DRAFT
                        FOR
MISCELLANEOUS CHEMICALS INDUSTRY
           f 4T*  \
           "W
 D^IRDWEKTAL PRJ1ECTION AGENCY
          FEBRUARY 1975
              DRAFT

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                          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

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                                                                   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

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                                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 Cซ

 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

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                                          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*ป
              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*ป                    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

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                             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

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                             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

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                             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

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                             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

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                             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

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                             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

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                             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 Aฃ

VIIIE-5       Wastewater Treatment Costs for BPCTCA, BADCT and      VIM-102
              BATEA Effluent Limitations (ENR 1780 - August,
              1972 Costs)
              Explosive Industry
              Subcategory B
                                  xxv

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                             LIST OF TABLES
                              (continued)

Table                       .     Title                              Page
                                                                                    ซ
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

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                              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

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                             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

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                                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 ฃ- 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.

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 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

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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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AND FURTHER INTERNAL REVIEW BV EPA.

-------
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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HOT ICE •   THESE AM TENTATIVE DECONHCNOATIIINS IASED UPON  INFORMATION
IN THIS  ซEPORT AND AW SUBJECT TO CHANCE BASED UPON COHMENTS KECEIVEO
AND FURTHER INTERNAL REVIEW IV EPA.

                         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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                                    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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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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HOTICC;  THtSt AW TINTATIVt MCOMMINMTIONS MS(D WON  INfOIIMTION
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



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        NOT|CE:   THESE  ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION

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-------
                                      FIGURE IIA-2

                             CATEGORY A - BATEA EFFLUENT

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                    THESE ARE TENTATIVE RECOMMENDATIONS BASED UPON INFORMATION
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                                          H-5

-------
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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.
                                          II-6

-------
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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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IN THIS REPORT  AND ARE SUBJECT TO  CHANGE BASED UPON COMMENTS RECEIVED
AND FURTHER  INTERNAL REVIEW BY EPA.
                                   11-11

-------
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                                                 11-12

-------
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                                                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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                                       11-15

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                                          11-16

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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               ฃ
     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

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                                     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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                                                  11-23

-------
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  IN THIS  REPORT  /NO  ARE SUBJECT TO  CHANGE BASED UPON COMMENTS  RECEIVED
  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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       IN  THIS  REPORT AND  ARE  SUBJECT TO  CHANGE  BASED UPON COMMENTS  RECEIVED
       AND FURTHER  INTERNAL REVIEW BY EPA.
                                                  11-27

-------
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                                               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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                                                  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

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 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

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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

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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

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     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

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                                    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

-------
   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

-------
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

-------
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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

-------
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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_Oฃenated_ AJJphat_iฃ Hyd_rฃca_rb_oฃs

                                   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

                 ฃ^ho_sฃha_te_s_and_Phpsphpn_ates_
                        R0
    Dichlovos, Dicrotophos,  Ciodrin*,  Trichlorfon,  Ethephon,  Gardona*,
    Mevinphos, Naled, Nia 10637,  TEPP,  Phosphamidon

               P_hosp_ho_rothM oates  and_ Phosฃhonothjoat_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)

                                       Cpmpฃimdฃ
                              (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        ฃ   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: sulฃur)

                              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
\  ป*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
    Scaldป, 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

-------
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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

 *ซ5                                                     +             +
 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

-------
                                                               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-Jป3

-------
                                                               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 *ป5 percent of this total
capacity was in Texas, 3^ป 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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             FURNACE
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             THERMAL
             TOTAL
 1952         1956         1960          1964          1968


                                  YEAR
                                                                        1972

-------
                                                                      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

-------
                                                             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

-------
                                                               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

-------
                                                                  DRAFT
                               SECTION IV

                         INDUSTRIAL CATEGORIZATION


The  goal  of  this  study la  the mflrit  of  nflliiซfH  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

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                                                               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

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                                                              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.

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                                                              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

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                                                              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

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                                                                     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

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                                                               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

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                                                              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 Gฃ:  $ub-
cateory Gฃ 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

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                                                               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

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                                                               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

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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
                              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
 I I +  I II-W      II
I  I I

I  I 1-2-3

111-3



IV-1
           globulins and some
           6  globulins
I I 1-1       isoagglutinins

I I 1-2       prothrombin  (thrombin)
    Demonstrated Users
                                                      treatment of  hemophilia
immune globulins against
measles and infectious
hepatitis; other anti-
bodies

blood grouping

blood coagulation;  hemo
VI
           (fibrinogen,  which  yields    in  neurosurgery
            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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                                              IV-17

-------
                                                              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 10ฐF 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
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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TYPICAL CHEMICAL SYNTHESIS PROCESS




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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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 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

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                                                              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

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                                                               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

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                           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

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                                                                   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

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                            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
      ฃ100 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

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                                                                              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

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                                                                   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 270ฐC,  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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          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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                                                                  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

-------
                                                          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.
                              IV-63

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                                                          DRAFT
 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.

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 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 155ฐC, liberating
hydrogen chloride.
                            IV-68

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                                                          DRAFT
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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                                                          DRAFT
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

-------
                                                          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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                                                          DRAFT
               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
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
               Scrubber water from the air pollution
                   control equipment used in formulation
                   areas
               Production area washdowns
               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).
                              1V-89

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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

-------
                                       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

-------
                                                          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 |Mปi
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.

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                                                          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.

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                                                                   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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                                                                      DRAFT
                              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 ซmd  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 proeซ>*&(!"ป, 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

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                                                                DRAFT
 an  indication  of the complex  changes  that  take  place,  proceeding  from
quite  variable raw materials  to  almost  as variable products.

