United States Effluent Guidelines Division EPA 440/1-83/400
Environmental Protection WH-552 October 1983
Agency Washington DC 20460
Water
Summary
of Available Information
on the Levels and Control
of Toxic Pollutants Discharges
in the
Printing and Publishing
Point Source Category
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SUMMARY OF AVAILABLE INFORMATION ON THE
LEVELS AND CONTROL OF TOXIC POLLUTANT DISCHARGES
IN THE PRINTING AND PUBLISHING
POINT SOURCE CATEGORY
Rebecca W. Hanmer
Acting Assistant Administrator
Office of Water
Jeffery D. Denit
Director, Effluent Guidelines Division
Gregory N. Aveni
Project Officer
September 1983
Effluent Guidelines Division
Office of Water
U.S. Environmental Protection Agency
Washington, D.C. 20460
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago, !L 60604-3590
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ABSTRACT
This document presents the findings of a study of the printing
and publishing point source category conducted in fulfillment of
the requirements of the Settlement Agreement in Natural Resources
Defense Council, Inc. v. Train, 8 ERC 2120 (D.D.C. 1976),
modified, 12 ERC 1833 (D.D.C. 1979).
The information presented in this document supports the
determination that uniform national effluent limitations
reflecting the best available technology economically achievable
(BAT), new source performance standards (NSPS), and pretreatment
standards for new and existing sources (PSNS and PSES) are not
appropriate for six subcategories of the printing and publishing
point source category pursuant to the provisions of Paragraph 8
(a)(iv) of the Settlement Agreement. This report summarizes data
gathering efforts, industry subcategorization, water usage
information, toxic pollutant discharge data, and control and
treatment technologies employed in the printing and publishing
industry.
111
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TABLE OF CONTENTS
SECTION TITLE
I CONCLUSIONS
SUBCATEGORIZATION 1
PARAGRAPH EIGHT DECISION 1
II INTRODUCTION 3
PURPOSE AND AUTHORITY 3
STANDARD INDUSTRIAL CLASSIFICATION 4
PREVIOUS STUDIES 4
PARAMETERS INVESTIGATED IN THIS STUDY 5
SUMMARY OF METHODOLOGY 5
Introduction 5
Literature and Other Sources of Infor-
mation 1 1
Data Request Survey 11
Plant Visitation and Sampling Program 12
Subcategorization 14
Identification of Control and Treatment
Technology 14
Analysis of Treatment Alternatives, Cost,
and Energy Data 14
III DESCRIPTION OF THE INDUSTRY 15
INTRODUCTION 15
PROCESS DESCRIPTIONS 15
Introduction 15
Art and Copy Preparation and Composition 18
Photoprocessing 18
Platemaking 21
Printing 30
Finishing and Binding 33
INDUSTRY PROFILE 34
General 34
Geographic Distribution 39
Process Operations Statistics 39
Plant Age 39
Plant Size 39
Waste Generation and Disposal 39
IV SUBCATEGORIZATION 53
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TABLE OF CONTENTS
SECTION TITLE PAGE
V WASTEWATER CHARACTERISTICS 57
INTRODUCTION 57
GENERAL CHARACTERISTICS 57
PHOTOGRAPHIC PROCESSING WASTEWATER 58
PLATEMAKING WASTEWATER 58
PRINTING WASTEWATER 59
Lithographic Fountain Solutions 59
Press Cleanup 59
OTHER WASTEWATERS 60
RAW WASTEWATER DATA 61
Screening and Verification Sampling Data 61
Historical Data 62
VI CONTROL AND TREATMENT TECHNOLOGY 77
INTRODUCTION 77
SUMMARY OF AVAILABLE DATA 77
General 77
Plant 5478 84
Plant 8190 85
Plants 6653 and 9012 86
Plant 5430 86
VII BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE (BAT), NEW SOURCE PERFORMANCE
STANDARDS (NSPS), AND PRETREATMENT
STANDARDS FOR NEW AND EXISTING SOURCES
(PSNS AND PSES) 95
INTRODUCTION 95
ART AND COPY PREPARATION AND COMPOSITION
SUBCATEGORY 95
Decision Not to Establish National
Regulations 95
PHOTOPROCESSING AND NONMETALLIC PLATEMAKING
SUBCATEGORIES 96
Decision Not to Establish National
Regulations 96
Data Evaluation 96
Photoprocessing Subcategory Plant Profile 96
Nonmetallic Platemaking Subcategory
Plant Profile 96
VI
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SECTION
VIII
IX
APPENDIX
TABLE OF CONTENTS
TITLE PAGE
PRESSROOM (NONWATER-BASED INKS) SUBCATEGORY 98
Decision Not to Establish National
Regulations 98
Data Evaluation 98
Pressroom (Nonwater-Based Inks) Sub-
category Plant Profile 98
PRESSROOM (WATER-BASED INKS) SUBCATEGORY 98
Decision Not to Establish National
Regulations 98
Data Evaluation 100
Pressroom (Water-Based Inks) Subcategory
Plant Profile 100
FINISHING AND BINDING OPERATIONS SUBCATEGORY 100
Decision Not to Establish National
Regulations 100
ACKNOWLEDGEMENTS 103
REFERENCES 105
REFERENCES CITED IN TEXT 105
ADDITIONAL REFERENCES 106
GLOSSARY 119
HISTORICAL RAW WASTEWATER DATA 123
HISTORICAL DATA FROM PLANTS VISITED AND/OR
SAMPLED 123
Plant 5247 123
Plant 9010 123
Plant 8301 124
HISTORICAL DATA FROM PLANTS NOT VISITED
AND/OR SAMPLED 124
VII
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NUMBER
SECTION II
II-l
SECTION III
III-l
III-2
III-3
III-4
III-5
III-6
III-7
III-8
III-9
111-10
LIST OF TABLES
TITLE PAGE
Toxic Pollutants Investigated in
EPA Studies of the 21 Major
Industries
Specific SIC Codes Investigated in
EPA's Study of the Printing and
Publishing Industry 16
Estimated Number of Establishments
with Primary Operations in SIC Major
Group 27 35
Status of Establishments with Primary
Operations in SIC Major Group 27 36
Geographical Distribution of U.S.
Printing and Publishing Plants 41
Estimated Number of Plants Employing
Eight Printing Process Operations 43
Wastewater Flows Reported by Data
Request Survey Respondents 44
Number of Direct Dischargers with
NPDES Permits or Applications on File
in 1977 45
Selected Data Request Survey Information
for Direct Dischargers 46
Summary of Industry Discharge Status 50
Toxic Pollutants Present in Raw Materials
Used in Printing and Publishing
Manufacturing Processes 51
IX
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NUMBER
SECTION V
V-l
V-2
V-3
V-4
V-5
V-6
V-7
V-8
V-9
SECTION VI
VI-1
VI-2
VI-3
LIST OF TABLES
TITLE PAGE
Printing Plants Sampled in Screening and
Verification Program 63
Number of Toxic Pollutants Detected in
Screening and Verification Program 64
Available Screening
Sampling Raw Waste
Data - Photoprocessing Subcategory
Operations at Plant 4975 65
Screening Sampling Raw Waste Data -
Photoprocessing Subcategory Operations
at Plant 6372 66
Sampling Site Descriptions for Plants
in the Photoprocessing and Nonmetallic
Platemaking Subcategories 67
Toxic Pollutant Screening Sampling
Raw Waste Data - Combined Photoprocessing
and Nonmetallic Platemaking Subcategories 68
Toxic Pollutant Screening Sampling Raw
Waste Data - Pressroom (Nonwater - Based
Inks) Subcategory 71
Toxic Pollutant Raw Waste Data - Pressroom
(Water-Based Inks) Subcategory 74
Verification Sampling Conventional and
Nonconventional Pollutant Raw Waste Data
Pressroom (Water-Based Inks) Subcategory 76
Summary of Plants with Treatment Systems
Sampled 78
Toxic Pollutant Removal in Batch Metals
Treatment System at Plant 5478 81
Toxic Pollutant Removal in Biological
Treatment System at Plant 5478 82
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NUMBER
VI-4
VI-5
VI-6
VI-7
VI-8
SECTION VII
VII-1
VII-2
VII-3
APPENDIX
A-l
A-2
A-3
A-4
A-5
LIST OF TABLES
TITLE PAGE
Conventional and Nonconventional
Pollutant Removal in Biological
Treatment System at Plant 5478 83
Reduction of Toxic, Conventional, and
Nonconventional Pollutants in Physical/
Chemical Treatment System at Plant 8190 89
Reduction of Toxic Pollutants in
Limestone Filter at Plant 6653 90
Reduction of Toxic Pollutants in Limestone
Filter at Plant 9012 91
Reduction of Toxic Pollutants in Metals
Treatment System at Plant 5430 93
Toxic Pollutant Raw Waste Loads From
Photoprocessing and Nonmetallic
Platemaking Operations 97
Toxic Pollutant Raw Waste Loads
From Pressroom (Nonwater-Based Inks)
Operations 99
Toxic Pollutant Raw Waste Loads From
Pressroom (Water-Based Inks) Operations 101
Historical Raw Wastewater Data for
Plant 8190 125
Historical Raw Wastewater Data for
Plant 5430 126
Historical Raw Wastewater Data for
Plant 5247 127
Historical Raw Wastewater Data for
Plant 9010 128
Historical Raw Wastewater Data for 129
Plant 8301
XI
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LIST OF TABLES
NUMBER TITLE PAGE
A-6 Historical Raw Wastewater Characteristics
From Plants not Visited or Sampled -
Lithographic Printing Operations
(Conventional and Nonconventional
Pollutants) 130
A-7 Historical Raw Wastewater Characteristics
From Plants not Visited or Sampled -
Lithographic Printing Operations
(Metals and Cyanide) 133
A-8 Historical Raw Wastewater Characteristics
From Plants not Visited or Sampled -
Letterpress Operations 134
A-9 Historical Raw Wastewater Characteristics
From Plants not Visited or Sampled -
Letterpress and Lithographic Printing
Operations (Conventional and Nonconventional
Pollutants) 136
A-10 Historical Raw Wastewater Characteristics
From Plants not Visited or Sampled -
Letterpress and Lithographic Printing
Operations (Metals and Cyanide) 141
xn
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NUMBER
SECTION III
III-l
SECTION VI
VI-1
VI-2
VI-3
VI-4
LIST OF FIGURES
TITLE PAGE
General Manufacturing Steps
for Printing Processes which
Involve Photomechanical
Platemaking 17
Metals Treatment System at
Plant 5478 79
Biological Treatment System at
Plant 5478 80
Physical/Chemical Treatment System
at Plant 8190 88
Metals Treatment System at Plant 5430 92
Xlll
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SECTION I
CONCLUSIONS
SUBCATEGORIZATION
In order to determine whether uniform national effluent
regulations were appropriate for the printing and publishing
point source category, it was necessary to subcategorize the
industry. The Agency established the following preliminary
subcategorization scheme based on production processes used in
the printing and publishing industry:
Art and Copy Preparation and Composition
Photoprocessing (printing and/or publishing facilities
engaged in internal photoprocessing operations)
Nonmetallic Platemaking
Pressroom (Nonwater-Based Inks)
Pressroom (Water-Based Inks)
Finishing and Binding Operations
Metallic Platemaking (now studied as part of metal finishing
point source category)
Gravure Cylinder Preparation (now studied as part of metal
finishing point source category)
As discussed below, the Agency has decided not to promulgate
uniform national regulations for six subcategories of the
printing and publishing point source category. If the toxic
pollutant raw waste load data gathered by the Agency had shown
that regulations were warranted, it is possible that this
subcategorization scheme may have been revised to account for
such fcictors as cost of treatment, size and age of facilities, or
economic impact.
