employ biological treatment
were surveyed during the Gum and Wood Chemicals study. Neither of
these plants had sufficient historic data to perform the statistical
analysis to determine performance factors for treatment plant operation.
The performance factors developed for the Pharmaceutical industry are
not considered applicable for the Gum and Wood industry because of
significant differences in production processes and wastewater varia-
bility. The Petroleum Refining industry more closely resembles the
Gum and Wood Chemicals industry in that both employ continuous or batch
continuous distillation operations. Organic load variability on
end-of-pipe treatment facilities for these two industries ar°, therefore
anticipated to be closely related.
The performance factors for the Petroleum Refining industry have been
published by EPA^ as follows:
Performance Factor Performance Factor
Level of Effluent for Maximum Monthly for Maximum Daily
Treatment Parameter Effluent Value Effluent Value
BPCTCA BODc 1.7 3.2
COD 1.6 3.1
TSS 1.7 2.9
BATEA BOD5 1.7 2.1
COD 1.6 2.0
TSS 1.7 2.0
BADCT BOD5 1.7 2.1
COD 1.6 2.0
TSS 1.7 2.0
The proper performance factors were applied to long-term average daily
BPCTCA effluent limitations in order to generate effluent limitations
guidelines based on the maximum average of daily values for thirty
consecutive days and the maximum for any one day as presented in
Table IXB-1.
"Development Document for Effluent Limitations Guidelines and New Source
Performance Standards for Petroleum Refining Point Source Category,
Issued April, 197^, EPA - kkOI7^-01^-A, EPA, Washington, D.C. 20^60.
XIII-7
-------
DRAFT
The applicability of this established treatment plant performance
variability data for the Petroleum Refining industry to the Gum and
Wood Chemicals industry will be substantiated as additional plant
performance data become available.
Activated Carbon Wastewater Treatment
During the survey of the Gum and Wood Chemicals industry, no plant
employed activated carbon after biological treatment. Consequently,
no long-term performance data were available for this industry. As
a result, the performance factors developed for BATEA and BADCT for
the Petroleum Refining industry were applied to BATEA and BADCT effluent
limitations guidelines. The effluent limitations guidelines based
on maximum average of daily values for thirty consecutive days and maxi-
mum for any one day in Tables XB-1 and XIB-1 were similarly calculated
from the long-term average daily BATEA and New Source (BADCT) efflu-
ent limitations guidelines.
XIII-8
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
Insufficient historical data were avaiilable to perform a statistical
analysis to determine variability factors for annual treatment plant
performance.
Characteristic of the manufacturing facilities in the Pesticides and
Agricultural Chemicals industry are batch type operations, a very
diverse product mix, and seasonal production variation. As these
process variations are similar to those in the Pharmaceutical industry,
the organic load variability on end-of-pipe treatment plants for the
Pesticides and Agricultural Chemicals industry and the Pharmaceutical
industry are, therefore, anticipated to be closely related. For the
same reason, the performance of end-of-pipe treatment plants in these
two industries should be similar. Consequently, the performance
factors of treatment plant operations as developed for the Pharmaceu-
tical industry from the long-term performance of biological treatment
plant operations have been applied to this industry also. These per-
formance factors are as follows:
Performance Factor Performance Factor
for Maximum Monthly for Maximum Daily
Parameter Effluent Value Efluent Value
2.3 **.1
COD 2.1 2.9
TSS 2.6 5.0
As additional treatment plant performance data in this industry become
available, such data should be used to reevaluate the performance
factors used in this document.
Since there is not enough performance data available from phys i cal/chenical
treatment systems reported at this time to determine performance factors
for BATEA and BADCT effluent limitations guidelines, the factors establish*
for BPCTCA biological treatment systems have been used for BATEA and
BADCT effluent limitations guidelines. As performance data become avail-
able, the performance factors used in this document should be reevaluated.
The performance factors presented in this section were applied to the
long-term average daily effluent limitations to develop the effluent
limitation guidelines for the maximum average daily values for thirty
consecutive days and the maximum for any one day, as presented in
Sections II, IX, X, and XI of this document.
XII1-9
-------
DRAFT
D. Adhesive and Sealants Industry
Biological Wastewater Treatment
*'''
No wastewater treatment plants which employed biological treatment
were surveyed during the adhesive and sealants study. Therefore,
there were no historic data available as a basis for statistical
analysis to determine variability factors for annual treatment plant
performance in this category.
Characteristic of the manufacturing facilities in the Adhesive and
Sealants industry are batch type operations, a very diverse product
mix, and seasonal production variation. As these process variations
are similar to those in the Pharmaceutical industry, the organic load
variability on end-of-pipe treatment plants for the Adhesive and
Sealants industry and the Pharmaceutical industry are, therefore,
anticipated to be closely related. For the same reason, the perform-
ance of end-of-pipe treatment plants in these two industries should
be similar. Consequently, the performance factors of treatment plant
operations as developed for the Pharmaceutical industry from the
long-term performance of biological treatment plant operations have
been applied to this industry. These performance factors are as
follows:
Performance Factor Performance Factor
for Maximum Monthly for Maximum Daily
Parameter Effluent Value Effluent Value
6005 2.3 4.1
COD 2.1 2.9
TSS 2.6 5.0
As additional treatment plant performance data in this industry become
available, such data should be used to reevaluate the performance
factors used in this document.
Since there is not enough performance data available from physical/chemical
treatment systems reported at this time to determine performance factors
for BATEA and BADCT effluent limitations, the factors established for
BPCTCA biological treatment systems have been used for BATEA and BADCT
effluent limitations guidelines. As performance data become available,
the performance factors used in this document should be reevaluated.
The performance factors presented in this section were applied to the
long-term average daily effluent limitations to develop the effluent
limitation guidelines for the maximum average of daily values for thirty
consecutive days and the maximum for any one day, as presented in Sections
II, IX, X, and XI of this document.
XIII-10
-------
DRAFT
Explosives Industry
Variability in historic effluent data from an exemplary biological
treatment plant treating propellant wastes was statistically analyzed.
The results of this analysis are shown below. Ratios of the 95 percent
probability of occurrence to the 50 percent probability of occurrence,
Were computed for this plant, with the average of the daily and monthly
BOD and COD ratios as follows:
Ratio of Probabi1 ity Dai1y Monthly
95/50 3.8 2.k
For lack of data, variability in suspended solids could not be
developed by historical means. Because of the similarity of their
treatment systems, TSS variability for the Explosives industry was
assumed to be similar to the Pharmaceuticals industry. The following
performance factors are to be multiplied by long-term average effluent
guidelines to ascertain effluent limitations. These factors represent
a ratio of the 95 percent probability of occurrence to 50 percent
probability of occurrence for daily and monthly values of TSS.
Ratio of Probabi1ity Da?ly Monthly
95/50 5.0 2.6
These performance factors were applied to the long-term average daily
effluent limitations to develop the effluent limitations guidelines
presented in Sections II, IX, X, and XI.
XIII-11
-------
DRAFT
F. Carbon Black Industry
No historic data were obtained during the study of the Carbon Black
industry on which to base a statistical analysis to determine vari-
ability factors for annual treatment plant performance on segregated
process streams in this category. Therefore, no performance factors
are recommended at this time since the character of the suspended
solids from this industry cannot be related to any other industrial
category. They should be developed as soon as data become available
in the industry.
XIII-12
-------
DRAFT
G. Photographic Processing Industry
*
It is apparent from the performance data collected on the large-
scale activated sludge unit during the field study that BOD and COD
reductions were variable during the first two years of performance.
Following the installation of the sand filters in the second year,
BOD reduction in percent brought about by the combined Installation
varied from 78 percent to 91 percent; during a different period, COD
reduction varied from 4-5 percent to 70 percent. These data were
reported as ten-week averages and were not available in a more
usable form to determine variability.
The Photographic Processing industry is characterized by batch
type operations, a very diverse product mix, and seasonal production
variation. As these process variations are similar to those in the
Pharmaceutical industry, the organic load variability on end-of-pipe
treatment plants for the Photographic Processing industry and the
Pharmaceutical industry are, therefore, anticipated to be closely
related. For the same reason, the performance of end-of-pipe treat-
ment plants in these two industries should be similar. Consequently,
the performance factors of treatment plant operations as developed
for the Pharmaceutical industry from the long-term performance of
biological treatment plant operations have been applied to this
industry also. These performance factors are as follows:
Performance Factor Performance Factor
for Maximum Monthly for Maximum Daily
Parameter Effluent Value Effluent Value
2.3 4.1
COD 2.1 2.9
TSS 2.6 5.0
As additional treatment plant performance data in this industry be-
come available, such data should be used to reevaluate the performance
factors used in this document.
Sufficient historical data were not available to perform a statistical
analysis to determine variability factors for silver and ferrocyanide
in treatment plant effluent. The draft development document for
effluent limitations guidelines for the Metal Finishing industry (G-14)
establishes a variability factor of 2.0 between the maximum for any
single day average and the thirty-day average. However, it does not
establish any variability relationship between annual daily average
values and the thirty-day average. Since silver and ferrocyanide in
treatment plant effluent are more likely to be in the form of TSS, the
XIII-13
-------
DRAFT
same performance factors used for TSS were applied to silver and
ferrocyanide to develop the maximum average of daily values for any
period of thirty consecutive days and maximum value for any one day
shown in Tables IIG-1 and IIG-2. j
Since there is not enough performance data available from physical/
chemical treatment systems at this time to determine performance
factors for BATEA and BADCT effluent limitations, the factors
established for BPCTCA biological treatment systems have been used
for BATEA and BADCT effluent limitations. As performance data
become available, the performance factors used in this document
should be reevaluated.
The performance factors presented in this section were applied to the
long-term average daily effluent limitations to develop the effluent
limitation guidelines for the maximum average of daily values for
thirty consecutive days and the maximum for any one day, as presented
in Sections II, IX, X, and XI of this document.