     C102H11*9ฐ38N31   +  H2ฐ    '•ซ         C102H151ฐ39N31
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-*ป.  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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-------
                        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

-------
                                                                   DRAFT
                           FIGURE IVD-4

                    FORMALDEHYDE-RESIN BATCH
                MANUFACTURING PROCESS FLOW CHART
   RAW
   MATERIAL
   STORAGE
   TANK
WEIGH
TANK.
                                                    RAW MATERIAL
                                                    STORAGE TANKS
                        1
                      STEAM-
                      JACKETED
                      PROCESS
                      VESSEL
                                        VACUUM PUMP



                      COOLING
                      TANK
                                                              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

-------
                                                               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

-------
                                                                   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

-------
                                                               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

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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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                                         IV-127

-------
                                                               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
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                           DIGESTOR
                          FILTER
                          I
                         H2O
                                                        PETN
                                                         DISSOLVER
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                                                        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
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  DISSOLVING
    TANKS
             CHALK

             • ACETONE
                                  SEPARATION
                                     TANK

PRECIPITATION
TANK
r
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RECOVERY




                  WASTE
                                    FILTER
                                                 HNM WASH
                  HNM OR
                  ISOSORBIDE
                  DINITRATE

-------
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-------
                                                                   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

-------
                                                                   DRAFT
 The  raw material used  In the manufacture of thermal blat.k I 
-------
                                                                   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

-------
                                                                   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

-------
                                                                   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  *+00ฐF.   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
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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                                                                    DRAFT
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
-ป.
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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-------
                                                                     DRAFT
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 hซHs 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

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                                                                 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

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                               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  iซ   .'   'i 'ic' .er  . pie !ป••  •,  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'ปt
 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 vvasLevปater  qen • t o
 c!u:"'.';tj  v.icc'n*. product;.1!") a re  spent rnecia  hroth,  spent eqr:->,  ซ| 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  ซ. 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' lฃ^ 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
<ง""]"" 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_Mซ
  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

<ฃ
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
ง
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-
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                                                                          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-ป  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
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-------
                                                  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
Subcปtปgory 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*tซgory 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
0.5
0.03
0.10
0.006
—
—
2.2
0.14
Subcategory F -
Rosin
Derivatives
319
51
0.016
7,270
2.32
357
0.11
815
0.26
--
13.1
0.004
13.00
0.006
0.06
0.00002
0.7
0.00021
--
12.8
0.004
59.8
0.019
40.8
0.0130
8.84
0.0028
--
6.67
0.0021
17.2
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

-------
                                                                                                               DRAFT
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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 chซanincj 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
<ป5
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 - - - - - -
5ฃ00 - - - - -
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
Mป,
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

-------
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-------
                                           Table VC-10

                                         Raw Waste Loads
                                    Formulators and Packagers
                                         (Subcategory E)
  Plant1



    69


Literature^


Literature5ซฐ
        Flow2ป3
       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.  Neeซuise wrt**tevป 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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-------
                                                                    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

-------
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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

-------
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^ulx.itซ'<|ury Al - lM'l"*ivi M.inuUi. turr
',1

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01
0','
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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 'dซy
(i.ปl'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*ฐ)

unavailable




UMf VI • ?
Fxplmlve Industry
ow
L/kkq product
(oal/t ,000 prod) BOOt,

3,190
(3ซ2) ฐ-"'
tซ
(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
'•I9ฐ ,.*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**
<ฃ:ฃ>
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 (kซ/kปci 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 "ซ"-•
.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

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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






rปgr 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)
ซHO
(06)
(07)
Raw Waste Load
1*7
ซ
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
ซ
50
NHN & 150
LHR
PETN I DIAZO
Twin Cities
Uki- Clt lpซ
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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                                                             V-71

-------
                                                                                                                         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

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                                                                                                    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

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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

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                                                               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

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                                                                                                                            DRAFT
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                                                                            V-8A

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                                                                   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.
                                    VI-1

-------
                                                     DRAFT
            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
                 VI-2

-------
                                                                   DRAFT
         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:
                                     VI-3

-------
                                                                   DRAFT
     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.
                                    VI -

-------
                                                                   DRAFT
 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 20ฐC,
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 20ฐC 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
                                   VI-5

-------
                                                                   DRAFT
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
                                    VI-6

-------
                                                                   DRAFT
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 150ฐC.  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 950ฐC,  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.
                                   VI-7

-------
                                                                   DRAFT
      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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                                                                   DRAFT
 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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                                                                  DRAFT
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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                                                                  DRAFT
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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                                                                  DRAFT
           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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                                                                  DRAFT
 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.
                                                      ป
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.
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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 -
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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  (86ฐF).  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 90ฐF.  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.
                            VI-27

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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.
                             VI-29

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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.
                             VI-30

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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)ฃ  , 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

-------
                                                               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 ป
                                                             COOLING  WATER
FOR 10-MILLION-BTU/HR DUTY,
COOLING WATER AT  85ฐ,
OUTLET TEMPERATURE  AT 125ฐ
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

-------
                                                              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 Nฃ 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

-------
                                                              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.

*ป.  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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                                                              DRAFT
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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-------
                                                          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"     ฐ" 2


These valves are based on 1.^2 Ibs COD,   0.53 1 bs TOC,    . „__   _ 0 __-
                          	    —ib~vss—  and vss = ฐ-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, 2lป-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*ป 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

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                                                              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

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                                                                    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

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                                                                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

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                                                           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