PARAGRAPH EIGHT DECISION
The Agency has excluded six subcategories of the printing and
publishing point source category from national effluent
regulations pursuant to the provisions of Paragraph 8 (a)(iv) of
the Settlement Agreement in Natural Resources Defense Council,
Inc. v. Train 8 ERC 2120 (D.D.C. 1976), modified, 12 ERC 1833
C. 1979). (1)(2)
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Art and copy preparation and composition operations do not
involve the use of water and finishing and binding operations are
essentially dry processes. Because these two subcategories are
dry or result in the discharge of very small quantities of toxic
wastewater pollutants, they have been excluded from national
regulations under the authority of paragraph 8(a) (iv) of the
Settlement Agreement.
Discharge of heavy metals and other toxic pollutants may occur
from plants in the photoprocessing, nonmetallic platemaking,
pressroom (nonwater-based inks), and pressroom (water-based inks)
subcategories. The median discharge volume from individual
facilities is between 26 and 50 gallons per day. Even for large
plants of which there are few in these subcategories, the total
raw wastewater discharge contains less than 1.2 pounds of toxic
pollutants per day per plant. Based on EPA's review of all
available data, the Agency has excluded these four subcategories
from national regulations because the amount and toxicity of the
pollutants contained in the raw wastewater discharges do not
justify developing national regulations.
The information and data gathered to date regarding the gravure
cylinder preparation and metallic platemaking subcategories were
not sufficient to make regulatory decisions; however, the data do
show that further study of these subcategories is warranted and
that these operations are similar to certain metal finishing
processes. Therefore, gravure cylinder preparation and metallic
platemaking will be further studied in the second phase of the
rulemaking effort for the metal finishing point source category.
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SECTION II
INTRODUCTION
PURPOSE AND AUTHORITY
The Federal Water Pollution Control Act Amendments of 1972 (P.L.
92-500; the Act) established a comprehensive program to "restore
and maintain the chemical, physical, and biological integrity of
the Nation's waters" (see Section 101(a)). By July 1, 1977,
existing industrial dischargers were required to achieve
"effluent limitations requiring the application of the best
practicable control technology currently available" (BPT) (see
Section 301(b)(1)(A)). By July 1, 1983, these dischargers were
required to achieve "effluent limitations requiring the
application of the best available technology economically
achievable (BAT), which will result in reasonable further
progress toward the national goal of eliminating the discharge of
pollutants" (see Section 301(b)(2)(A)). New industrial direct
dischargers were required to comply with new source performance
standards (NSPS), established under authority of Section 306,
based on best available demonstrated technology. New and
existing dischargers to publicly owned treatment works were
subject to pretreatment standards under Sections 307(b) and (c)
of the Act. While the requirements for direct dischargers were
to be incorporated into National Pollutant Discharge Elimination
System (NPDES) permits issued under Section 402 of the Act,
pretreatment standards were made enforceable directly against
dischargers to publicly owned treatment works (indirect
dischargers).
Although Section 402(a)(l) of the 1972 Act authorized the setting
of requirements for direct dischargers on a case-by-case basis in
the absence of regulations, Congress intended that, for the most
part, control requirements would be based on regulations
promulgated by the Administrator of the United States
Environmental Protection Agency (EPA). Section 304(b) of the Act
requires the Administrator to promulgate regulations providing
guidelines for effluent limitations setting forth the degree of
effluent reduction attainable through the application of BPT and
BAT. Moreover, Sections 304(c) and 306 of the Act require
promulgation of regulations for NSPS, and Sections 304(f),
307(b), and 307(c) require promulgation of regulations for
pretreatment standards. In addition to these regulations for
designated industry categories, Section 307(a) of the Act
requires the Administrator to promulgate effluent standards
applicable to all dischargers of toxic pollutants. Finally,
Section 501(a) of the Act authorizes the Administrator to
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prescribe any additional regulations "necessary to carry out his
functions" under the Act. '
The Agency was unable to promulgate many of these toxic pollutant
regulations and guidelines within the time periods stated in the
Act. In 1976, EPA was sued by several environmental groups and,
in a settlement of this lawsuit, EPA and the plaintiffs executed, a
"Settlement Agreement", whicti was approved by the Co.urt. Ttiis
Agreement required EPA to develop a program and adhere to a
schedule for promulgating,' for 21 major industries, BAT .effluent
limitations guidelines, prefcreatment standards^ and new source
performance standards for 6/5' * tOxic : pollutants ?and classes" . of
toxic pollutants [see Natural Resources Defense Councilj' ind. v.
Train/ 8' ERC 2 1 iO ( D . D . C. 1:976), modified, 1 2 EEC iHI 'TD?D . G .
rl979)]:M;T)t2) : ' . -;. ,' ' ~1 a. , V -: ;; '"
On December, 27, H977, tile" President signed into law :t:he Clean
'Water Act 0f: 1 977 (P.L. 95-^.217)'. .Although '.this .laV make^ "seviral
.important changes irt "the federal water pollution Coritrcjl ^tdgram,
its most significant feature is its incorporation into tJhe^Ct/ of
mariy of the basic ' elements 6f the Settlement Agreement prqgirkm
for 'toxic • pollution , qqtttrol. Sections 36j (b) (2) ( A) 4nd
3Q1 (b)'f2) (C>"of th;e Act ,n6wrrequire the achievement : by; July 1,
1984, of effluent limitations, requiring application of\.BAT for
''toxic" pollutants, including: th'e '65 "priority", pollutants and
;cl4sses Of pollutants whi;ch Congress declared "toxic"\under
"^ecti'on 307(a) of the Act. ^Likewise, E?Ar:s programs 'for' _ new
^source performance standards and pr^treatment staridards ar^'now
;dl:rdcted principally aft tpx'ic pollutant 'controls'! ,tl !,: ;.
STANDARD INDUSTRIAL CLASSIFICATION J i? ' ;
Thi ptinting and publishing [industry is in •"Staridaird Iridustrial
'Classification (SIC) l^ajor Gr!oiip 27, ;andl is : 'coiner iSed ;0f
Establishments ferigagid irt printing by orte or m6ifef<5f ^t;he "Common
'p^^esses/ such ; as J letterpress, ^f lexog^r^phy," ' lithography,
Vgravqre, .or sgreen, and,' thos^".,estaBi is^tnents, ^here seryictes.; T such
'as bqqkbinding, '. typ^Settifl^, engraVirt^ phc?toengrtavisngj and
;:electrqtypfrtg are~, :*perf6rm^ ^o't ; the .pVfntincjr trade. (3)^;:Also
inc|u4^- ^^ establishments 'eng^e.d in 'publishfng heyfspap^s,
cbooks; af}d :p"eriodi^ilSj °re^|irdless q^rwhlther they' dlo their5 ;o|m
':''; c "' r " ' "'•' •"-'•'- '" •'-'••".-" *--
PREVt OUS STUDJES
conseqllence:, had not'assessed industry practices' Or* treatment
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system performance, and had>made, no attempt to subcategorize the
industry. Published studies included only an abbreviated report
on waste cha,rac[te|rA-f^i,on,.,-pr,e|?firer«,.,.^'nMany^ ga<^f!?o!f\!Pupub^ic or
private agency had done so, jEl*A "and ' "i,t^ ,^'^p^at.Qrie^r' and
consultants had to develop analytical methods for toxic pollutant
detection and measurement. EPA then gathered, te^cj^igajl;&ata
about the industry and proceeded to ,^y^uat^ 74hj& ;hee4 for
regulations. . ,!, ,i, ,,,,,!._'
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TABLE II-l
TOXIC POLLUTANTS INVESTIGATED IN EPA STUDIES
OF THE 21 MAJOR INDUSTRIES
COMPOUND NAME
1. *acenaphthene
2. *acrolein
3. *acrylonitrile
4. *benzene
5. *benzidine
6. *carbon tetrachloride
(tetrachloromethane)
*CHLORINATED BENZENES (other than dichlorobenzenes)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
*CHLORINATED ETHANES
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. chloroethane
*CHLOROALKYL ETHERS
17. bis(chloromethyl) ether
18. bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
*CHLORINATED NAPHTHALENE
20. 2-chloronaphthalene
*CHLORINATED PHENOLS (other than those listed
elsewhere; includes chlorinated cresols)
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
23 *chloroform (trichloromethane)
24. *2-chlorophenol
*DICHLOROBENZENES
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
* Specific compounds and chemical classes as listed in the consent
degree.
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TABLE II-l
TOXIC POLLUTAKTS INVESTIGATED IN EPA STUDIES
OF THE 21 MAJOR INDUSTRIES
(Continued, Page 2 of 5)
COMPOUND NAME
*DICHLOROBENZIDINE
28. 3,3'-dichlorobenzidine
*DICHLOROETHYLENES
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. *2,4-dichloropheno1
*DICHLOROPROPANE AND DICHLOROPROPENE
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. *2,4-dimethylphenol
*DINITROTOLUENE
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. *1,2-diphenylhydrazine
38. *ethylbenzene
39. *fluoranthene
*HALOETHERS (other than those listed elsewhere)
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
*HALOMETHANES (other than those listed elsewhere)
44. methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. trichlorofluoromethane
* Specific compounds and chemical classes as listed in the consent
degree.