XIII-14
-------
DRAFT
Hospi ca1s
Historic effluent data from activated sludge plants treating hospital
wastes were statistically analyzed to determine variability. The
results of the analyses are shown in Table X1IIH-1. Ratios of the
99 percent probability of occurence to the 50 percent probability,
the 95 percent to the 50 percent value, and the 90 percent to the
50 percent value were computed for each hospital. The average ratios
are as f ollows:
Ratio of BODg TSS
Probabi 1i ty Dai ly Monthly
99/50 2.2 1.8
95/50 1.6 }.k
SO/50 1.5 1.2
The 50 percent probability of occurrence values and the maximum
daily values shown in Table XIIIH-1 are based on analysis of weekly
grab sample data over a long period. The 99 percent, 95 percent and
90 percent probability of occurrence values for the monthly average
were based on "normalized data"; that is, data values were assumed
to follow a normal distribution. However, it should be emphasized
that no ddta points were discarded. The maximum daily values were
not normalized, as adequate long-term data were available to form
definite distribution patterns. The occurrence of these abnormally
high vdlueb, causing the skewing in the data distribution, is indica-
tive of unusually poor treatment performance, probably caused by some
sort of process upset. Because of this phenomenon, selection of
99 percent probability of occurrence values as a basis for establish-
ing daily variability is not recommended, since the 99/50 ratios of
probability would be abnormally high. Use of 95 percent probability
of occurrence values results in 95/50 rations of probability more
within a range considered reasonable in statistical analysis of treat-
ment plant data. Use of 95 percent probability of occurrence values
for establishing monthly variability is also recommended because use
of 95 percent probability suggests that a plant could be in violation
less than one month/year.
The following performance factors are proposed for the following
parameters and time intervals:
Performance Factors Performance Factors
for Maximum for Maximum
Parameter Daily Eff1uent Daily Effluent
BOD5 1.6 !.**•
TSS 1.5 1.^
95/50 ratio of probability
XM1-15
-------
DRAFT
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XIII-16
-------
DRAFT
Although these performance factors are. somewhat low in comparison
to values found in other industries, they appear responsible in view
of the fact that waste discharges from hospitals are relatively
continuous and activated sludge systems treating such wastes are
rarely subjected to shock loadings; hence, their performance tends
to be more consistent.
The following is an illustration of how the EPA Regional Offices
would employ the performance factors:
BODg TSS
lbs./1000 Ibs.71000
occupied occupied
beds beds
Average BPCTCA Effluent Limitations 41 22
Daily Effluent Adjusted Factor 1.6 1.5
Monthly Effluent Adjustment Factor 1 .if 1 .k
Acceptable Maximum for Any One Day 65.6 33.0
Acceptable Average of Daily Values
for Any 30 Consecutive Days Shall
Not Exceed 57.^ 30.8
There is not enough performance data available from dual-media
filtration treatment systems at this time to determine variability
for BATEA and BADCT effluent limitations; consequently, the ratios
established for BPCTCA have been used. As performance data become
available, these ratios should be reevaluated.
The adjustment factors in this section were applied to the
term average daily effluent limitations to develop the effluent
limitations guidelines as presented in Sections II, IX, X, and XI
1-17
-------
-------
DRAFT
SECTION XIV
ACKNOWLEDGEMENTS
Roy F. Weston, inc. wishes to express appreciation to the following
organizations and individuals for the valuable assistance which they
provided throughout the study:
The Pharmaceutical Manufacturers Association and personnel of selected
plants in the Pharmaceutical industry who provided valuable assistance
in the collection of data relating to process RWL and treatment plant
performance.
The Pulp Chemicals Association for providing valuable information on the
tall oil industry, and the personnel of selected plants of the Gum and
Wood Chemicals industry for their help in the collection of data relating
to process RWL and treatment plant performance.
Acknowledgement is made of the cooperation of personnel in many plants
in the Pesticides and Agricultural Chemicals industry who provided
valuable assistance in the collection of data relating to process
raw waste loads and treatment plant performance.
The Adhesives and Sealants Council for assisting in the development of
logical effluent limitations and standards by providing an industry
breakdown which made possible the subcategorization of the industry, and
also for their aid in obtaining volunteer plants to participate in
field investigations. Acknowledgement is also made of the personnel
in selected plants of the Adhesives and Sealants industry for their
cooperation in the collection of data relating to process RWL.
The personnel of selected plants of the Explosives industry for their
assistance in obtaining pertinent data necessary in the writing of this
documen t.
The personnel of the Carbon Black industry who aided in the collection
of data related to manufacturing processes, RWL and treatment plant
performance.
The Photographic Processing industry for not only providing valuable
information used in the development of the effluent guidelines of this
document, but for the cooperation of personnel in selected plants who
aided in the collection of data relating to process RWL and in-plant
pollution abatement techniques.
The American Hospital Association and the Veteran's Administration for
their assistance in the selection of representative hospitals, and the
personnel of surveyed hospitals who provided data relating to RWL and
treatment plant performance.
XIV-1
-------
DRAFT
Roy F. Weston, Inc. also wishes to acknowledge the assistance of the
personnel at the Environnental Protection Agency's Regional Centers,
who helped identify those; plants in the miscellaneous chemicals in-
dustry known to be achieving effective waste treatment, and whose
tireless efforts provided much of the research necessary for the
treatment technology review.
Special acknowledgement \s also made of the assistance and direction
of Mr. Joseph Vital is, Proj'ect Officer, and others in the Effluent
Guidelines Division: Messrs. Allen Cywin, Ernst Hall, Walter Hunt,
John Nardella, John Ciancia, Don Wilson, Raymond Loehr, Martin
Halper, Bruno Kaier, George Jett, David Becker and others, for their
helpful suggestions and comments.
WESTON would like to extend its appreciation for the time and effort
the following governmental organizations displayed:
- EPA-Effluent Guidelines Branch, Washington, D.C.
- EPA-Region I-Industrial Waste Treatment Research
Laboratory
- American Defense Preparedness Association - Ad Hoc
Commi ttee
- U.S. Army Environmental Hygiene Agency
- Manufacturing Technology Directorate, U.S. Army
Picatinny Arsenal
- Headquarters U.S. Army Armaments Command
- U.S. Army Material Command
- Headquarters Department of the Army
In addition WESTON would like to extend its gratitude to the following
individuals for the significant input into the development of this
document:
- Gerry Eskulund
- Tom Wash (HAAP) U.S. Armament Commander
- Lt. Col. Ronald Snyder, HAAP
- Don Emig
- Irvi ng Forsten
- Sheldon Meyers - Director, Office of Federal Activity - EPA
- Charles Sell
- H. R. Smith - Acting Deputy Assistant Secretary of Defense
(Environmental Quality)
XIV-2
-------
DRAFT
- John. Pace
- Col. William Gardiner - Headquarters Department of the
Army
- Lt. Col. Victor J. Gongola - Counselor, HAAP
- John R. Evans - Holsten Defense Corporation
- Col. Marshal Steinberg - U.S. AEHA
- Lt. Col. Waldimir Gulevich - U.S. AEHA
- Lt. Col. Roy Reuter - U.S. Army Medical R&D Command
- Marvin Robin - U.S. AEHA
This study was conducted and the report prepared for the Environmental
Protection Agency under the direction of Project Director, James H.
Dougherty, P.E., and Technical Project Manager, Jitendra R. Ghia, P.E.
The following individual members of the staff of Roy F. Weston, Inc.
made significant contributions to the overall effort:
Roy F. Weston, Chairman of the Board
Paul H. Woodruff, President
James E. Germain, Vice President
Pharmaceutical Industry and Hospitals
D. R. Junkins
D. W. Grogan
Gum & Wood Chemicals Industry
C. M. Mangan
J. G. McGovern
R. P. Stevens
Pesticides & Agricultural Chemicals Industry
D. C. Day
J. J. Davies
J. R. Piskura
Adhesive and Sealants Industry
E. L. Stover
Explosives Industry
J. A. Defi 1 ippi
K. J. Phillips
XIV-3
-------
DRAFT
Carbon Black Industry
P. A. Haderer
Cost Estimates
T. E. Taylor
Laboratory Services
P. J. Marks
K. K. Wahl
Techn ica1 Ed i t i ng
J. L. Simons
A. M. Tocci
F. T. Russo
Internal Consultants
D. A. Baker
Y. H. Lin
D. S. Small wood
R. R. Wright
M. Ramanathan
-------
DRAFT
SECTION XV
BIBLIOGRAPHY
A. Pharmaceutical Industry
A-l. Anderson, D. R. et al, "Study of Pharmaceutical Manufactur-
ing Wastewater Characteristics and Aerated Treatment System,"
Proceedings 25th Purdue Industrial Waste Conference, May 1970,
26.
A-2. "Antibiotics" Industrial Wastes - Their Disposa1 and Treat-
ment , Reinhold Publishing Corporation, New York, 1953.
A-3. Breaz, E., "Drug Firm Cuts Sludge Handling Costs," Water and
Wastes Engineering, January 1972, Appendix 22 - 23.
f\-k. Brown, W. E., "Antibiotics," Encyclopedia of Chemical Tech-
nology, Kirk-Othmer, Vol. 2, 533-5^0.
A-5. "Cooling Tower," Power, Special Report, March 1973, 51-523.
A-6. "Economic Priorities Report," In Whose Hands, Vol. k, Council
on Economic Priorities, New York.
A-7. Herion, R.W., Jr, "Two Treatment Installations for Pharmaceu-
tical Wastes," Proceedings 18th Purdue Industrial Waste Con-
ference, 1963.
A-8. Holmberg, J. D. and Kinney, D. !_., Drift Technology of Cool-
ing Towers, Marley Company, Mission, Kansas, 1973.
A-9. Lederman, P. B., Skovronek, H., and desRosiers, P. E.,
"Pollution Abatement in the Pharmaceutical Industry,"
Pharmaceutical Symposium of the American Institute of
Chemical Engineers' National Meeting, Washington, D.C., 197^.
A-10. Nemerow, N.L., Liquid Waste of Industry - Theories, Practices
and Treatment, Addison-Wesley Publishing Company, Reading,
Massachusetts, 1971.
A-ll. Mayes, J. H., "Characterization of Wastewaters from the
Ethical Pharmaceutical Industry," EPA 67012-7^-057, National
Environmental Research Center, Cincinnati, Ohio, July
A-12. Mohanrao, G. J., et al., "Waste Treatment at a Synthetic
Drug Factory in India," JWPCF, Vol. k2, No. 8, Part 1,
August 1970, 1530-15^3.
XV-
-------
DRAFT
A-13. Shor, L. A. ard Magee, R. J., "Veterinary Drugs,"
Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 21,
241-254.
A-14. Shreve, R. N., Chemical Process Industries, Third Edition,
McGraw-Hill, 196?.
A-15. Strong, L. E., "Blood Fractionation," Encyclopedia of Chemi-
cal Technology, Kirk-Othmer, Vol. 3, 576-602.
A-16. Taber, C. W., Tabers' Cyclopedic Medical Dictionary, Tenth
Edition, F. A. Davis Company, Philadelphia, Pa., 1965.