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"JH" TABLE II-l
^lC pqlttJTANTS INVJ^IPA'TED itt EtA STUDIES
; S 0; • •'» OF Tlffi 21 MAJOR^ INDUSTRIES
teontintied/p'age 3 of 5)
COMPOUND NAME
50. dichlorodif luoromethane
51. ch 1 or odibromom ethane
52. *hexachlorobutadiene
53. *hexachlorocyclopentadiene '
54. *isophorone
55. *naphthalene
56. *nitrobenzene ' '
*NITROPHENOLS '"* ;
57. 2-nitrophenol
58. 4-nitrophenol
59. *2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
*NITROSAMINES
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylatnine
64. V;pentachlorophenol
65. *phenol
*PHTHALATE ESTERS "" '• " :-'<.
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate •"•"•-
68. di-n-butyl phthalate ""
69. di-n-octyl phthalate
70. diethyl pttttiafaty ' v; "! "J' " ;
71. dimethyl phthalate"; * '""''
*POLYNUCLEAR AROMATIC HYDROCARBONS1
72. benzo( a)anthracene (1, 2-be"nzan;ttifa"6erie)
73. benzo(a)pyrene (3,4-benzopyrene)
"••: f A " .'- it' > i •
* Specific .compounds and chemical classes as listed in the consent
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TABLE II-l
TOXIC POLLUTANTS INVESTIGATED IN' EPA STUDIES
': OF THE 21 MAJOR INDUSTRIES
(Continued, Page 4 of 5)
COMPOUND NAME
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthene (11,12-benzofluoranthene)
76. chrysene
77. acenaphthlene
78. anthracene
79. benzo(ghi)perylene (l,12-benzoperylene)
80. fluorene
81. phenanthrene
82. dibenzo(a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene (2,3-o-phenylenepyrene)
84. pyrene
85. *tetrachloroethylene
86. *toluene
87. *trichloroethylene
88. *vinyl chloride (chloroethylene)
PESTICIDES AND METABOLITES
89. *aldrin
90. *dieldrin
91. *chlordane (technical mixture & metabolites)
*DDT AND METABOLITES
92. 4,4'-DDT
93. 4,4'-DDE (p,p'-DDX)
94. 4,4'-DDD (p,p'-TDE)
*ENDOSULFAN AND METABOLITES
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
*ENDRIN AND METABOLITES
98. endrin
99. endrin aldehyde
*Specific compounds and chemical classes as listed in the consent
degree.
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TABLE II-l
TOXIC POLLUTANTS INVESTIGATED IN EPA STUDIES
OF THE 21 MAJOR INDUSTRIES
(Continued, Page 5 of 5)
COMPOUND NAME
*HEPTACHLOR AND METABOLITES
100. heptachlor
101. heptachlor epoxide
*HEXACHLOROCYCLOHEXANE (all isomers)
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (lindane)-Garama
105. g-BHC-Delta
*POLYCHLORINATED BIPHENYLS (PCB's)
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. *toxaphene
114. *antimony (total)
115. *arsenic (total)
116. *asbestos (fibrous)
117. *beryllium (total)
118. *cadmium (total)
119. *chromium (total)
120. *copper (total)
121. *cyanide (total)
122. *lead (total)
123. *mercury (total)
124. *nickel (total)
125. *selenium (total)
126. *silver (total)
127. *thallium (total)
128. *zinc (total)
129. *2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
*Specific compounds and chemical classes as listed in the consent
degree.
10
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Information and data were collected in a three-step program, as
follows:
1. The potential for toxic pollutant use and discharge in
the printing industry was investigated in an extensive
literature review;
2. A data request survey was mailed to 6,995 plants (at
least ten percent of the estimated total number of
plants in the industry); and
3. Individual facilities were visited and sampled to
collect raw waste data and information on control and
treatment system performance.
This program resulted in the compilation of the industry profile
presented in Section III, the raw waste data presented in Section
V, and the control and treatment data presented in Section VI.
Literature and Other Sources of Information
Available literature was reviewed for information on raw material
usage and process chemistry, with particular emphasis on the
identification of toxic pollutants contained in raw materials or
produced during plant operations. The literature consisted of
published texts, trade association and chemical supplier manuals,
and information obtained by EPA in a study of the ink industry
and toxic pollutants contained in inks. Although comprehensive
data regarding most of the proprietary compounds used by the
printing industry were unavailable, production processes and
potential discharges of significance were identified in the
literature.
In addition to the literature review, pollutant information was
requested from the ten EPA regional offices and 12 state
environmental authorities. Historical pollutant data were
obtained from representatives of individual plants, municipal
sewer district offices and NPDES permit authorities. Information
regarding printing industry contributions to publicly owned
sewage systems was requested from 16 large municipalities. In
most cases, no analyses of toxic pollutants, with the exception
of certain heavy metals, were included in these data.
Data Request Survey
According to Dun and Bradstreet, the printing industry consisted
of 57,008 manufacturing establishments in 1976.(6) The Agency
developed a mailing list which provided representative coverage
11
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of these establishments by product, process, size, and SIC code,
and mailed a data request survey to approximately ten percent" of
the industry. ,, , _ ;
During preparation of 'the data request survey and the mailing
list, 52 trade association contacts were made. A meeting, which
resulted l/isin valuable industry input to the survey, was held with
representatives,pf the:followihg' association^:
Printing Industries of America' (PIA)
., Pr.inting Industries of Connecticut, (PIC)
, Graphic Arts Technical Foundation tGATF)
National Association of Pointers $nd tithographers, Inc. (NAPL)
Flexographic Technical Association (FTA)
Grayure Technical Association ,(GTA), ,
, Girayure Research Institute tGRI)
'' American Newspaper Publishing Association (ANPA) J :"
An industry committee, known as the Environmental Conservation
Board was formed. It was comprised of concerned representatives
from severa.1 groups within the printing and publishing industry
and , included representatives, from various graphic art trade
association?;,, chemical suppliers, and equipment manufacturers, as :
well as individuals from prpminent, printing and publishing' firms
throughout the .^country. The committee, meeting regularly with
EPA from. the fall' pf 1977 until the, fall of 197?, provided
valuable 'technical information and served as a forum fpr exchange
of , irifprmatlpn and ppin ions. The committee participated in the
review_,,a.nd .developmejit of the survey form tand had considerable
input "' intp its ., coritent. . The committee and, its member
organizations also provided suggestions regarding the selection ,
of plants to be sampled.
As mentioned .previously, EPA mailed survey, forms to 6^995' plants.
Of the 5,,;j5'75 "fprms returned (J3.8.2 per bent), 5,004 proVi'd.ed usable
inf,arma,tibn. Pata from t)ie" o't^er plants _were hot usable if or
saclv3 rietappns ais (a) the, pXant had, "gone ,out of"/ business .6r (b)
pri-Ht^ng was not performed ."on, site. The results of the survey
forined the primary -b,asis for the industry profile presented in
;?" ' " ' ' '''- l "• '"
Plant Visitation and Sampling pVogram -
Sixty-two plants were visited and 17 were sampled,. The ^urjpose.s
of the visitations were to: gain a better understating5 -ofi ^h^-
iilLdustry^ , its processes, and, ,its3 jCon^ple^x iti.es ; qualify historical
dat,as raVnd. . .obtain current process!, J iiXfcyrmatlon; , and determine '
wh^etKiWr ,-the plant was a candidate r£oK sampling,. Two sampling
programs, screening and verif idation, were implemented based on
12
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information obtained froffi. pl'aht visits and the data recfuest
sdrvey. * ''•-'**• '••' • •'"'•- :" '""•'"• •• _ •' -; ~ -*' '• '' ' r/
The purpose of the screening sampling program was to establish
the presence or absence of toxic pollutants in printing, and
publishing wastewater discharges. Plants selected for scr^efti'ng
employed various processes for which the maximum amount of ^.OX.JLC
poll'utjant information"' cOuld be' obtained." Specif it criteria" f.0jr,
select! :hg^: pi ants were as follows: ' / , ~",
K;r"'jlfhe plant 'should' be" representative in terms , pfl\$ize,.
' j age^ geogrdphiccal"Ilbcatipfl(, and processes, ' "" ."„'"/'
";• 2. ;< Opera tions': at the plant1 'should involve the gr|cite$t
:*" '"' l° n'owber 'of ' commonly used 'chemical ; adid|tive;s,
• "- ' "i^resetrvatives, anti-foamants, and cleaning solutibtts
(•>(,: '--(this allows EPA to obtain the maximuA amount 6f toxip
' politjtant ' information) , ;• .'"','',
3. The plant should have segregated process and npnprocess
wastewater streams', -:>. . -. -••'•-- '.-''
' 4'. -The 'plant sh'ould have complete treatment to provide;
1 data on toxic polliitant reduction through application
o'f^ various treatment alternative^, ' ' '
5. '.The plant^s raw wastewater and 'treated effluent should
be physically accessible.
- \ ' , >": ,' ' . > X ..' < ' - • ' '"•}.' ' • . : ' ' - . . ' / • ,
All" sampling * and 'analyses procedures for screening as well as
vteriflcatioh followed the Sampling and Analysis ': Procedures fotr
Se'e'ehlngr <#*•• Industrial Effluents for Priority Pollutants, (U-St
Protection Agency, Cincinnati, Ohio, April t977).
' • '
-. . . .
Up"6n' r^View of the":screening sampling data, : the'" Agency decided to
e^<*lu^e"':i: tWe phbtoprpc^ssing, honmetalliC platemaking, and
l -c
( nohwkter-faaS^cJ inks) subcategories from national
regulations pursuant to the provisions of Paragraph 8 (a)(iv> Of
the Settlement Agreement; therefore, no verification sampling was
conducted for these subcategories. The data also showed that
further investigation of the pressroom (water-based inks)
subcategory was warranted and verification sampling was conducted
at two plants to obtain additional information.
The purposes of verification sampling were to (a) verify results
obtained in the screening sampling program, (b) quantify
pollutant loadings of raw and treated wastewater, (c) provide
additional information to aid in industry subcategorization, and
13
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(d) determine pollutant reduction and treatment efficiency of
in-place treatment technology. Specific criteria applied in
selecting a plant were the same as for screening sampling.
Subcategorization
The accumulated information and data were assessed to determine
whether differences in raw materials, final products,
manufacturing processes, equipment, water usage, wastewater
constituents, or other factors required the development of
separate effluent limitations and standards of performance for
different segments (subcategories) of the industry. This
required the identification of raw waste and treated effluent
characteristics, including: (a) the sources and volumes of water
used, the manufacturing processes employed, and the sources of
pollutants and wastewaters within the plant; and (b) the toxic
pollutant constituents of wastewaters. Subcategorization is
addressed in Section IV of this document.
Identification of_ Control and Treatment Technology
Raw waste load data are presented in Section V of this document.
Reduction of toxic pollutants in treatment systems employed at
plants visited during this study is discussed in Section VI.
Analysis of Treatment Alternatives, Cost, and Energy Data
Because the Agency determined that the amount and toxicity of the
pollutants contained in the raw wastewater discharges do not
justify developing national regulations, study of this industry
was terminated in its early stages. Control and treatment
options were not developed, nor were cost, energy, or nonwater
quality aspects evaluated in detail. Effluent reduction
attainable through application of specific control and treatment
technologies also was not determined; however, Section VI of this
document presents effluent data for existing pretreatment and
treatment systems employed in the printing and publishing
industry.
14
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SECTION III
DESCRIPTION OF THE INDUSTRY
INTRODUCTION
The printing and publishing point source category includes
manufacturing establishments whose operations fall within Major
Group 27 of the 1972 Standard Industrial Classification Manual.
(3) The SIC list is oriented toward the collection of economic
data related to gross production, sales, and unit costs. The
list is useful because it divides American industry into discrete
product-related segments. It is, however, only generally related
to the nature of the industry in terms of actual plant
operations, production processes, or water pollution control
considerations.
Major Group 27 consists of (a) manufacturing establishments
primarily engaged in printing, using one or more of the common
processes such as letterpress, flexography, lithography, gravure,
or screen, and (b) those establishments which perform services
for the printing trade such as typesetting, engraving,
photoengraving, electrotyping, and binding. Table III-l lists
the 17 specific SIC codes investigated during this study and the
more common mixes of products and processes that are likely to
occur because of similarities in equipment and expertise; almost
any combination of printing processes is possible.
A substantial amount of in-plant printing is performed by
establishments whose major activities fall outside the definition
of SIC 27. Examples of industries extensively using graphic arts
technologies include: the converted paper industry, the textile
industry, and the growing field of circuit printing. In many
instances, it is difficult to classify a plant due to the
diversity and overlap of processes and products. For the
purposes of developing the industry profile, only data from
plants whose primary line of business falls within SIC 27 were
used.
PROCESS DESCRIPTIONS
Introduction
This section presents information on printing plant operations
with emphasis on the chemical and water usage aspects. Many of
the technical terms used in this discussion are defined in the
glossary. The basic production steps (process operations) common
to lithographic, letterpress, flexographic, gravure, and screen
printing are illustrated in Figure III-l.
15
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TABLE,.JJI-1
^ ,"' ,*"'
)DES INVEST I<
STUDY 0? THE PRINTING ANT) PUBLISHING INDUSTRY
SPECIFIC SIC .CODES INVESTIGATED, IN EPA'S
Primary SIC Code - -,1 : ,. ' Secondary. Ac £ i vl t i, eV ,
*:„-,„• ' •_';.', '^'•'•}, ' -'. :•' ' " ,.„ :, . "~: ' 97SI
7 . t ^ z/. Jl,9
•* * ! - Tt"" ' ,. "• ~ J '/-) r- - ^ ' <'' *•
L ~ '* ~* - f-> , O"7Q'1 '
"' • i- : • ' .. . . t'C " •"•• -• • 27-a-l.,
;2J32 IBook Printing ; ;, ' '• t ' ;,; :L '; .;.' 2751, 27^52, 27?4^J '•-'-
,,-•'. , i)
'-'2^41 MifecellaiiSous'Publishitig * '"'
2751 Commercial Printing, Letterpress 2732, 2752, 2754
'~~ ' :2752i1 *Cpmq§fcial Printinjj* titlipgraphic ^^ " , 273.2, 2751, ^753,, %2
•~ • • f; "H ' ; =: • ."i4 j ,,'.;; :.v'.;:'O^ ; ' ^3 j;.-\ ;•:- ** ' :2771^ 2791'^ 2795--•"''•" -:
; ~' 2733*" Engraving "and T^Iate Pointing: ,,."* " "^., ^-^ , 27,54,, ,2752 \^r:^
r j;, 2754 CbmroeraiaifcPrintiflg'i; Grawirbs.jf- .onir-v ~i > ".27^51,- 279^ ''-•-T':-n-: ;o« >
'/' 2761' Manifold B"us.iness Fpr.iiis^ !,".. j, .'" Vr-,
„ :; )'"27>71 Greeting, Caifd'Pub*lisM;rig.;: "' ic> ; .3
2782 Blankbooks,' Looseleaf Bihders'V an -.-ri . - 2753;' 2754'^ '•
••-•>t. - -., '; : ',>j -v- •;/--.-;)- t,". ;.f", ;-:j ,.1 •-'••<: ?•'- ': -.' b;, '-• T s -.-Uf; i
•*. * 27^4 E,lece,rotyp',ing^; and Stjgreqtypirig . r^.^ , r, ; > 27^53 ;J ^,.C ac,;;, ^
?•:, 2795 Lith6graphia'?lat-eiaraking?;^Re"iEat^d Serviced 2793 'f '• v- ;,--??; i1.
' '
, ; :; ,1 i i,; . . <; i J- Bo":/'! . ,-•,,
1 Converted Paper Products—SIC 2649.
2 Stationery Products—SIC 2648.
Source: Dun and Bradstreet, 1976.
16
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Material to be Reproduced- ''••'
i
> . r, "i -,• f fc "
'Art am Copy Preparation
arid'/' or
Composition
, .;.-.. „ - '
~~ " •» r '
' ; - "5 i;-: , '.- -• •, •>
"""* ;A- ' -' , " • ^ i ',•';"; L '' ' *~ * ' ' * ; '
Photoprocessing
i. *':
, :• .. «„ x ,'-.>!
' >''''« -' / , \ '* i. t * ''
<, . .... 1.,., , , , ,
--",-,-,. --j i!'.1-"
Art and Copy Preparat j,oji ,,
i
i
1,. - • '•-'•• "c: - .•"• c,i: ,>_;*.,: -s- j
,, Platemak,ingi r ? ,?:
-3j,' -'I .• '. -" .t,i
, -, ••» 1 K :. _(
,.- •„-; Stioting-.. - •;;
.. - ,_-!•»
1
h<; D',:X' '• '
i , ".'>,"".'
: ^Finishing -and; Bi?dding o.-v.-
" • " P. > ' i f " i : ! - v "r "; ;'•>. ( i ;. ,
' i ' ^ , '
,-- i-;-< . .- it,.',
..' iv f.«, -.-: -
,-:=>vi;r; ;< -:.., •
, • ' • ' '- J ", ?'" ' t
Firiished ^fodtfct >lj, C!> 1
i,ni
FIGURE III-l. GENERAL MANUFACTURING STEPS FOR PRINTING PROCESSES WHICH
INVOLVE PHOTOMECHANICAL PLATEMAKING
17
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Art and Copy Preparation and Composition
Art and copy preparation involves manual operations employed to
transform original materials into a camera ready form and to
prepare the transparencies, which are subsequently developed, for
platemaking. Camera work, copy layout, and transparency
stripping are some examples. Water is not used in art and copy
preparation.
Composition is the assembly and justification of type. In the
traditional sense, this term refers to the manufacture of
letterpress printing plates from individual metallic type faces.
This outdated method of composition is rapidly becoming obsolete.
Modern composition is performed with phototypesetting machines or
cathode ray tube equipment. After the manuscript is composed, it
is photographed and transparencies are developed. Printing
plates are manufactured from the transparencies by
photomechanical processes.
Photoprocessing
Photoprocessing operations are performed at printing plants to
produce transparencies from exposed photographic films. In
printing, transparencies are the templates from which the images
on printing plates are created. Color printed products are
manufactured from transparencies which are produced by color
separation photography. Four separate exposures, each through a
different color filter, are made for every original. Using
special inks and the four printing plates made from the
transparencies thus produced, the printer can reproduce the
entire visible spectrum.
In general, black and white rather than color film is used in the
graphic arts industry. Black and white film consists of a base
material which is coated with a light-sensitive emulsion (a
colloidal suspension of silver halide crystals in gelatin). When
the emulsion is exposed to a light image, electrons are ejected
from the impacted halide atoms. The free electrons are trapped
by crystal imperfections. The trapped electrons attract
positively charged free silver ions and clusters of metallic
silver form at the trap sites. These clusters of metallic
silver, still very small, form a latent image of the original
light exposure pattern.
During processing, the developer solution causes additional
silver to be formed at the cluster sites to the extent that the
clusters grow, aggregate, and form a visible image. The most
common developer for black and white film is hydroquinone (p-
18
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dihydroxybenzene). Metol (methyl-para-aminophenol sulfate) is
another commercially important developing agent. These compounds
ionize in alkaline solutions and are capable of reducing exposed
silver halides to metallic silver at a rate which is much greater
than the rate at which they reduce unexposed silver halides.
Potassium or sodium carbonate is used to increase the pH of the
solution, thus increasing the activity of the developing agent.
A preservative, usually sodium sulfite, inhibits aerial oxidation
of the developing solution. Potassium bromide or another
restrainer is used to minimize chemical fogging of the film.
When the film is contacted with a fixing solution, development
stops and the silver images formed during development become
permanent. The major constituents of a typical fixing solution
are acetic acid, thiosulfate salts, and potassium alum. Acetic
acid arrests the developing action which depends on alkaline
conditions. A thiosulfate salt, usually ammonium thiosulfate,
converts unexposed silver halides to a water soluble form.
Potassium alum hardens the gelatin and renders it insoluble in
water. After it is fixed, the finished transparency is washed
with water and dried.
Current industry trends are toward automatic film processing as
opposed to tray developing. Rinse water usage in automatic film
processors ranges from 4 to 15 liters per minute (1 to 4 gallons
per minute) per processor. The water may run continuously;
however, many processors are equipped with water-saving solenoid
valves so that rinse water only runs when film is in the
processor. Almost all automatic film processors are equipped
with silver recovery units. Silver recovery is discussed below.
Silver Recovery. The fix and wash water solutions contain
essentially all of the silver removed during photoprocessing.
The most common methods of silver recovery are metallic
replacement and electrolytic recovery.
Metallic Replacement - Metallic replacement occurs when a
metal, such as iron, comes in contact with a solution containing
dissolved ions of a less active metal, such as silver. The
dissolved silver, which is present in the form of a thiosulfate
complex, reacts with solid metal (iron). The more active metal
goes into solution as an ion, and an ion of the less active metal
becomes solid metal (silver).