A-17. Windheuser, J. J., Perrin-John, "Pharmaceuticals," Encyclo-
pedia of Chemical Technology, Kirk-Othmer, Vol. 15, 112-132.
A-18. Patterson, J.W. and Minear, R.A., "Wastewater Treatment
Technology" 2nd Edition Jan. 1973 for State of Illinois,
Institute for Environmental Quality.
A-19. "Pollution Abatement Practices in the AAP", by I. Forster,
Environmental Science & Techno logy, summer of 1973.
A-20. "A Primer on Waste Water Treatment", Environmental Protection
Agency, Water Quality Office, U. S. Government Printing Office
1971, 0-419-407.
A-21 . "Industrial Process Design for Pollution Control", Volume 4,
Proceedings of Workshop organized and held under the auspices
of the AlChE Environmental Division, October 27-29, 1971,
Charleston, West Virginia.
A-22. "Making Hard-to-Treat Chemical Wastes Evaporate", Chemical
Week. May 9, 1973.
A-23. Cost of Clean Water, Industrial Waste Profile No. 3, GWQA,
U. S. Department of the Interior (November 1967).
A-24. "Development of Operator Training Materials", Prepared by
Environmental Science Services Corp., Stanford, Conn., under
the direction of W. W. Eckenfelder, Jr. for FWQA (August 1968).
A-25. Quirk, T. P., "Application of Computerized Analysis to Compara-
tive Costs of Sludge Dewatering by Vacuum Filtration and
Centrifuge," Proc., 23rd Ind. Waste Conf., Purdue University
1968, pp. 691-709.
XV-2
-------
DRAFT
A-26. "Compilation Industrial and Municipal Injection Wells in
U.S.A.", EPA-520-9-7^-020, Vol. 1 and Vol. 2, Industrial
Waste, January - February 1975.
A-27- Davis, K. E., Funk, R. J., "Deep Well Disposal of Industrial
Waste", Industrial Waste, January - February 1975.
A-28. Ajit Sadana, "Multi-Effect Evaporation and Pyrolyzation of
Industrial Wastewater Residues and Energy Recovery", Enviro-
engineering, Inc., Somerville, New Jersey, Paper Presented
at National Conference on Management and Disposal of Residues
from the Treatment of Industrial Wastewaters, Washington, D.C.,
February 3-5, 1975.
A-29. Engineering-News Record. Published Weekly by McGraw Hill,
Inc., Highstown, New Jersey.
A-30. Barnard, J. L. , "Treatment Cost Relationships for Industrial
Waste Treatment", Ph.D. Dissertation, Vanderbilt University,
Tennessee (1971)•
A-31. Swanson, C. L., "Unit Process Operating and Maintenance Costs
for Conventional Waste Treatment Plants," FWQA, Cincinnati,
Ohio (June 1968).
A-32. "Estimating Staff and Cost Factors for Small Wastewater Treat-
ment Plants Less than 1 MGD". Part 1 and Part II. "Staffing
Guidelines for Conventional Municipal Wastewater Treatment
Plants Less than 1 MGD". By Department of Industrial Engineer-
ing and Engineering Research Institute, Iowa State University.
EPA Grant No. 5P2-WP-195-0^52, June 1973.
A-33. EPA 625/1-7^-006 "Process Design Manual for Sludge Treatment
and Disposal", U. S. EPA - Technology Transfer, October 1974.
A-3^. "Process Design Manual for Carbon Adsorption", U. S. EPA
Technology Transfer, October 1973.
A-35. EPA, "Development Document for Effluent Limitations Guidelines
and Standards of Performance - Organic Chemicals Industry",
June 1973.
A-36. EPA, "Draft Development Document for Effluent Limitations
Guidelines and Standards of Performance - Steam Supply and
Noncontact Cooling Water Industries", October
XV-3
-------
DRAFT
A-37. "Water Quality Criteria, 1972", National Academy of Sciences
and National Academy of Engineering for Environmental
Protection Agency, Washington, D.C., 1972 (U.S. Government
Printing Office, Stock No. 5501-00520).
A-38. "Process Design Manual for Upgrading Existing Wastewater
Treatment Plants", EPA, 197^.
-------
DRAFT
B. Gum and Wood Chemicals Industry
B-l. Kent s J. A., ed. Riegel's Industrial Chemistry, Reinhold
Publishing Corporation, New York, 1962.
B-2. Publicity Committee (Zachary, L. G., et al.) "Tall Oil and
its Uses," Tall Oil Products Division, Pulp Chemicals Associ-
ation, F. W. Dodge Company, New York, 1965.
B-3. Shreve, R. N., Chemical Process Industries, Third Edition
McGraw-Hill Book Company, New York, 1967.
B-4. Encyclopedia of Chemical Technology, 2nd Edition, Kirk-Othmer,
Interscience Publishers Division, John Wiley and Sons, Inc.
XV-5
-------
DRAFT
C. Pesticides and Agricultural Chemicals Industry
C-1. "Pesticide Handbook - Entoma", Entomological Society of
America, 24th Edition, 1974.
C-2. 'The Pollution Potential in Pesticide Manufacturing": Pesti-
cide Study Series - 5, Technical Studies Report (TS-00-72-04),
Environmental Protection Agency, June 1972.
03. "Pesticides '72", Chemical Week, Part 1, June 21, 1972.
C-4. "Pollution Control Technology for Pesticide Formulators and
Packagers", Grant No R-801577, Office of Research and Monitor-
ing, Environmental Protection Agency, 12 June 1974.
C-5. "Development Document for Proposed Effluent Limitations Guide-
lines and New Source Performance Standards for the Major Organ-
ic Products", U. S. Environmental Protection Agency, EPA
440/1-73/009, December 1973.
C-6. "Pollution Control at the Source", Chemical Engineering,
August 6, 1973.
C-7. "Currents - Technology", Environmental Science and Technology,
Volume 8, No. 10, October 1974.
C-8. "Development Document for Effluent Limitations Guidelines and
Standards of Performance", draft, Organic Chemicals Industry
Phase !i, Environmental Protection Agency, under contract,
number 68-01-1509, February, 1974.
C-9. "The Pesticide Manufacturing Industry - Current Waste Treatment
and Disposal Practices", Water Pollution Control Research
Series (12020 FYE 01/72), U. S. Environmental Protection
Agency, January 1972.
C-10. Anon., "Activated - Sludge Process Solves Waste Problem",
Chemical Engineering, 68 (2), 1961.
C-11. "Biological Treatment of Chlorophenolic Wastes", Water Pol-
lution Control Research Series (12130 EGK 06/71), U. S.
Environmental Protection Agency, June 1971.
C-12. "Process Design Manual for Upgrading Existing Wastewater
Treatment Plants", EPA 1974.
XV-6
-------
DRAFT
C-13. EPA internal Memorandum, "Variability in BOD Concentration
from Biological Treatment Plants", To: Lilliam Regelson,
From: Charles Cook, March 1974.
C-14. "Proauct ion , Distribution, Use and Environmental Impact
Potential of Selected Pesticides", Midwest Research
Institute Report, Final Report, 25 February 1973,
15 March 1974, Contract No. EQC-311, Council on Environ-
mental Qual i ty , 1974.
C-15. "Pesticides in the Aquatic Environment", Environmental
Protection Agency, April 1972.
C-16. "Metabolism of Pesticides", U.S. Department of Interior,
July 1969.
C-17. "Water Quality Criteria, 1972", #5501-00520 National Academy
of Science.
C-18. Sittig, M., "Pesticides Production Processes", Noyes Develop-
ment Corporation, Park Ridge, New Jersey, 19&7.
C-19. "Pesticides and Pesticide Containers", Federal Register,
October 15, 1974, Volume 39, Number 200, Part 1.
C-20. "Chlorinated Insecticides", Volumes I and II, Technology
and Application, G.T. Brooks, The University of Sussex,
Brighton, Sussex, England, CRC Press, Inc., Cleveland, Ohio,
8 (1974).
C-21. "Guidelines For The Disposal of Small Quantities of Unused
Pesticides" - Part A and Part B. Contract 68-01-0098,
Project 15090 HGR, by Midwest Research Institute, Kansas City,
Mo. for EPA., Cincinnati, Ohio, Published by Midwest Research
Institute, Kansas City, Mo. 64110.
C-22. "Interaction of Heavy Metals and Biological Sewage Treatment
Process", Environmental Health Series, Water Supply and
Pollution Control, U.S. Department of Health, Education,
and Welfare, May 1965.
XV-7
-------
DRAFT
U. S. Patent No. Date Patented Title of Patent
2,699,451 1-11-55 Process for the Production
of Organic Amino Diol
Derivatives
2,694,089 11-9-54 Process for the Recovery of
dl-Threo-l-p-Nitrophenyl-2-
Amino-1,3-Propanediol
2,692,897 10-26-54 Process for the Production of
Acylamido Diol Compounds
2,692,896 10-26-54 Process for the Production
of N-Acylamido Diols
2,687,434 8-24-54 Production of 1-(Nitrophenyl)-Z
Acylamidopropane-l-3-Diols
2,686,802 8-17-54 Dichloracetimino Thioethers
and Acid Addition Salts
Thereof
2,681,364 6-15-54 Process for the Production
of 1-p-Nitrophenyl-Z-
Acylamidopropane-1,3-Diols
2,662,906 12-15-53 Chloramphenicol Esters and
Method for Obtaining Same
2,b68,571 9-18-51 Haloacetylamidophenyl-Halo-
Acetamido propandiol
2,562,107 6-24-51 Derivatives of Organic
Amino Alcohols and Methods
for Obtaining the Same
2,546,762 3-27-51 Acylamino Acetophenones and
Preparation Thereof
2,538,792 1-23-51 Preparation of Phenylserinol
2,538,766 1-23-51 Triacyl-Phenylpropane-
aminodiols
2,538,765 1-23-51 Diacyl Phenylpropane-
aminodiols
XV-8
-------
DRAFT
U. S. Patent No. Date Patented
2,538,764
2,515,241
2,515,239
2,514,376
2,513,346
2,483,885
2,483,884
1-23-51
7-18-50
7-18-50
7-11-50
7-4-50
10-4-49
10-4-49
Title of Patent
Acylamido-Phenylpropanediols
Nitrophenyl Acylamino
Acyloxy Ketones
a-Acylamido-p Hydroxy
Nitro Substituted Propio-
phenones
Triacyl Nitrophenylpropane-
aminodiols and Preparation
Thereof
Process for Obtaining Organic
Amino Diols
Nitrophenyl Acyl Amido
Alkane Diols
Method for Making Nitrophenyl
Acylamido Alkane Diols
xv-g
-------
DRAFT
D. Adhesive and Sealants Industry
D-l. Adhesives Red Book, Palmerton Publishing Company, Inc.,
New York, 197^-1975.
D-2. Skeist, I., Handbook of Adhesives, Reinhold Publishing Corp-
oration, 1966.
D-3. "Effluent Limitations Guidelines and Standards of Performance
for the Organic Chemicals Industry," Phase 1, Development
Document, RFW.
Q-k. Shreve, R. N., Chemical Process Industries, Third Edition,
McGraw-Hill, Inc., New York, 1956.
D-5. Clarke, J. S., "New Rules Prevent Tank Failures, " Hydrocarbon
Processing. .50 (5), 1971, 92-9^.
D-6. Crocker, B. B., "Preventing Hazardous Pollution During Plant
Catastrophes," 4, 1970.
D-7. McDermott, G. N., "Industrial Spill Control and Pollution
Incident Prevention," J. Water Pollution Control Federation,
kl (8), 1971, 1629.
D-8. "Effluent Limitations Guidelines and New Source Performance
Standards for the Timber Products Industry Veneer/Plywood
and Hardboard Wood Preserving," Development Document, Environ-
mental Science and Engineering, Inc.
D-9. Bodien, D.G., Plywood Plant Glue Wastes Disposal, Federal
Water Pollution Control Administration,Pacific Northwest
Water Laboratory, U.S. Department of the Interior, 1969.
D-10. Haskell, H. H., "Handling Phenolic Resin Adhesive Wash Water
in Southern Pine Plywood Plants," Forest Products Journal.
Vol. 21, No. 9, September, 1971.
D-ll. "Proposed Effluent Limitations Guidelines and New Source
Performance Standards for the Synthetic Materials Manufactur-
ing Point Source Category1,1 Development Document, Report No.
EPA 440/1-73/010, Effluent Guidelines Division, Office of Air
and Water Programs, U.S. EPA, Washington, D.C., September,
1973.
D-12. Ullrich, A. H., and Smith, M. W., "The Biosorption Process of
Sewage and Waste Treatment ," Sewage and Industrial Wastes, 23,
1951, 1248-1253.
XV-10
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DRAFT
E. Explosives Industry
E-l. "Industrial Waste Treatment Facilities, Holston Army Ammunition
Plant, Volume I i," The Army Corps of Engineers, Mobile Dis-
trict, Clark Dietz and Assoc., January 197^.
E-2. "Annotated Bibliography Development Of Methods To Minimize
Environmental Pollution, MM5T Project 5k]\k,n Facilities and
Protective Technology Div., Manufacturing Technology Director-
ate, Picatinny Arsenal, Dover, N.J., January 197^.
E-3. Harris, R., "Abatement Of High Nitrate Concentrations At
Munitions Plants: A State Of The Art Review," Picatinny
Arsenal, Dover, N.J., August 1973.
E-4. "Pollution Status Report," U.S. Army, Radford Army Ammunition
Plant, Radford, Va., August 197^.
E-5. Maybury, D. H. and Evans, J. L. , "Propellant Plant Pollution
Abatement Improvement Of Water Utilization," December 1973.
E-6. "Pollution Abatement Engineering Program For Munition Plant
Modernizat iorV. 3 ,4 £- 5 Briefings for Senior Scientist Steering
Group," Picatinny Arsenal, Dover, N.J., February 1973, 197^, 1
E-7. Eskelund, G. R., et al., "A Laboratory Study Of Carbon Adsorp-
tion For Elimination Of Nitrobody Waste From Army Ammunition
Plants," Picatinny Arsenal, Dover, N.J., January 1973.
975.
E-8. Information Package, Radford AAP,
E-9. Information Package, HAAP, 1974.
E-10. Reed, S., "Wastewater Management By Disposal On The Land,"
Special Report 171, U.S. Army Corps of Engineers, Cold Regions
Research and Engineering Laboratory, May 1972.
E-ll. Patterson, J. W. and Minear, R. A., "Pollution Control In The
Commercial Explosives Industry," April 197^. (EPA Publication)
E-12. Smith, L. L. and Dickenson, R. L., "Biological And Engineering
Investigation To Develop Optimum Control Measures To Prevent
Water Pollution," Final Engineering Report - Propellant Plant
Pollution Abatement, Radford Army Ammunition Plant, April 1972.
XV-11
-------
DRAFT
E-13. "Concept Engineering Report - TNT Waste Control Program,"
Catalytic, Inc. for U.S. Naval Ammunition Depot, Crane,
Indiana, October 1972.
E-l4. Patterson, J. W., et al, "Wastewater Treatment Technology,"
Illinois Institute of Environmental Quality, August 1971.
E-15. Neal, L. G., "Army Munitions Plants Modernization Program
Pollution Abatement Review" Final Report No. 96020 007,
Picatinny Arsenal, Dover, N.J., August 1973.
E-16. "Carbon Column System Removal Efficiency Study, Iowa Army
Ammunitions Plant, Burlington, Iowa," Environmental Hygiene
Agency No. 24-033-73/74, U.S. Army, Aberdeen Proving Grounds,
Md., June 1973.
E-17. "Pollution Abatement Engineering Program For Munition Plant
Modernization," U.S. Army, Picatinny Arsenal, Dover, N.J.,
February 1974.
E-18. "Propellent Plant Pol 1ution Abatement Engineering Investi-
gation To Develop Optimum Control Measures To Prevent Water
Pollution," U.S. Army Final Engineering Report On Production
Engineering Project PE-249 (Phase II), Radford Army Ammuni-
tion Plant, May 1974.
E-19. "EPA Guidelines Group Meeting At Radford Army Ammunition
Plant Water Pollution Abatement And Control," U.S. EPA,
November 1974.
E-20. "U.S. Environmental Protection Agency Report On Waste Disposal
Practices Radford Army Ammunition Plant, Radford, Virginia,"
U.S. EPA, Middle Atlantic Region - III, Philadelphia, Pa.
July 1972.
E-21. Klausmeier, J. L., "The Effect Of TNT On Soil Microorganisms,"
U.S. Navy, 1973.
E-22. "Pollution Abatement Engineering Program for Munition Plant
Modern! zat ion','5th Briefing for Senior Scientist Steering
Group, Picatinny Arsenal, Dover, N.J., February 1975.
XV-12
-------
'^^
DRAFT
E-23. "A Characterization Study of the Wastewater Effluents of the
Military Explosives & Propel lants Production Industry",
Vol. !, li, III, (unpublished) prepared by Adhoc Committee of
the American Defense Preparedness Association, February 1975.
E-24. U.S. EiJA ''Process Design Manuel for Carbon Adsorption",
Technology Transfer, October 1973-
E-25. Rosenblatt, David H., "Investigations Related to Prevention
and Control of Water Pollution in the U. S. TNT Industry," in
Pollution, Engineering and Scientific Solutions , E . S .
Barrekette, Plenum Press, N. Y., 1973.
E-26. Schuite, G. R., Hoehn, K. C., and Randall, C. W., "The Treat-
ability of a M in i t ions-Manuf actur i ng Waste with Activated
Carbon," Proc, 28th Purdue Industrial Waste Conference,
Purdue University, W. Lafayette, Indiana, May 2k, 1973.
E-27. Kozlorowski, B. and Kucharski, J., Industrial Waste Diaposal,
Pergamon Press, New York, 1972.
E-28. Edwards, G., and Ingram, W. T., "The Removal of Color from
TNT Wastes," Journal Sanitary Engineering, American Society
of Civil Engineers, 81, Separate No. 645,1955.
E-29. Rudolfs, W., Industrial Wastes Their Disposal and Treatment
Reinhold Publication Company, New York, 1953-
E-30. Osman, J. L., and Klausmeir, R. E., "The Microbial Degradation
of Explosives," Developments in industrial Microbiology,
14:247-252, 1973.
E-31 . Nay, M. W., Jr., Randall, C. W. and King, P. H., "Biological
Treatability of Trinitrotoluene Manufacturing Wastewater,"
Journal Water Pollution Control Federation, 46:3485-497,
1974.
E-32. Ruchhoft, C. C., LeBosquet , M., Jr., and Meckler, W. G.,
"TNT Wastes from She 1 1 -Load i ng Plants," Industrial Engineering
Chemical 37:937, 1945.
E-33- Sol in, V. and Burianek, K., "The Removal of TNT from Industrial
Waste," Journal on Water Pollution Control Federation. 32:-:110,
1960.
E-34. U. S. Army Corps of Engineers, "Wastewater Management by
Disposal on the Land." Special Report #171, May 1972.
XV-13
-------
DRAFT
E-35- Transportation and Environmental Operations, "Army Munitions
Plants Mocerni zat ion Program Pollution Abatement RevieW»
August 1973.
E-36. Radford AAP, "Production Engineering Project PE2^9 (Phase II)"
Radford, Virginia, May
E-37- Hoffsommer, J. C., "B iodegradabi 1 i ty of TNT", Naval Ordinance
Laboratory, Maryland, November 1973-
E-38. U. S. AEHA, "Carbon Column System Removal Efficiency Study",
Iowa AAP, May, June 1973-
E-39- EPA, "Group Meeting at Radford AAP - Water Pollution Abatement
and Control , November 18,
E-40. Hercules, Inc., "Production Engineering Project PE2^9 (Phase I)",
Radford AAP, Apr! 1 1972.
E-41 . Catalytic, Inc., "Concept Engineering Report TNT Waste Control
Program", Crane Naval Ammunition Depot, October 1972.
E-42. Construction Engineering Research Laboratory, "Technical
Evaluation Study, Industrial Wastewater Treatment Area A,
Holston AAP.", Kingsport, Tennessee, December 1973-
E-43. Holston Defence Corporation, "Material Balance and Waste
Characterization on Explosives Finishing and Analytical
Laboratories", Kingsport, Tennessee.
E-U^f. Holston Defence Corporation, "Materials Balance and Waste
Characterization - Explosive Manufacturing", Kingsport,
Tennessee, September 1972.
E-45. EPA, "Report on Holston AAP", Kingsport, Tennessee, March 1973.
E-U6. EPA, "Report on Waste Source Investigations", Kingsport,
Tennessee, March 1973.
E-^7. Hercules, Inc., "Production Engineering Project PE210
Alleviation of Pollution in Water From Solvent Recovery and
Water Dry Operations", RAAP, August 1972.