Silver ions will displace ions of many of the common metals from
their solid state. Because of its economy and convenience, iron
in the form of steel wool is most often used. Zinc, as a
replacement metal, can also be effective, but it is seldom used
because of its relatively higher toxicity and greater cost.
19
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Aluminum is not commonly used as a replacement metal because of
the simultaneous generation of hydrogen gas.
For most efficient operation, the pH of the solution passing
through the metallic replacement unit should be between 4 and
6.5, with an optimum between 5 and 5.5. Below a pH of 4, the
dissolution of the steel wool is too rapid. Above a pH of 6.5,
the replacement reaction may be so slow that an excessive amount
of silver would be lost because of the long reaction time
required.
Silver recovery by metallic replacement is most often carried out
using commercially available units consisting of a steel wool
filled plastic bucket with appropriate plumbing. Typical
practice is to feed waste fix to two or more canisters in series
or series-parallel combinations. For two canisters in series,
the first canister removes the bulk of the silver and the second
unit polishes the effluent of the first and acts as a safety
factor if the first unit is overused. When the first unit is
exhausted, it is common to replace it with the second and put a
new unit in place of the second. It has been reported that
silver concentrations in the effluent from a single unit average
40 to 100 mg/1 over the life of the unit versus a range of 0.1 to
50 mg/1 when two canisters are used in series.(8)
Desilvered fix is not recycled because of the iron contamination.
The average iron concentration in the canister effluent, over the
life of the canister, is 4,000 mg/1.
Electrolytic Recovery - The application of direct current
across two electrodes in a silver-bearing solution causes
metallic silver to deposit on the cathode. Sulfite and
thiosulfate are oxidized at the anode as follows:
H20 + S03-2 = S04-2 + 2e- + 2H+ (Anode)
S03-2 + SZ03~2 = S306~2 + 2e- (Anode)
Ag+ + e- = Ag° (Cathode)
Approximately 1 gram of sodium sulfite is oxidized for each gram
of silver plated. Considerable agitation and large plating
surface areas are necessary to achieve good plating efficiency
and high quality silver (up to 96-98 percent pure). If multiple
units are used in series, lower silver purity levels are
generally achieved in the tail cells. The cathodes are removed
periodically, and the silver is stripped off. To prevent
"sulfiding", the current density in the cell must be controlled.
Sulfiding is the result of decomposition of thiosulfate at the
20
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cathode. The sulfide contaminates the deposited silver and
reduces recovery efficiency. The higher the silver
concentration, the higher that the current density can be without
danger of sulfiding. As the silver is plated out of solution,
the current density must be reduced.
Batch electrolytic recovery units can be used for primary or
secondary silver recovery. Overflow fix from a process line or
lines is collected in a tank. When sufficient volume is
reached, the waste fix is pumped to an electrolytic cell for the
silver removal process. The desilvered fix is either discharged
or reused. Primary batch system cells are usually designed to
desilver the fix at fairly high starting silver concentrations of
about 5,000 mg/1. The silver concentration in the effluent is
typically about 200-500 mg/1, but can be reduced to 20-50 mg/1
with additional treatment time and careful control of current
density. A secondary batch system cell typically achieves the
lower range because the process can be optimized for low starting
silver concentrations.(8)
Continuous electrolytic recovery units remove silver from the fix
solution at approximately the rate at which silver is being added
by processing. The recovery cell is included "in-line" as part
of a recirculation system. This continuous removal technique has
the particular advantage of maintaining a relatively low silver
concentration in the fix processing solution so that the amount
of silver carried out with the processed material into the wash
tank is minimized. The silver concentration in the fix can be
maintained in the range of 500 to 1,000 mg/1, the lower limit
being primarily a function of residence time in the cell (i.e.,
system flow rate).
The recycling of desilvered fix solution, whether by an "in-line"
continuous system or by a batch system, requires adequate
monitoring and process control to protect product quality.
Parameters which should be monitored to maintain the physical and
chemical properties of the fix solution include pH, silver, and
sulfite concentrations.
Platemaking
An image carrier is a plate, cylinder, or screen used on a
printing press to transfer an ink image to a substrate. The
various methods of image carrier manufacture are collectively
termed "platemaking". Most platemaking methods are based on the
principles of photomechanics.
In photomechanics, the plate is coated with a light-sensitive
material and exposed to light transmitted or reflected from
21
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transparencies. The physical properties of the material change
upon exposure to light. In most cases, the exposed areas harden
proportionally to the amount of exposure. An image is formed
when the unexposed areas dissolve in water or other solvents
during subsequent processing. This image may become the image
carrier or may serve as a template which allows acid solutions to
etch the uncovered areas of the underlying metal. In the latter
case, the light-sensitive material is called a resist and the
etched metal serves as the image carrier. Photomechanical and
other image carrier preparation processes are discussed below.
Lithographic Platemaking. On a lithographic printing plate, the
image areas are on the same plane as the non-image areas. The
image areas have an affinity for solvent-based inks and the
non-image areas are hydrophilic and repel solvent-based inks.
The printing plates used most often in large lithographic
printing operations are surface plates, deep-etch plates, and
bimetallic plates. Surface plates are used for short and medium
length press runs while deep-etch and bimetallic plates are
generally used for longer press runs.
Surface Plates - Surface plates are classified as
"presensitized" (coated by the manufacturer) or "wipe-on" (coated
by the printer). The plate backing is smooth or finely grained
aluminum which has been anodized or treated with silicates so
that the coating will adhere to the plate and not react with the
metal.
Presensitized and wipe-on plates are usually coated with
diazonium resins. Diazonium coatings are easy to work with and
are resistant to changes in physical properties caused by
temperature or relative humidity. Presensitized plates are the
most widely used but, because presensitized plates have limited
storage life, wipe-on plates are preferred for some applications.
A typical wipe-on coating is 4-diazo-diphenylamine polymerized
with formaldehyde. The coating is dissolved in a suitable
solvent, usually a mixture of denatured alcohol and water, and
applied .to the plate with a two-roll coater or a sponge. The
shelf life of the solution is not more than a few days and unused
portions are disposed of regularly.
22
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Diazo-coated plates are usually exposed to negative
transparencies and developed by one of a number of related
processes. A typical example is the emulsion developer process.
An emulsion developer is an acidic aqueous solution which
contains dissolved gum arabic and an emulsified lacquer. During
development, the lacquer deposits on the hardened (exposed)
coating, and gum arabic precipitates on the aluminum, which is
uncovered as the unexposed coating dissolves.
Following development, the plate is rinsed with water, treated
with an aqueous gum arabic solution, and allowed to dry. The
image area, which is covered with the dryed lacquer, accepts ink,
but refuses water. The aluminum in the non-image area is covered
by a thin film of gum arabic. Gum arabic serves to enhance the
ink repellance of the aluminum.
Although some printers process these plates manually, the use of
processing machines for diazo-coated plates is quite common. In
general, water usage is less when the plates are processed by
machine.
Photopolymer plates, which are always precoated by the
manufacturer, are capable of longer press runs than diazo-coated
plates. Two of the more common photopolymer coatings are (a)
polyacrylate compounds and (b) cinnamate esters. Polyacrylate
compounds are esters of acrylic acid derivatives and alcohols.
Photoinitiators accelerate the light induced hardening
(polymerization) of these compounds. The photoinitiator may be a
peroxide, a diazonium salt, a silver halide, or a polyhalogenated
alkane. Cinnamate esters, which do not require photoinitiators,
are another common photopolymer coating material. Photopolymer
plates are usually processed by machines; the processing
solutions are specific to the plate chemistry.
Deep-Etch Plates - Deep-etch platemaking is usually a manual
operation and requires skilled craftsman. It was once a
predominant process, but is now gradually becoming obsolete with
the advent of photopolymer plates which are capable of longer
press runs. In general, this process generates more wastewater
than any other lithographic platemaking operation. The term
deep-etch is a misnomer. The image areas on these plates are
only slightly below the non-image areas.
23
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A typical procedure for deep-etch platemaking is outlined below.
(a) The grained aluminum plate is counter etched (i.e.,
cleaned and conditioned with harsh chemical solutions).
The plate is immersed in an aqueous solution of three
percent phosphoric acid by volume. This is followed by
treatment in an 11 liter (3 gallon) aqueous bath
containing 0.09 liters (0.02 gallons) of 48 percent
hydrofluoric acid and 0.80 liters (0.21 gallons) of 20
percent aqueous ammonium dichromate.
(b) The plate is coated with a photographic resist on a
rotating table called a whirler. The pH of the
coating, an aqueous solution of gum arabic and ammonium
dichromate, is adjusted to nine with ammonium
hydroxide. The coating is poured onto the plate and
dries by the rotating action of the whirler. Excess
coating spins off the table and is cleaned up with
water.
(c) The plate is exposed to a positive transparency.
(d) The plate is developed in a solution which dissolves
the unexposed coating. The developing solution is an
aqueous mixture of calcium chloride and lactic acid.
After development, the aluminum in the unexposed areas
is bare, and the remainder of the plate is covered with
an acid resistant stencil.
(e) The plate is etched in an aqueous solution composed of
ferric chloride, hydrochloric acid, and calcium
chloride. An image is formed as the unprotected
aluminum is attacked.
(f) The plate is washed four or more times with anhydrous
alcohol, isopropanol, or Cellosolve and allowed to dry.
The stencil is destroyed in this step.
(g) In some cases, the image areas are copperized. Copper
increases the press life of the plate and is more
receptive to solvent-based inks and lacquers than is
aluminum. The copperizing solution consists of cuprous
chloride and hydrochloric acid dissolved in
isopropanol.
24
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(h) The entire plate is coated with a film of ink receptive
lacquer and allowed to dry. The lacquer is a vinyl
resin dissolved in a solvent such as methyl ethyl
ketone or Cellosolve.
(i) The plate is covered with a greasy ink.
(j) The plate is placed in a water bath and scrubbed with a
brush. This removes the lacquer and ink covering the
aluminum in the non-image areas but, does not remove
the lacquer and ink in the image areas.
(k) The plate is treated with an aqueous solution of
phosphoric acid and gum arabic. Gum arabic enhances
the ink repellance of the aluminum.
Bimetallic Plates - Bimetallic plates are the most expensive
lithographic printing plates and are capable of the longest press
runs. The image areas are copper, which has an affinity for
greasy inks, and the non-image areas are relatively hydrophilic
metals such as aluminum, chromium, nickel, or stainless steel.