E-48. Hercules, Inc., "Production Engineering Project PE275 (Phase I)
Propel lant Plant Pollution Abatement Engineering Study to
Establish Disposal Methods for Waste Acid Neutralization Sludge",
RAAP, March 1973-
-------
DRAFT
E-49. Hercules, Inc., "Production Engineering Project PE290 (Phase I!)".
* Propellant Plant Pollution Abatement Improvement of Water
Utilization at RAAP, November 1973.
E-50. EPA, "Report on Waste Disposal Practices at Radford AAP",
Virginia, May 1973.
™ E-51 . Report No. 24-034-72: Water Quality Engineering Special
Study, Twin Cities AAP, October 1972.
E-52. Report No. 24-033-72: Water Quality Engineering Special
Study, Volunteer AAP, August 1972.
^ E-53. Report No. 24-024-72: Water Quality Engineering Special
Study, Joliet AAP, June 1972.
E-54. Report No. 24-014-72: Water Quality Engineering Special
Study, Longhorn AAP, April 1972.
* E-55. Report No. 24-006-72: Water Quality Engineering Special
Study, Louisiana AAP, December 1971.
E-56. Report No. 24-001-72: Water Quality Engineering Special
Study, Radford AAP, October 1971.
*^^ E-57. Report No. 24-030-71: Water Quality Engineering Special
Study, Lake City AAP, August 1971.
E-58. Report No. 24-021-71: Water Quality Engineering Special
Study, Holston AAP, 19 March - 28 June 1971.
E-59. Report No. 24-009-71: Water Quality Engineering Special
Study, Scranton AAP, December 1970.
E-60. Report No. 24-005-71: Water Quality Engineering Special
Study, Louisiana AAP, 1 May - 15 August 1970.
* E-61 . Report No. 24-002-69: Special Study of Industrial Waste
at Sacramento, California, October 1968.
E-62. Report No. 24-024-73: Water Quality Monitoring 6- Installation
Laboratory Consultation at Riverbank AAP, December 1972.
* E-63. Report No. 24-010-70: Report of General Sanitary Survey
at Sunflower AAP, September 1969.
E-64. Report No. 24-023-73: Water Quality Monitoring & Installation
Laboratory Consultation Visit at Twin Cities AAP, October 1972.
XV-15
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DRAFT
E-65. Report No. 24-019-71: Follow-up Study of Storm Survey
Pollution at Burlington AAP, November 1970.
E-66. Report No. 24-010-71: Sanitary Engineering Survey at
Cornnusker AAP, December 1970.
E-6/'. Report No. 24-029-70/71: Sanitary Engineering Survey
at Lake City AAP, October 1970.
E-68. Report No. 24-026-70: Sanitary Engineering Survey at
Holston AAP, January 1970.
E-69. Report No. 24-003-71: Sanitary Engineering Survey at
Volunteer AAP, August 1970.
E-70. Report No. 24-010-73: Water Quality Biological Study
at Holston AAP, August 1972.
E-71 . Report No. 24-001-71: Sanitary Engineering Survey at
Joliet AAP, July 1970.
E-72. Report No. 24-002-71: Sanitary Engineering Survey at
Indiana AAP, July 1970.
E-73. Report No. 24-003-72: Water Quality Engineering Survey
at Iowa AAP, September 1971.
E-74. Repo.-t No. 24-009-73: Water Quality Biological Study
at Iowa AAP, July 1972.
E-75. Report No. 24-004-72: Water Quality Engineering Special
Study at Badger AAP, April - October 1971.
E-76. Report No. 24-038-70/71: Sanitary Engineering Survey &
Industrial Waste Special Study at Badger AAP, May 1970.
E-77. Report No. 24-038-73/74: Water Quality Monitoring &
Consultation at Badger AAP, April 1973.
E-78. Report No. 24-007-71: Sanitary Engineering Consultation
Visit at Louisiana AAP, October 1970.
E-79- Report No. 24-024-70: Sanitary Engineering Survey at
Louisiana AAP, January 1970.
E-80. Report No. 24-029-72/73: Water Quality Engineering Survey
at Lone Star AAP, May 1972.
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E-81. Report No. 24-004-73: Water Quality Engineering Survey at
Kansas AAP, August - September 1972.
E-82. Report No. 24-009-70: Report of General Sanitary Engineering
Survey at Kansas AAP, September 1969.
E-83. Repo t No. 24-032-72/73: Water Quality Engineering Special
Study at Joliet AAP, June 1972.
E-84. Report No. 24-030-72/73: Water quality Monitoring 6-
Installation Laboratory Consultation at Joliet AAP, June 1972.
E-85. Report No. 24-027-72: Water Quality Engineering Special
Study at Longhorn AAP, December - January 1972.
E-86. Report No. 24-011-73/74: Water Quality Engineering Survey
at Mi Ian AAP, March 1973.
£-87. Report No. 24-039-73/74: Water Quality Monitoring &
Installation Laboratory Consultation at Lavenna AAP, April 1973.
E-88. Report No. 24-005-70: Report of General Sanitary Engineering
Survey at Ravenna AAP, April 1973.
E-89. Report No. 24-025-73: Water Quality Monitoring & Installation
Laboratory Consultation at Louisiana AAP, January 1973.
E-90. Report No. 24-026-72: Water Quality Engineering Special Study
at Louisiana AAP, March - April 1972.
E-91. Report No. 24-030-73: Water Quality & Installation Laboratory
Consultation at Milan AAP, March 1973.
E-92. Report No. 24-041-73/74: Water Quality Monitoring & Installa-
tion Laboratory Consultation at Longhorn AAP, June 1973-
E-93- Report No. 24-023-70: General Sanitary Engineering Survey at
Longhorn AAP, January 1970.
E-94. Report No. 24-025-70: Sanitary Egnineering Survey at
Mi Ian AAP, January 1970.
E-95. Technical Report 4554, Project No. 54114: A Laboratory Study
of Carbon Adsorption for Elimination of Nitrobody Waste at
Dover AAP, January 1973.
E-96. Technical Report 4552, Project No. 54114: Pilot Aeration &
Neutralization at Joliet AAP, April 1973.
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E-97. EPA: Report on Waste Source Investigations, Kingsport,
Tennessee. National Field Investigation Center - Denver,
Cincinnati, Region IV Atlanta, Georgia, April 1973.
E-98. Report No. 24-005-73: Water Quality Monitoring S- Installation
Laboratory Consultation at Holston AAP, August 1973.
E-99. Report No. 24-006-73: Water Quality Monitoring & Installation
Laboratory Consultation Visit at Volunteer AAP, August -
September 1972.
E-100, Report No. 24-031-72/73: Water Quality Engineering Special
Study at Volunteer AAP, May 1972.
E-101. Report No. 24-002-70: Water Quality Engineering Special
Study, Burlington AAP, 18-19 August
E-102. Report No. 24-011-69: Water Quality Engineering Special
Study, Radford AAP, 13-21 June 1969.
E-103. Report No. 24-009-68: Special Study of Industrial Wastes
at Radford AAP, May 1968.
E-104. Report No. 24-017-67: Report of Industrial Waste Survey,
Sunflower AAP, 16-27 October 1967. A
E-105. Report No. 24-013-73: Water Quality Biological Study at
Newport AAP, September 1972.
E-106. Report No. 24-004-71: Sanitary Engineering Study at
Newport AAP, August 1970.
E-107. Report No. 24-007-69: Water Pollution Evaluation Visit at
Newport AAP, February 1969.
E-108. Report No. 24-027-73: Water Quality Monitoring & Installation
Laboratory Consultation at Newport AAP, January 1973.
E-109. Report No. 24-007-73: Water Quality Monitoring & Installation
Laboratory Consultation at Radford AAP, September 1972.
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F. Carbon Black Industry
F-l. Encyclopedia of Chemical Technology, Kirk Othmer, Inter-
science Publishers Division, John Wiley and Sons, Inc.,
Second Edition.
F-2. Minerals Yearbook, U.S. Department of Interior, 1973.
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Photographic Processing Industry
G-l. "Information Form For Requesting Assistance In Pollution
Abatement," Photographic Technology Division, Eastman Kodak
Company, Rochester, N.Y.
G-2. "Wolfman Report on the Photographic Industry in the United
States," Modern Photography Magazine, 1973-74.
G-3. Bard, C. E., et al, "Silver in Photoprocess ing Effluents,"
Eastman Kodak Company, Rochester, N. Y.
G-4. Dagon, T.J., "Biological Treatment Of Photoprocess i ng Effluents,"
JWPCF, Vol. 15, No. 10, October 1973.
G-5. "Pretreatment of Pollutants Introduced Into Publicly Owned
Treatment Works," EPA, October 1973.
G-6. Fulweiler, S. B., "The Nature of Photographic Processing,"
Presented at Photoprocess ing and the Environment Seminar,
June
G-7. "American National Standard on Photographic Processing Ef-
fluents, Drafts, ANSI, November
G-8. Terhaar, C. J., et al, "Toxicity of Photographic Processing
Chemicals to Fish," Photographic Science and Engineering,
Vol. 16, No. 5, September - October 1972.
G-9. Cooley, A. C., "Reuse and Recovery of Processing Chemicals,"
Presented at Photoprocess ing and the Environment Seminar,
June
G-IO. Ayers, G. L., "How Processor Waste Loads Can Be Minimized,"
Presented at Photoprocess ing and the Environment Seminar,
June
G-l I. Dagon, T. J., "Specific Applications Of Photographic Process-
ing Effluent Treatment," Presented at Photoprocess ing and the
Environment Seminar, June
G-12. Duff icy, T. J., "The Federal Water Pollution Control Act of
1972. Its Effect on Photographic Processing Operations,"
Photoprocess ing and the Environment Seminar, June 197^.
G-13. Cook, C., "Variability in BOD- Concentration From Biological
Treatment Plants."
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"Effluent Limitations Guidelines and Standards of Perfor-
mance - Metal Finishing Industry," Draft Development Docu-
ment, January
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DRAFT
H. Hospitals
H-l. Guide to the Health Care Field, American Hospital Associ-
ation,
H-2. "A Survey of a Sewage Treatment Plant at a Tuberculosis
Hospital," U.S. Army Medical Research and Development Command,
June 1959.
H-3. "Control of Mercury Pollution," American Hospital Associ-
ation, July, 1971 .
H-k. "Survey of Water Charge Practices," American Hospital Associ-
ation, 1952.
XV-22
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SECTION XVI
GLOSSARY
A. Pharmaceutical Industry
Activated Sludge Process. In this process, wastewater is stabilized
biologically in a reactor under aerobic (in the presence of oxygen)
cond i t ions.
Aerob ic. Ability to live, grow, or take place only where free oxygen
is present.
Alkylat ion. The addition of an aliphatic group to another molecule.
The media in which this reaction is accomplished can be vapor or
liquid phase, as well as aqueous or non-aqueous.
Ampules. A small glass container that can be sealed and its contents
sterilized. Ampules are used to hold hypodermic solutions.
Anaerob ic. Ability to live, grow, or take place where there is no
air or free oxygen present.
Antagonistic Effect. The simultaneous action of separate agents
mutually opposing each other.
Ant ib iot ic. A substance produced by a living organism which has
power to inhibit the multiplication of, or to destroy, other organisms,
especially bacteria.
Aqueous Solution. One containing water or watery in nature.
Bacter i a. Unicellular, plant-like microorganisms, lacking chlorophyll.
BADCT Effluent Limitations. Limitations for new sources which are
based on the application of the Best Available Demonstrated Control
Techno logy.
Batch Process. A process which has an intermittent flow of raw
materials into the process and a resultant intermittent flow of product
from the process. This is the most common type process employed by the
Pharmaceutical industry to manufacture medicinal chemicals.
BATEA Effluent Limitations. Limitations for point sources, other than
publicly owned treatment works, which are based on the application of
the Best Available Technology Economically Achievable. These limita-
tions must be achieved by July 1, 1983.
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Biological Treatment System. A system that uses microorganisms to
remove organic pollutant material from a wastewater.
Blowdown, Water intentionally discharged from a cooling or heating
system to maintain the dissolved solids concentration of the circu-
lating water below a specific critical level.
BODS. Biochemical Oxygen Demand (BOD) is the amount of oxygen re-
quired by bacteria while stabilizing decomposable organic matter
under aerobic conditions. The BOD test has been developed on the
basis of a 5-day incubation period (i.e. BODj-).
BPCTCA Effluent Limitations. Limitations for point sources, other
than publicly Owned treatment works, which are based on the applica-
tion of the Best Practicable Control Technology Currently Available.
These limitations must be achieved by July 1, 1977.
Capsules. A gelatinous shell used to contain medicinal chemicals
and as a dosage form for administering medicine.
Catalyst. A substance which changes the rate of a chemical reaction
but undergoes no permanent chemical change itself.
Ce1lulose. The fibrous constituent of trees which is the principal
raw material of paper and paperboard.
Centrate. The liquid fraction that is separated from the solids
fraction of a slurry through centrifugation.
Centrifuqat ion. The process of separating heavier materials from
lighter ones through the employment of centrifugal force.
Chemical Synthesis. The processes of chemically combining two or
more constituent substances into a single substance.
C1ar i f icat ion. The process of removing undissolved materials from a
liquid specifically either by settling or filtration.
Contact Process Wastewaters. These are process-generated wastewaters
which have come in direct or indirect contact with the reactants used
in the process. These include such streams as contact cooling water,
filtrates, centrates, washwaters, etc.
Continuous Process. A process which has a constant flow of raw
materials into the process and a resultant constant flow of product
from the process.
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Crystal 1i zat ion. The formation of solid particles within a homo-
geneous phase. Formation of crystals separates a solute from a
solution and generally leaves impurities behind in the mother liquor.
Crystallization from solution is important in the pharmaceutical
industry because of the variety of materials that are marketed in
crysta11ine form.
Cu 1 ture. A mass of microorganisms growing in a media.
Cyan i de. Total cyanide as determined by the test procedure specified
in kO CFR Part 136 (Federal Register,Vol. 38, no. 199, October 16,
1973).
Cyanide A. Cyanides amendable to chlorination as described in
"1972 Annual Book of ASTM Standards" 1972: Standard D 2036-72,
Method B, p. 553.
Den i tr i f i cat ion. Bacterial mediated reduction of nitrate to nitrite.
Other bacteria may act on the nitrite reducing it to ammonia and
finally N? gas. This reduction of nitrate occurs under anaerobic
conditions. The nitrate replaces oxygen as an election acceptor
during the metabolism of carbon compounds under anaerobic conditions.
Perivat ive. A substance extracted from another body or substance.
D i s infectant. A chemical agent which kills bacteria.
D i st i1lat ion. The separation, by vaporization, of a liquid mixture
of miscible and volatile substances into individual components, or,
in some cases, into groups of components.
Ester i f icat ion. This generally involves the combination of an alcohol
and an organic acid to produce an ester and water. The reaction is
carried out in the liquid phase, with aqueous sulfuric acid as the
catalyst. The use of sulfuric acid has in the past caused this type
of reaction to be called sulfation.
Fermentat ion. Oxidative decomposition of complex substances through
the action of enzymes or ferments produced by microorganisms.
F i 1 trate. The liquid fraction that is separated from the solids
fraction of a slurry through filtration.
Fungus. A vegetable cellular organism that subsists on organic
material, such as bacteria.
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Gland. A device utilizing a soft wear-resistant material used to ^^
minimize leakage between a rotating shaft and the stationary portion 4
of a vessel such as a pump.
Gland Water Water used to lubricate a gland. Sometimes called
"packing water."
In-Plant Measures. Technology applied within the manufacturing <|
process to reduce or eliminate pollutants in the raw waste water.
Sometimes called "internal measures" or "internal controls".
Medicament. Medicine or remedy.
Mycelium. The mass of filaments which constitutes the vegetative |
body of fungi.
Neutra 1 izat ion. The treatment of wastewaters with either caustic
or acid to adjust the wastewater pH to approximately 7.0.
N i tr i f icat ion. Bacterial mediated oxidation of ammonia to nitrite. |
Nitrite can be further oxidized to nitrate. These reactions are
brought about by only a few specialized bacterial species. N i t ro-
somon ias sp. and N i trococcus sp. oxidize ammonia to nitrite which is
oxidized to nitrate by Nitrobacter sp.
N i tr i fiers. Bacteria which causes the oxidation of ammonia to
nitrites and nitrates.
Nitrogen Fixation. Biological nitrogen fixation is carried on by
a select group of bacteria which take up atmospheric nitrogen (^)
and convert it to amine groups or for amino acid synthesis.
Noncontact Process Wastewaters. Wastewaters generated by a manu-
facturing process which have not come in direct contact with the
reactants used in the process. These include such streams as non-
contact cooling water, cooling tower blowdown, boiler blowdown, etc.
NPDES. National Pollution Discharge Elimination System. A federal
program requiring industry to obtain permits to discharge plant
effluents to the nation's wastecourses.
Parenteral. Injection of substances into the body through any route
other than via the digestive tract.
pH. A symbol for the degree of acidity or alkalinity of a solution;
expressed as the logarithm of the reciprocal of the hydrogen ion
concent rat ion.
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Physica1/Chemical Treatment System. A system that utilizes physical
(i.e., sedimentation, filtration, centrifugation, etc.) and/or
chemical means (i.e., coagulation, oxidation, precipitation, etc.)
to treat wastewaters.
PI asma. The liquid part of the lymph and of the blood.
PMA. Pharmaceutical Manufacturers Association. The PMA represents
110 pharmaceutical manufacturing firms, who account for approximately
95 percent of the prescription products sold in the United States.
Raw Waste Load (RWL). The quantity (kg) of pollutant being discharged
in a plant's wastewater, measured in terms of some common denominator
(i.e., kkg of production or m^ of floor area).
San i tary Landf ill. A sanitary landfill is a land disposal site
employing an engineered method of disposing of solid wastes on land
in a manner that minimizes environmental hazards by spreading the
wastes in thin layers, compacting the solid wastes to the smallest
practical volume, and applying cover material at the end of each
operating day.
Saprophytic Organism. One that lives on dead or decaying organic
matter.
Seed. To introduce microorganisms into a culture medium.
Serum. A fluid which is extracted from an annual rendered immune
against a pathogenic organism and injected into a patient with the
disease resulting from the same organism.
Solvent. A liquid which reacts with a material, bringing it into
solution. The Pharmaceutical industry uses solvents extensively
in product extraction processes.
Solvent Extraction. A mixture of two components is treated by a
solvent that preferentially dissolves one or more of the components
in the mixture. The solvent in the extract leaving the extractor
is usually recovered and reused.
Standard Raw Waste Load (SRWL). The raw waste load which character-
izes a specific subcategory. This is generally computed by averaging
the plant raw waste loads within a subcategory.
Steroi d. Term applied to any one of a large group of substances
chemically related to various alcohols found in plants and animals.
XVI-5
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Synergistic Effect. The simultaneous action of separate agents which,
together, have greater total effect than the sum of their individual
effects.
Tab let. A small, disc-like mass of medicinal powder used as a
dosage form for administering medicine.
Thermal Oxidation. The wet combustion of organic materials through
the application of heat in the presence of oxygen.
Toxo id. Toxin treated so as to destroy its toxicity, but still
capable of inducing formation of antibodies.
Trypsinized. To be hydrolyzed by trypsin, an enzyme in pancreatic
j u i ce.
Vacci ne. A killed or modified live virus or bacteria prepared in
suspension for innoculation to prevent or treat certain infectious
d i seases.
V i rus. The specific living diseased agent by which infectious
disease is transmitted.
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8. Gum and Wood Chemicals Industry
Carbon i zat ion. A process whereby a carbon residue is produced via
the destructive distillation of wood.
Cyclone. A conical shaped vessel for separating either entrained
solids or liquid materials from the carrying air or vapor. The
vessel has a tangential entry nozzle at or near the largest diameter,
with an overhead exit for air or vapor and a lower exit for the
more dense materials.
Destructive Distillation. Decomposition of wood (or a hydrocarbon)
by heat in a closed container and the collection of the volatile
substances produced.
Entrainment Separator. A device to remove liquid and/or solids from
a gas stream. Energy source is usually derived from pressure drop
to create centrifugal force.
Essent i a 1 Oils. An oil composed mainly of terpene hydrocarbons
(turpentine), which are obtained by steam distillation of wood
chips, bark or leaves of select trees.
Ester Gum. A resin made from rosin or rosin acids and a polyhydric
alcohol, such as glycerin or pentaerythritol .
Exudate. Exuded matter.
Fractionation (or Fractional Distillation). The separation of con-
stituents, or group of constituents, of a liquid mixture of miscible
and volatile substances by vaporization and recondensing at specific
boiling point ranges.
Gum. The crystallized pine oleoresin or "scrape" collected from
scarified "faces" of trees being worked for turpentine, exudates
from living long leaf and slash pine trees.
Hardwood (or Deciduous Woods). Trees that lose their leaves annually.