The plate is coated with a resist, exposed to a positive
transparency, and developed. The non-image areas on the
developed plate are protected by an acid resistant stencil. The
image areas are formed by etching away the hydrophilic metal (in
the areas unprotected by the stencil) to uncover the copper. The
process is similar to deep-etch platemaking.
Le.tterpress and Flexographic Platemaking. Flexography is a
modern variation of letterpress, which is the oldest commercial
printing process. Letterpress and flexography are relief
printing methods; i.e., the image areas on the printing plates
are raised relative to the non-image areas. The primary
difference between the two methods is that flexographic plates
are rubber rather than metal or hard plastic. The porous
structure of rubber is ideal for certain printing applications.
The traditional letterpress plates (stereotypes and electrotypes)
are duplicates of original plates which are compositions of
metallic type faces or photoengravings. Because composition and
photoengraving are time consuming processes, it is convenient to
use the original to make duplicate plates which are used for the
actual printing.
Photopolymer plates are gradually replacing the traditional
plates. Photopolymer plates are manufactured by modern
photomechanical methods and, although they are sometimes used to
make duplicate plates, are generally used directly on the
printing press.
25
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Photoengraving - Photoengraving was the first
photomechanical platemaking process. First, zinc, copper, or
magnesium plates are coated with a resist and exposed to negative
transparencies. Next, the plate is developed and the exposed
coating forms an acid resistant stencil. Finally, a positive
relief image is formed by chemical etching of the plate areas
unprotected by the stencil. After the resist is removed the
original photoengraving can be used directly on the press, but is
more commonly used to make duplicate plates.
The most common resist is polyvinyl alcohol sensitized with a
diazonium salt or ammonium dichromate. The resist is applied on
a whirler in a manner similar to that previously discussed for
deep-etch platemaking. The developed stencil is usually hardened
by treatment with chromic acid. A typical aqueous etching
solution for magnesium and zinc contains between 10 and 20
percent nitric acid, 4.5 percent urea derivatives, and 1 percent
surfactant which is composed of sulfates and alkyl benzenes.
Aqueous solutions of ferric chloride and hydrochloric acid are
typically used for copper etching.
Stereotype Plates - Stereotype plates are lead alloys which
were once widely used for printing newspapers, books, and other
publications. A malleable matrix composed of paper pulp and
thermosetting phenolic resins is placed over the original plate
under pressure and heated. (Recall that the image areas on
letterpress plates are raised relative to the non-image areas.)
The mold thus produced is the intaglio counterpart of the
original relief plate. Molten lead is cast in the mold and a
stereotype is formed.
Electrotype Plates - The use of electrotype plates is
declining, but they are still employed to some extent in the
manufacture of high quality commercial products (e.g., books).
Electrotype platemaking is quite involved and is only briefly
discussed here. Intaglio molds are made from original relief
plates in a manner similar to that discussed previously for
stereotypes, except that the matrix is made of plastic rather
than paper pulp. The molds are sprayed with light coats of
silver to make them conductive and electroplated with copper,
nickel, or chromium. The metal shell thus formed is separated
from the mold and backed with a molten metal or plastic.
Finished electrotypes are high fidelity duplicate plates capable
of long press runs.
Plastic and Rubber Duplicate Plates - Duplicate plastic and
rubber printing plates are cast from intaglio molds. The molds
are made from original plates in a manner similar to that
26
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previously discussed for stereotypes. The mold matrix is
composed of paper pulp and thermosetting phenolic resins.
Photopolymer Plates - Photopolymer letterpress plates are
used to print beverage containers, certain types of books, and
many newspapers. Some of these plates are manufactured from
proprietary liquid photopolymers. The liquid is poured into a
trough on a plastic base and exposed to light through a
transparency. As the action of the light hardens the exposed
portion of the liquid, a compressed air stream removes the
unexposed portion, which is collected and reused.
Precoated letterpress photopolymer plates are exposed and
developed with aqueous solutions containing caustic and alcohols.
Typical coating materials include polyesters derived from acrylic
acid, esters based on the derivatives of cinnamic acid,
polyamides, and other proprietary compounds. A photoinitiator,
such as benzoin ethyl ether, is usually present in the coatings.
Flexographic photopolymer plates are used to print packaging
material, business forms, tags, labels, books, and wrapping
paper. These plates are manufactured in the same manner as
precoated letterpress plates. The only difference is that the
photopolymer coatings contain butadienes and other elastomers.
The presence of elastomeric compounds gives the flexographic
plates a rubbery character.
Gravure Cylinder Preparation. Gravure cylinders,, large heavy
steel cores coated with copper, are prepared for printing by
highly skilled craftsman. A general discussion of traditional
gravure platemaking is presented here; however, the reader should
realize that many variations exist in this intricate process.
New gravure cylinder preparation procedures, including laser
etching of .cylinders, are gradually coming into use.
Gravure printing is an intaglio process; the ink is transfered to
the paper from grooves or impressions which are etched into the
cylinder.
The steps involved in gravure cylinder preparation are outlined
below.
1. The cylinder is cleaned. In a typical procedure the
cylinder is scrubbed with caustic, rinsed with water, and
scrubbed with a solution of acetic acid and salt. Mild abrasives
may also be used.
2. A gravure resist is exposed to a fine transparent grid on an
otherwise opaque background. The resist hardens proportionally
27
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to the amount of light reaching it during exposure. The area of
the resist exposed to the grid hardens uniformly. The surface
area of the cylinder protected by the resist, which is thus
hardened, will become the cell boundaries on the finished
cylinder. The cell boundaries serve the mechanical purpose of
providing a surface of uniform height on the finished cylinder.
Such a surface is required to facilitate the doctor blade which
rides on the cylinder and removes ink from the non-image areas
during printing.
After the resist is exposed to the grid, it is then exposed to
positive transparencies and applied to the cylinder. (Note that
the resist may be applied to the cylinder prior to the exposures
to the grid and transparencies). Three commonly used gravure
resists are discussed below.
(a) Carbon tissue is a mechanical suspension of materials
in gelatin on a paper backing. The suspended materials
include pigment, dyes, and alum. This formulation is
not light-sensitive; it must be sensitized with
dichromates. This may be accomplished by soaking the
carbon tissue in an aqueous solution of 2 to 4 percent
potassium dichromate.
Following exposure, the hardened tissue is applied to
the cylinder with the gelatin r.ide in contact with the
copper surface of the cylincer. The cylinder is wet
with water so that the gelatin vill adhere. Denatured
alcohol is poured onto the cylinder until the carbon
tissue is saturated. The cylinder is then immersed in
warm water. The water soaks through the paper backing,
which is peeled off. Some of the unexposed gelatin
dissolves during this treatment. Finally, the cylinder
is soaked for about five minutes in an aqueous solution
of about 50 to 80 percent alcohol, and allowed to dry.
(b) Gravure resists may be aqueous-solutions of gelatin and
dichromates which are sprayed or poured onto the
cylinder and allowed to dry.
(c) A special photographic film developed for use as a
resist in gravure platemaking consists of a silver
halide emulsion separated from an acetate backing by a
layer of polyvinylpyrrolidone. (The polyvinyl-
pyrrolidone allows the acetate backing to be stripped
away without damaging the silver halide emulsion.) The
film is exposed, developed, and fixed manually by
conventional photoprocessing procedures (see
Photoprocessing). The processed film is applied to the
28
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cylinder with the emulsion side in contact with the
cylinder surface. After application, water and acetone
are poured onto the cylinder to facilitate removal of
the acetate base. Acetone also dissolves the
polyvinylpyrrolidone, thus baring the silver halide
emulsion.
3. The dichromate and gelatin resists discussed under (a) and
(b) above are developed with a warm water spray. This removes
coating in proportion to the amount of exposure. When developed,
the resist covers the entire cylinder surface and varies in
thickness and hardness except for the area which protects the
gravure cell boundaries.
4. In many cases, both type and continuous tone pictures are to
be reproduced and are etched in separate stages. The areas not
to be etched in a given stage are covered with an turpentine-
benzol-asphalt varnish.
5. The cylinder is etched, usually in aqueous solutions of
ferric chloride, ferric sulfate, and copper salts. Some etching
is performed electrolytically in aqueous baths of ammonium
chloride and sodium chloride. Etching solutions penetrate the
softest and thinnest areas of the resist more readily than they
penetrate the hardest and thickest areas. Wasterwater from
etching contains iron and copper salts.
6. The resist is removed from the cylinder manually, usually
with the aid of solvents.
7. The cylinder is inked, placed on a proof press, and used to
produce a proof. The proof is checked for errors.
8. After proofing, the areas which need correction are re-
etched. Corrections can be a significant source of wastewater.
9. The cylinder is electroplated with chrome to increase its
press life. The electroplating bath contains chromic acid,
sulfuric acid, and catalysts such as sulfates and fluorides.
Electroplating baths are easily renewed and are rarely wasted.
Oxide films must be removed from the cylinder before
electroplating. This is accomplished by scrubbing the cylinder
with hot caustic and then treating it with hydrochloric or
sulfuric acid.
After a press run, used gravure cylinders are reclaimed by
mechanically stripping off the chrome plating, grinding the
etched copper smooth, and then electroplating a new layer of
copper onto the cylinder. The metal wastes generated by grinding
29
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are usually sold. The copper electroplating solutions, which
contain copper sulfate and sulfuric acid, are wasted
occasionally.
Screen Preparation. Finely woven framed screens covered with
stencils are used in screen printing. The stencils can be
manufactured manually, without the use of water, or
photomechanically. Photomechanical stencils are discussed below.
The screen is coated with a light-sensitive material, usually an
aqueous solution of polyvinyl alcohol and diazonium salts, and
exposed to ultraviolet light through positive transparencies.
The light converts the exposed areas to a water insoluble form.
The screen is subjected to high-pressure water which washes away
the unexposed areas and produces a stencil. The stencil protects
the non-image areas. After a press run, the screen is reclaimed
by removing the stencil with hot caustic.
Printing
In printing, printing plates are placed on presses, inked, and
used to transfer an ink image to a substrate. The following
discussion contains brief descriptions of lithographic,
letterpress, flexographic, gravure, and screen printing.
Printing presses are either web-fed or sheet-fed. Web-fed
presses utilize a continuous roll of paper while sheet-fed
presses print on individual sheets of paper. Sheet-fed presses
are slower than web-fed presses.
Lithographic Printing. A lithographic printing plate consists of
an image area which is in essentially the same plane as the non-
image area. The image area is ink receptive and repels water.