Morphologically and chemically distinct from the conifers and commonly
referred to as hardwoods, despite the fact that certain species such
as basswood and poplar have woods that are relatively soft. Fibers
are substantially shorter that those of coniferous wood. Normally,
deciduous woods are not a source of turpentine.
Kraft (or Sulfate) Process. The digestion of wood chips with a solu-
tion of sodium hydroxide, sodium sulfide, and sodium carbonate to
product paper pulp. This process delignifies the wood chip and allows
XVI-7
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DRAFT
separation of the cellulose fibers from a caustic solution of lignin
degradation products (sugars, hemicel 1 ulose , resin, and fatty acids)
and unsapon i f iab les .
Naval Stores . Chemically reactive oils, resins, tars, and pitches
derived from the oleoresin contained in, exuded by, or extracted
from trees chiefly of the pine species (Genus Pinus), or from the
wood of such trees.
Noncondens i b les . Vapors or gases that remain in the gaseous state
at the temperature and pressure specified. These normally would be
considered the final vented gases under operating conditions.
Oleores rn. Pine gum, the non-aqueous secretion of rosin acids dis-
solved in a terpene hydrocarbon oil which is produced or exuded from
the intercellular resin ducts of a living tree or accumulated, to-
gether with oxidation products, in the dead wood of weathered limbs
and stumps.
P i ne Tar Oil. The oil obtained by condensing the vapors from the re-
torts in which resinous pine wood is destructively distilled (carbonized)
P i tch. A dark viscous substance obtained as a residue in the dis-
tillation of the volatile oils from retort pine oil or crude ta}} oil.
Pitch, Brewer's. A term used to designate a type of pitch made by
blending certain oils, waxes or other ingredients with rosin for the
coating of beer barrels.
Pyrol igeneous Acid. A product of the destructive distillation of
hardwoods composed primarily of acetic acid, crude methane! , acetone,
tars and oils, and water.
Res i n . A large class of synthetic products that have properties
similar to natural resin, or rosin, but are chemically different.
Retort . A vessel in which substances are distilled or decomposed
by heat.
Ros in. A specific kind of natural resin obtained as a nitreous water-
insoluble material from pine oleoresin by removal of the volatile oils,
or from tall oil by the removal of the fatty acid components thereof.
It consists primarily of tricyclic monocarboxy 1 ic acids having the
general empirical formula &2Q H^Q £>2' w'th small quantities of com-
pounds saponifiable with boiling alcoholic potassium or sodium
hydroxide, and some unsapon if i able. The three general classifica-
tions or kinds of rosin in commerce are: gum rosin, obtained from
the oleoresin collected from living trees; wood rosin, from the
oleoresin contained in dead wood, such as stumps and knots; and tall
oil rosin, from tall oil.
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Rosin, Modified. Rosin that has been treated with heat or catalysts,
or both; wi ;h or without added chemical substances, so as to cause
substantial change in the structure of 'the rosin acids, as isomeriza-
tion, hydrogenation, dehydrogenation, or polymerization; without
substantial effect on the carboxyl group.
Seal Leg. The line through which an underflow liquid flows, con-
structed to maintain a liquid trap that will not empty upon nominal
pressure changes in the vessel.
Separator. The vessel connected to the vent-relief to separate
wood fines carried over in the vent-relief gases, and which permits
the steam and turpentine vapors (including noncondensables) to pro-
ceed in vapor form to the condenser.
Steam D i st i11 at ion. A distillation or fractionation in which steam
is introduced as one of the vapors or in which steam is injected to
provide the heat of the system.
Tall Oil. A generic name for a number of products obtained from the
manufacture of wood pulp by the alkali (sulfate) process or more pop-
ularly known as the kraft process. To provide some distinction between
the various products, designations are often applied in accordance
with the process or composition, some of which are crude tall oil,
acid refined tall oil, distilled tall oil, tall oil fatty acids, and
tall oil ros in.
Tall Oil, Crude. A dark brown mixture of fatty acids, rosin, and
neutral materials liberated by the acidification of soap skimmings.
The fatty acids are a mixture of oleic acid and linoleic acid with
lesser amounts of saturated and other unsaturated fatty acids. The
rosin is composed of resin acids similar to those found in gum and
wood rosin. The neutral materials are composed mostly of polycyclic
hydrocarbons, sterols, and other high-molecular weight alcohols.
Terpenes. The major chemical components of turpentine. A class of
unsaturated organic compounds having the empirical formula C^Q H-j^,
occurring in most essential oils and oleoresinuous plants. Struc-
turally, the important terpenes and their derivatives are classified
as monocyclic (dipentene), bicyclic (pinene), and acyclic (myrcene).
Turpent i ne. A light-colored, volatile essential oil from resinuous
exudates or resinous wood associated with living or dead coniferous
trees, particularly those commonly called pines. There are four
kinds of turpentine as follows: (1) gum turpentine, obtained by
distilling the gum collected from living pine trees; (2) steam-
distilled wood turpentine, from the oleoresin within the wood of
pine stumps or cuttings, either by direct steaming of mechanically
XV I-9
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DRAFT
disintegrated wood or after solvent extraction of the oleoresin from
the wood; (3) sulfate wood turpentine, recovered during the con-
version of wood pulp by the kraft (sulfate) process. (Sulfate wood
turpentine is somewhat similar to gum turpentine in composition);
and (k) destructively distilled wood turpentine, obtained by frac-
tionation of certain oils recovered from the destructive distilla-
tion of pine wood.
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DRAFT
C. Pesticides and Agricultural Chemicals Industry
Act i ve Inqred ient. The element or compound on which a particular
pesticide is based to perform its specified function. The active
ingredient makes up only a small percentage of the final product
which consists of binders, fillers, diluents, etc.
Adj urant. A material which enhances the action of another material.
Aerosols. Gaseous suspensions of minute particles of a liquid or
sol id.
A! g ic ide. Chemical agent used to destroy °r control algae.
Alkaline Hydrolysis. A process whereby wastes are detoxified by
extended heat treatment in an alkaline medium. Generally used in
the organo-phosphorus pesticide industry.
Ami nat ion. The preparation of amines which are derived from ammonia
by replacement of one or more hydrogens or organic radicals.
Attractants. Chemical agents which dry or attract insects or other
pests to them.
Boiler B1owdown. Wastewater resulting from purging of solid and
waste materials from the boiler system. A solids build up in con-
centration as a result of water evaporation (steam generation) in
the boiler.
Broad Spectrum. A wide-range when referring to a pesticde; it
means the effectiveness covers a wide-range of pests.
Chlorination. A chemical process where chlorine is introduced
into a chemical species by substitution or addition.
Contact Insecticide. Insecticide which requires direct contact
with the insect to be affective.
Contract D i sposa 1 . Disposal of waste products through an outside
party for a fee.
Decanting Operations. Process whereby heavy (light) liquid frac-
tions are drained from a reactor or vessel allowing the lighter
(heavier) liquid layer to remain.
Defo1i ants. A category of chemical agents which when sprayed on
plants causes the leaves to fall off prematurely.
XVI-11
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DRAFT
Des iccants. Chemical used as a drying agent. Substances which have
such a great affinity for water that it will abstract it from a great
many fluid materials.
Detox if icat ion. A process to remove or neutralize components in
a waste stream which inhibit or stop biological growth.
Dust. Dry, solid powder. When applied to pesticide production
implies a dry, powder form product.
Emulsiffable Concentration. Pesticide in the concentrate liquid
form which when added to another liquid forms a stable colloidal
discharge form application.
Formulators. A segment of the Pesticide industry which does not
manufacture pesticides but mixes and blends active ingredients with
binders, fillers, and diluents to produce the final product for
d i stribut ion.
Fumi gant. A chemical compound which acts in the gaseous state to
destroy insects and their larva and other pests.
Fung ic i des. A category of chemical agents jsed to destroy fungi.
Granular. For a grainy texture or composition.
Halogenated-Organic Pesticides. A category of pesticides which
uses halogenated, primarily chlorinated, organic compounds as the
active ingredients.
Herb ic ide. Category of chemical agents used to destroy or control
undesirable plant life such as weeds.
Insect ic ide. Chemical agent used to destroy insects.
LD5Q. Abbreviation for lethal dose 50 - a dose of substances which
is fatal to 50% of the test animals.
Meta 1 lo-Orqanic Pesticides. A category of pesticides structured
around a heavy metal as the active species.
Nemataude. A chemical agent used to kill plant - parasitic nematodes
(i.e., unsegmented worms).
Noncontact Wastewater. Wastewater which does not come in direct
contact with process materials.
XVI-12
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DRAFT
Non-Process Water. Waters which do not come in contact with the
product, or by-products such as cooling water, boiler blowdown, etc.
Operations and Maintenance. Costs required to operate and maintain
pollution abatement equipment including labor, material, insurance,
taxes, solid waste disposal, etc.
Organo-Nitrogen Pesticides. A category of pesticides which uses
nitrogenous compounds as the active ingredients.
Organo-Phosphorus Pest ic i des. A category of pesticides which uses
phosphate or phosphorus compounds as the active ingredients.
Packagers. The last step in preparing a pesticide for distribution
to the consumer. This segment of the industry takes the final formu-
lated product and puts it into a marketable container such as drums,
bottles, aerosol cans, bags, etc.
Pest ic i des. General term describing chemical agents which are used
to destroy pests. Pesticides includes herbicides, insecticides,
fungicides, etc., and each type of pesticide is normally specific
to the pest species it is meant to control.
P 1 ant V i s i tat ion. Part of data collection phase of the study in-
volving a visit to a pesticide production facility.
Pri 1 led. To have been formed into pellet-sized crystals or spherical
part icles.
Process Water. All waters that come in direct contact with the raw
materials and intermediate products.
Rodent i c i des. Category of chemical agents which are used to kill
and destroy rodents, i.e., rats and mice.
Solut ion. A single phase, homogeneous liquid that is a mixture in
which the compounds are uniformly destroyed.
St r i pper. A device in which relatively volatile components are
removed from a mixture by distillation or by passage of stream
through the mixture.
Wet Air Pollution Control. The technique of air pollution abatement
utilizing water as an absorptive media.
XVI-13
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DRAFT
D. Adhesive and Sealants Industry
Adherend. The term adherend is generally used to refer to the body
held to another body by the adhesive. The process of attaching one
adherend to another by means of adhesive is generally referred to as
bond i ng.
Adhes ive. Current usage defines an adhesive as a substance capable
of holding materials together by surface attachment. The term ad-
hesive is now considered to be a general term that includes other
materials, such as cement, glue, mucilage, and paste.