Conversely, the non-image area is receptive to water but repels
ink.
The major categories of lithographic printing are direct and
offset. In direct lithography, the printed image is transferred
directly from the plate to the printed material, whereas in
offset lithography the image is transferred first to a blanket,
or roller, and then from the blanket to the printing stock. The
ink repellance of the non-image areas on lithographic printing
plates must be maintained chemically by dampening the plate with
fountain solutions.
The conventional and Dahlgren dampering systems are used in long-
run lithographic printing. In the conventional system, the
fountain solution is applied to the plate from a rubber roller.
In the Dahlgren system, the dampening solution is applied to an
ink covered roller; then the fountain solution and ink are
30
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simultaneously applied to the plate. Conventional fountain
solutions are aqueous solutions containing gum arabic, phosphoric
acid, a bactericide, and an etch. The etch, usually a dichromate
or magnesium nitrate, minimizes the corrosion of aluminum plates.
Dahlgren dampening solutions are similar to the conventional
solutions, except that they contain up to 35 percent isopropanol.
Fountain solutions readily accumulate ink constituents and, as a
result, must be replaced periodically. At a large lithographic
printing plant, 57 to 76 liters (15 to 20 gallons) of spent
fountain solutions may be disposed of each week.
Lithographic printing inks used on sheet-fed presses are composed
of pigment, polyethylene wax, plasticizer, solvents, drying oil,
and a catalyst. The catalyst, which is a naphthenate of cobalt
and manganese, accelerates the polymerization of the drying oil.
These inks dry by evaporation of the solvents and by
polymerization of the drying oil. The inks used on web-fed
presses are composed of pigment, solvated resins, and a varnish.
These inks dry by evaporation of the varnish, without a
polymerization reaction.
Letterpress Printing. In this process, the ink is transferred to
the printing stock from the image surface, which is raised
relative to the non-image area of the plate. The plate is inked
in the press, and the image is transferred directly to the paper
under pressure. Letterpress ink characteristics vary with press
speed, paper, and job type. These inks are, in general, very
similar to web-fed lithographic inks and include news inks (the
single largest type of ink manufactured), oxidative drying inks,
and moisture set inks. Moisture set inks are a special class of
water-based letterpress inks. Water insoluble resins are made
soluble in moisture set inks with glycols such as ethylene
glycol, diethylene glycol, propylene glycol, or dipropylene
glycol. When the printed product is exposed to steam or a fine
water mist, the resin precipitates and forms a permanent image.
Flexographic Printing. In flexographic printing, ink is
transferred to the printing stock from a raised plate surface as
in letterpress. The primary difference between letterpress and
flexography is that flexographic plates are rubber, rather than
metal or plastic. Flexography is used extensively to print
flexible packages. The porous surface structure of the rubber
plates permits the use of fluid inks. Thus, the inking system of
flexographic presses is much simpler than of presses on which
highly viscous inks are used. Most flexographic inks are
classified as either alcohol or water-base. Alcohol inks consist
of pigments, vehicles, and binders. Shellac, which is often used
as the primary resin, is made water soluble by caustic soda or an
amine such as triethanolamine. A typical water-based ink
31
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formulation consists of a pigment such as calcium lithol (19
percent), alkali solubilized shellac and water varnish (60
percent), polyethylene wax (5 percent), water (15.75 percent),
and silicone oil (0.25 percent).
Gravure Printing. In gravure printing, an etched cylinder is
placed on a high speed press and rotated in ink to fill the
etched image areas with ink. Excess ink on the cylinder surface
is wiped clean with a doctor blade, a strip of metal running the
length of the cylinder. The doctor blade touches the rotating
cylinder, wiping off excess ink without disturbing the ink in the
cells.
The ink is volatile, of low viscosity, and contains solvents such
as toluene and xylene (with benzene impurities). It is generally
circulated in closed piping systems from storage to the press,
because of its volatility. Solvent evaporation can create air
pollution problems. Solvents are usually recovered by piping the
exhaust fumes to activated carbon solvent recovery beds.
Activated carbon adsorption is currently the most widely used
method for the control of solvent vapor emissions from gravure
printing presses. Activated carbon air pollution control systems
involve the use of at least two packed bed adsorption vessels.
At any time, solvents are being adsorbed in one bed while another
bed is being regenerated.
Activated carbon is a highly porous solid. The adsorption
process is a physical phenomenon in which Van der Waals' forces
cause the solvent molecules to adhere to surface of the pores.
Initially, the adsorption process is rapid and complete. During
the course of the adsorption cycle, the outlet solvent vapor
concentration remains relatively constant until breakthrough
occurs. The percent breakthrough is defined as the percentage of
the inlet solvent vapor concentration measured at the outlet.
Before an unacceptable level of breakthrough is reached, the air
flow is transferred to a fresh bed and the saturated bed is
regenerated.
Regeneration is usually accomplished by backflushing the carbon
bed with low-pressure steam. This operation is generally called
the stripping cycle. The steam heats the bed and provides the
heat of desorption of the solvent. The steam also functions as a
diluent, lowering the partial pressure of the solvent. The
solvent-laden steam is condensed and the organic and aqueous
phases are allowed to separate by gravity. The solvent is
recovered by decanting the immisible liquid phases.
32
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Screen Printing. Screen printing is used primarily for printing
on materials of odd sizes and shapes. The screens are finely
woven cloths and metals. A stencil protects the non-image areas.
Printing is accomplished by spreading a viscous ink over the
screen, forcing it through the areas not covered by the stencil
onto the printing stock. A typical screen printing ink is
composed of chalk, linseed oil, mineral spirits, and a drying
agent.
Finishing and Binding
Except in small jobs, such as the printing of handbills,
finishing and binding operations follow printing. Even though
some form of finishing or binding operation is employed at nearly
all printing plants, printers also purchase these services from
independent paper converting businesses as the need arises.
The term finishing refers to a wide variety of decorative
processes, some of which also enhance the products durability.
Although finishing operations can be performed manually, they are
more often performed with specialized machinery.
The typical finishing of a printed piece may include liquid
coating operations (such as lacquering, varnishing, and waxing),
other coating operations (e.g., laminating), or other decorative
processes (such as flocking, die cutting, and embossing).
Laminating differs from the other coating processes mentioned in
that the coating is a thin transparent piece of plastic applied
with glue, heat, and pressure, rather than a liquid applied with
a roller. Flocking is the process of adhering colored textiles
to greeting cards or similar printed goods.
Die-cutting means cutting printed materials into irregular
shapes. Steel-dies are placed on special machines which force
the die upon the printed material under pressure. Embossing is a
method of raising a printed image above the plane of the paper.
This effect is achieved by pressing the material to be embossed
between a female die and a male bed. Embossing is used on
speciality products, such as business cards, or resumes.
Except for wastewater generated during cleanup operations or from
excess lacquers and varnishes, finishing operations do not
involve the use of water or other solvents. From observations
during visits, at most plants where extensive lacquering or
varnishing operations are employed, the resulting wastes are
drummed and contract hauled. Those finishing operations
involving liquids generate extremely small volumes of wastewater,
generally less than 95 liters per week (25 gal per week).
33
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The vast majority of binding operations are performed on high
speed machines where paper is folded, collated, sewed, glued,
rounded, and backed. During the binding process, solid wastes
are produced from paper cutting and trimming. However, little or
no liquid wastes are generated. As indicated in the Data Request
Survey, the most common types of glues used are hot melt glues,
supplied in solid form, and animal glues. Animal glues utilized
were approved by the Food and Drug Administration for food
processing. Representatives of 15 of the 2,944 plants where it
was indicated on the Data Request Survey that binding operations
are used, reported on-site formulation of some or all glues.
Small volumes of wastewater may be discharged from cleanup or
wasting of excess glue mixes.. In general, however, binding is a
dry process.
INDUSTRY PROFILE
General
The printing and publishing industry is the largest of the 20
United States manufacturing industries defined in the SIC
manual.(3) Tables III-2 and III-3 present estimates of the number
and the status of establishments whose primary operations are in
SIC 27.(6) In 1976, approximately 86 percent (49,198) of the
manufacturers were single location operations. Economic
forecasts predicted an average growth ranging between 5 and 6
percent through the 1970's. By 1980, graphic industries
shipments totalled at least $49 billion dollars. Economic
performance during the past two decades has closely followed that
of the total economy. For the most part, the industry is
characterized by a large number of small businesses, although the
large printing and publishing companies are among the largest
companies in the nation. At least 80 percent of all United
States printing is done by about 20 percent of the companies.
The industry is continually undergoing rapid technical change as
a result of new products and innovations by chemical and
equipment suppliers, resulting in faster more highly automated
printing. (9)(10)(11)(12)(13)(14)
Web offset lithography has experienced enormous growth in recent
years due to the advent of phototypesetting equipment, cathode
ray tube composers, and other electronic equipment. Most of the
success of lithographers came at the expense of letterpress
operations, especially in the newspaper field where
computerization and new platemaking methods have replaced the
traditional lead relief plate.(15) Automated platemaking, cheaper
and better plates, and faster and better presses have also been
instrumental in the growth of lithography.
34
-------
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35
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TABLE III-3
STATUS OF ESTABLISHMENTS WITH PRIMARY OPERATIONS
IN SIC MAJOR GROUP 27
SIC
2711
2721
2731
2732
2741
2751
2752
2753
2754
2761
2771
2782
Status* Manufacturers Non-Manufacturers
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
7,163
1,167
1,244
2,526
417
288
2,554
335
267
300
32
58
1,775
240
176
16,408
727
695
12,693
716
575
815
47
64
270
8
20
342
79
160
223
38
29
367
42
99
179
35
63
85
31
13
116
29
8
8
2
1
68
16
10
256
28
20
222
23
16
14
3
0
3
0
1
6
9
6
10
1
0
7
5
6
Total No. Plants
7,342
1,202
1,307
2,611
448
301
2,670
364
275
308
34
59
1,843
256
186
16,664
755
715
12,915
739
591
829
50
64
273
8
21
348
88
166
233
39
29
374
47
105
Status Code A = Not multi-unit affiliated (single location operation)
B = Headquarters location of a multi-unit operation.
C = Branch location of a multi-unit operation.
36
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TABLE III-3
STATUS OF ESTABLISHMENTS WITH PRIMARY OPERATIONS
IN SIC MAJOR GROUP 27
(Continued, Page 2 of 2)
SIC
2789
2791
2793
2794
2795
TOTAL
Status1
A
B
C
A
B
C
A
B
C
A
B
C
A
B
C
Manufacturers
983
31
44
1,998
72
56 .