Carrier. A carrier is usually a thin fabric or foil used to support
adhesive composition in order to provide a dry film adhesive.
Catalysts. Catalysts are substances which markedly speed up the
cure of an adhesive when added in minor amounts as compared to the
amounts of the primary reactants. Catalysts are commonly used to
speed up the curing of cross-linking of urea-formaldehyde wood
adhes i ves.
Cement. The term cement is commonly used to refer to adhesives
based on rubbers or thermoplastic dispersed in organic solvents
and which set by loss of solvent.
Double-Effect Evaporators. Double-effect evaporators are two eva-
porators in series where the vapors from one are used to boil
1iquid in the other.
Emu 1s ion. Emulsion is a suspension of fine droplets of one liquid
in another.
Extenders. Extenders are substances generally having some adhesive
action. They are added to an adhesive to reduce the amount of pri-
mary binder required per unit area.
F i1lers. Fillers are relatively nonadhesive substances added to an
adhesive to improve its working properties, permanence, strength, or
other quali t ies.
Fort i f iers. Fortifiers are materials which are added to an adhesive
binder primarily to improve the permanence of the resultant bond.
Glue. The term glue originally referred to adhesives prepared from
animal proteins, such as hides, hoofs, cartilage, and tendons.
XVI-Ht
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DRAFT
Hardeners. Hardeners are substances or mixtures of substances added
to an adhesive to promote or control the curing reaction by taking
part in it. A hardener is ar\ actual chemical reactant in the curing
reaction as compared to the catalyst which does not react directly
but merely controls the rate of reaction.
Humectant. Humectant is an agent which adsorbs water. It is often
added to resin formulations in order to increase water absorption
and thereby minimize problems associated with electrostatic charge.
Hue ilage. A mucilage is an adhesive prepared from vegetable gums
and water and is mainly used for bonding paper.
Phenol. Phenol is a class of cyclic organic derivatives with the
basic chemical formula C^H OH.
Polymer. Polymer is a high molecular weight organic compound,
natural or synthetic, whose structure can be represented by a re-
peated small unit + the (HER) 1.
Preservat i ves. Preservatives are agents added to certain adhesives
to retard or prevent decomposition by microorganisms, either while
the adhesive is being stored or applied or during service of the
completed bond. These agents are usually most important in formu-
lations containing carbohydrates or proteins, such as flour, starch,
casein, or animal proteins that are readily attacked by mold, fungi,
or bacteria.
Res in. Resin is any of a class of solid or semi-solid organic prod-
ucts of natural or syntnetic origin, generally of high molecular
weight with no definite melting point. Most resins are polymers.
Solvents. Solvents are needed in most adhesives to disperse the
binder to a spreadable liquid form. In most wood-and-paper bonding
adhesives the solvent is water. In many adhesives based on synthetic
resins, rubbers, and even natural gums, a variety of organic solvents
are required to achieve the necessary solubility and to provide some
minimum percentage of base solids.
Thinners or Dilvents. Thinners or dilvents are volatile liquids
added to an adhesive to modify the consistency or other properties.
TKN (Total Kjeldahl Nitrogen). Includes ammonia and organic nitrogen
but does not include nitrite and nitrate nitrogen.
XVI-15
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DRAFT
E. Explosives Industry
Aluminum. Metal used to increase the energy of a propellant and
explos ive.
Bagasse. Plant residue used to bind explosives.
Ba11 Powder. Small arms powder made by emulsifying a mixture of
propellant and solvent in a liquid in which they are not soluble.
Evaporation of the emulsifying liquid and the solvent yields quite
uniform round balls of powder.
B i nder. In composition propellent, the solid matrix in which the
granular ingredients are held.
Booster Charge. A charge igniter that is ignited by the electric
match and, in turn, initiates combustion or detonation in the pro-
pel lant.
Deterrent. A propellant additive that reduces the burning rate.
DNT. Dinitrotoluene. Added as a deterrent to propellant grains;
reduces burning rate.
Double Base. A propellant which is made from two explosive sub-
stances, e.g., nitrocellulose, gelatinized with nitroglycerin.
Electric Hatch. A bead of easily-ignited explosives formed on a
thin wire used as an igniter.
Exp1os i ves. A substance mixture capable of rapid conversion into
more stable products, with the liberation of heat and usually the
formation of gases.
Extruded Propellant. Any propellant made by pressing solvent soft-
ened or gelatinized nitrocellulose through a dye to form grains.
Grains. A single piece of formed propellant, regardless of size.
"Green". Describes a batch of cotton that was not given enough time
to fully nitrate, or a cost grain not yet fully cured.
Inh i b i tor. A coating on a propellant grain which prevents burning
at that point.
XVI-16
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DRAFT
Metal Modifiers. Metals used in explosives or propellants to modify
their property, i.e. aluminum increases the energy of an explosion.
NC Fines. Fine nitrocellulose particles as a result of the purifi-
cation of nitrocellulose.
Pink Water. After loading TNT into munitions, the loading bays are
washed. TNT particles in concentrations of 100-150 mg/L produce in
sunlight an orange or light-rust colored effluent termed "pink water",
P r i me r. A small charge of easily-ignited material used to ignite
the working charge of a gun or rocket.
Propellant. Any substance which can react to form more stable sub-
stances in the absence of atmospheric oxygen, giving off hot com-
bustion gases capable of doing useful work.
Red Water. The effluent coming from the sellite wash of crude TNT.
Sellite has a selective affinity for the unsymmetrical, unwanted
isomers of TNT. The result is a blood red effluent high in sulfate
concentrat ion.
Se11i te. Sodium sulfite, used in the finishing operation of TNT.
S ingle Base. A propellant which contains only one explosive in-
gredient.
Smokeless Powder. Nitrocellulose base propellant.
Solvent. As used in propellents either: (1) a substance added to
nitrocellulose to soften it so that it can be formed; or (2) a sub-
stance that dissolves both propellant and inhibiting materials and
is used to bond inhibitors to grain.
Stab i1i zer. A substance added to nitrocellulose propellants to pre-
vent decomposition product from catalyzing further decomposition.
Triple Base. A propellant that contains three explosives bases,
e.g., NC-NG-nitroguanidine small-arms powder.
Yellow Water. The effluent coming from the first wash of crude TNT
in its purification process.
XV I-17
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DRAFT
F. Carbon Black Industry
Blowdown. Water intentionally discharged from a cooling or heating
system to maintain the dissolved solids concentration of the circu-
lating water below a specific critical level.
Carbon Black. A family of industrial carbons used principally as
reinforcing agents in rubber and as black pigments in inks, coatings
and plastics.
Channel Black. Carbon black manufactured by the channel process.
It is produced by the incomplete combustion of natural gas, and is
deposited, then scraped off, a moving channel.
Colloidal. A solid, liquid, or gaseous substance made up of very
small, insoluble, nondiffusible particles (as single large molecules
or masses of smaller molecules) that remain in suspension in a
surrounding solid, liquid, or gaseous medium; of matter consisting
of such a substance dispersed in a surrounding medium. All living
matter contains colloidal material, and a colloid has only a negli-
gible effect on the freezing point, or vapor tension of the surround-
ing medium.
Furnace Black. Carbon black manufactured by the furnace process;
produced by partial combustion of hydrocarbons in insulated furnaces.
Impingement. To strike with a sharp collision.
Lamp Black. Carbon black manufactured by the burning of petroleum
or coal tar residues in open shallow pans.
Quas igraph it ic. Having graphite-1ike qualities.
Thermal Black. Carbon black manufactured by the thermal process;
produced by thermal decomposition (cracking) of natural gas.
XVI-18
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DRAFT
G. Photographic Processing Industry
Bleach i ng. A step in color film processing thereby the silver image
which is formed with the dye image is converted back to silver halide
by reactions with ferricyanide and sodium bromide or ferric EDTA.
Couplers. A group of organic chemicals which react with the oxidized
components of the developers to form color dyes. They are either
evaporated in the film emulsion at the time of manufacture (e.g. Ekta-
chrome film) or they are included in the color developing solution
(e.g. Kodachrome film).
Development. A step in photoprocessing whereby the latent image
is made visible in a developer solution.
"Dip and Dunk". An automatic processing machine whereby strips of
film are "dipped" into successive photoprocessing tanks and held
for development.
Dye Image. A color image formed when the oxidized developer combines
with the color couplers.
Fix. A step in photoprocessing whereby the unexposed and undeveloped
silver must be removed from the emulsion. Common among the solvent
fixers are sodium thiosulfate.
Incorporated Couplers. Common to color reversal films, whereby the
couplers are included in the film at the time of manufacture.
Negative Film Development. A two-step process whereby following the
negative development a controlled exposure of light is directed onto
paper through the negative creating a negative of a negative, or a
positive image on paper.
"Rack and Tank". See "Dip and Dunk".
Reversal Development. A method of obtaining a positive image on the
same film used for the original exposure.
Short Stop. A step in photoprocessing which follows development
whereby the basic activators in the developer are neutralized to
prevent further development.
5 i1ver Halide. Usually silver bromide, which upon exposure to light
converts to metallic silver, forming a latent image.
Three Layers. Common to color film which has three separate layers,
including red, blue and green sensitive layers.
XVI-19
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DRAFT
H. Hospi taIs
Amalgam. Any alloy of mercury with another metal or other metals.
Silver amalgam is used as a dental filling.
Cathart ic. A medicine for stimulating evacuation of the bowels.
Catheter. A slender tube inserted into the body passage, vessel or
cavity for passing fluids, making examinations, etc.
Developer. A chemical used to produce a picture from an exposed
film, plate or printing paper.
Diagnostic Services. The processing or deciding the nature of a
diseased condition by examination of the symptoms.
D i uret i c. A drug used to increase the secretion and flow of urine.
Fixer Solution. A chemical used to render photographic emulsions
insensitive to light.
Geriatric Hospital. A facility that specializes in the treatment of
diseases of old age.
"Hypo". A synonym for fixer solution.
Orthopedic Hospital. A facility that specializes in the treatment
of deformities, diseases, and injuries of the bones, joints, muscles,
etc.
Pathological Wastes. Waste material that is potentially infected.
Rad iograph. A picture produced on a sensitized film or plate by
X-rays.
Tissue Fixative. A chemical used to preserve tissue material for
subsequent examination.
XVI-20
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DRAFT
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U.S. ENVIRONMENTAL PROJECTION AGENCY (A-107)
WASHINGTON, D.C. 20460
POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
EPA-335
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