530
35
23
71
3
4
180
12
7
57,008
Non-Manufacturers
13
2
2
34
3
1
5
1
1
5
2
0
1
0
0
1,370
Total No. Plants
996
33
46
2,032
75
57
535
36
24
76
5
4
181
12
7
58,378
1 Status Code A = Not multi-unit affiliated (single location operation).
B = Headquarters location of a multi-unit operation.
C = Branch location of a multi-unit operation.
Source: Dun and Brad street, 1976.
37
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Letterpress is still commonly used to print periodicals, labels,
advertising materials, catalogs, and financial papers. This will
continue to be a major printing process primarily because it
generates less paper waste than lithography and allows the
printer the flexibility of making corrections on printing plates.
Gravure printing is primarily concentrated in the publication and
advertising markets. It is especially suited to high quality
color illustrations and, unlike lithography or letterpress, can
be used to print on almost any substrate. Because of its
flexibility, gravure is a printing process commonly employed in
the packaging industry and in other industries which print on
specialty items and are not included in SIC 27. New developments
in gravure cylinder technology include the use of dry processes
such as color scanners, automatic cylinder engraving, and
electronic engraving. This segment of the printing industry is
expected to experience steady growth.(16)(17)
Screen printing, the least used of the major printing processes,
is used primarily in the production of signs, displays, posters,
decals, pressure-sensitive labels, and, to a small extent, in the
greeting card industry. This segment of the printing industry is
expected to continue growing as more automatic screen printing
equipment comes into use.(13)
Segments of the industry rapidly declining in number of plants
and employees are in SIC Code 2794, Electrotyping and
Stereotyping, and SIC Code 2794, Photoengraving. These
operations are being replaced by modern technology as in-place
equipment is fully depreciated and replaced, mainly because of
the high cost of raw materials and scarcity of skilled labor.(11)
As discussed in Section II, EPA conducted a data request survey
to obtain basic data regarding plant operations, products and
processes, waste sources, treatment, and discharge methods. The
survey was sent to 6,995 plants (12 percent of those plants known
to be operating in the continental United States). The coverage
included facilities of all sizes engaged in the five major
printing processes and allied service trades. A total of 5,675
responses were received; 5,004 supplied usable information. The
remaining responses indicated that 671 facilities were not
engaged in operations covered by the study. The final data base
of 5,004 usable responses represented a survey of 8.9 percent of
the estimated total population of 56,337 United States
manufacturing sites. In some cases, where survey responses
needed clarification, contact was made by telephone to ensure
correct interpretation of the response. The results of the data
request survey are presented below.
38
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Geographic Distribution
Printing plants are located in all 50 states and are concentrated
in urban areas. Table II1-4 lists the number of manufacturing
sites in each state by SIC code. Ten states, including New York,
California, Illinois, Texas, Pennsylvania, Ohio, New Jersey,
Florida, Michigan, and Massachusetts, account for approximately
57 percent of all United States printing plants; over half of all
commercial printing is done in the four states of New York,
California, Illinois, and Pennsylvania.(6) The major production
areas for publishing of periodicals are in the cities of New
York, Philadelphia, and Chicago. Book publishing is concentrated
in these same cities and in Boston and Los Angeles.
Process Operations Statistics
As a result of the Agency's data gathering program, it was
determined that some combination of eight basic process
operations are used at most printing plants. An estimate of the
number of plants performing each process operation is shown in
Table III-5.
Plant Age
Almost 42 percent of the respondents indicated that their
facilities were more than 20 years old; of these, only 34 percent
had not been renovated within the past 10 years. A large number
of respondents, particularly those representing plants in the
allied service industries (especially lithographic platemaking),
indicated major plant renovations within the last 2 to 4 years.
Plant Size
The diverse nature of the printing and publishing industry makes
it difficult to identify standard production indicators which can
be used to calculate wasteloads on a mass discharge per unit of
production basis. Therefore, production data were not requested
in the survey.
Waste Generation and Disposal
The flow data obtained from the data request survey is summarized
in Table III-6. At approximately 70 percent of the plants
wastewater is not generated or the volume generated is 190 liters
(50 gallons) per day or less; at only four percent is the volume
greater than 19,000 liters (5,000 gallons) per day. The most
common sources of wastewater were photoprocessing and
lithographic platemaking. As shown in Table III-7, based on
NPDES permits or permit applications on file in 1977, there were
39
-------
84 printing plants where wastewater was discharged to navigable
waters. Upon inspection of the permits, the Agency determined
that 30 of these plants discharged only nonprocess wastewater and
that six plants were no longer operating. Data request surveys
were sent to the 48 remaining plants. Responses were received
from 35 of the 48 plants. Eighteen of the 35 respondents
reported direct discharge of process wastewaters. EPA learned
that the other 17 discharged only nonprocess wastewater. The 18
direct dischargers were all large multi-process facilities.
Table II1-8 lists some pertinent information regarding operations
at these 18 direct discharging plants.
An estimate of the number of indirect and zero dischargers is
presented in Table II1-9. More than 99.8 percent of the
estimated 56,337 printing and publishing plants discharge all
process wastewater to publicly owned treatment works or do not
discharge process wastewater. Approximately four percent of the
5,004 survey respondents reported some form of wastewater
treatment prior to discharge. Landfills are the primary method
of sludge disposal at these plants. One hundred thirty-five
respondents reported biological treatment and 262 reported
chemical treatment. In many instances, however, survey
respondents who reported chemical treatment were referring to
silver recovery of photoprocessing wastes for economic purposes.
Less than eight percent of the survey respondents reported
wastewater recycle of any degree. Only seven respondents
reported complete reuse of process wastewater. Eighty-seven
plants contained their process wastewater on site; landfills were
used at 18 of these plants; land disposal was used at 16 plants;
wastewaters were evaporated at 48 plants and wastewaters were
incinerated at three plants.1
Toxic pollutants present in raw materials used in printing and
publishing manufacturing processes are listed in Table 111-10.
This information was collected from literature, chemical supplier
manuals, EPA study of the ink industry, and from historical data.
Historical data were obtained wherever possible from
representatives of individual plants, municipal sewer district
offices, and NPDES permit authorities. In most cases, analyses
of toxic pollutants, other than of a few heavy metals, did not
exist. Historical data are presented in the Appendix.
*The terms "landfill", "land disposal", and "evaporation" are
defined in the glossary.
40
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42
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TABLE II1-5
ESTIMATED NUMBER OF PLANTS EMPLOYING
EIGHT PRINTING PROCESS OPERATIONS
Process Operation
Number of
Plants in
Survey Response
Extrapolated
Total Number
U.S. Plants1*2
Art and copy preparation
and composition 2,816
Photoprocessing 3,673
Nonmetallic platetnaking 3,853
Pressroom (nonwater-based inks) 4,062
Pressroom (water-based inks) 50
Finishing and binding operations 511
Gravure cylinder preparation 134
Metallic platemaking 751
32,000
41,000
43,000
46,000
600
6,000
1,500
8,500
1 Based on 5,004 responses and 56,337 total United States plants.
2 Inspection of the survey responses revealed that 671 of the
57,008 manufacturing establishments listed in Tables III-2 and III-3
were not engaged in operations covered by this study.
43
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44
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TABLE III-7
NUMBER OF DIRECT DISCHARGERS WITH NPDES PERMITS OR
APPLICATIONS ON FILE IN 1977
Plants1
Estimated Number Estimated Number with
Total No. Discharging Only Discharging Historical
SIC Code Plants Nonprocess Wastewater Process Wastewater Data
2711
2721
2731
2732
2741
2751
2752
2753
2754
2761
2771
2782
2789
2791
2793
2794
2795
Unknown
TOTAL
10
4
8
8
0
14
17
0
1
8
2
0
2
0
4
0
1
_5_
84
2
4
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8
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14
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2
54
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0
0
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0
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1
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0
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1
0
2
0
0
J_
7
•"•Conventional parameters and metals data only.
45
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a, KB- <"
S-iyjoij
jsj5o»Or-i&iTl.coaj
II II II II II II ii H II II
M-i 60 »
II II II
CO
49
-------
TABLE III-9
SUMMARY OF INDUSTRY DISCHARGE STATUS1.2
Type of Discharge
Direct
Indirect
Zero Discharge
TOTAL
No. Plants
843
38,679
17,574
56,337
Percentage of Industry
0.15
68.65
31.2
100.00
1 Data includes dischargers employing metallic platemaking and
gravure cylinder preparation processes.
2 The number of direct dischargers is based on NPDES permits on file
in 1977. The indirect and zero discharge numbers are based on an
extrapolation of the results of the data request survey.
3 Data from EPA regional NPDES files; includes 30 plants
discharging only nonprocess wastewater (see Table III-7).
50
-------
Toxic
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
TABLE III-
TOXIC POLLUTANTS PRESENT IN Ri
PRINTING AND PUBLISHING MANU1
Litera-
Pollutant Present ture
Acenaphthene X
Benzene X
Carbon Tetrachloride X
1,
1,
1,
1,
1,
1,
2,4-Trichlorobenzene X
2-Dichloroethane X
1 , 1-Trichloroethane X
1-Dichloroethane X
1,2-Trichloroethane X
1,2,2-Tetrachloroethane X
Chloroform X
1,
1,
1-Dichloroethylene X
2-Trans-Dichloroethylene X
Diraethylphthalate X
Ethylbenzene X
Methylene Chloride X
Isophorone X
Naphthalene X
Pentachlorophenol X
Phenol X
Bis(2-ethylhexyl)phthalate X
Butyl benzyl phthalate X
Di-n-butyl phthalate X
Diethyl phthalate X
Toluene X
Trichloroethylene X
Antimony X
Arsenic X
Cadmium X
Chromium X
Copper X
Cyanide X
Lead X
Mercury X
Nickel X
Selenium X
Silver X
Zinc X
0
W MATERIALS USED IN
ACTURING PROCESSES
Information Source
Chemical EPA
Supplier Ink Study
X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X
X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
Historical
Data
X
X
X
X
X
X
X
X
X
X
X
51
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SECTION IV
SUBCATEGORIZATION
The purpose of subcategorization is to group together plants of
similar characteristics to allow for the development of effluent
guidelines and standards representative of each group (sub-
category) of plants, enabling permits to be issued on a uniform
basis. The effluent limitations guidelines program for the
printing and publishing point source category has been active
since 1977. Prior to 1977, EPA had not collected historical data
of consequence, had not assessed industry practices or treatment
system performance, and had made no attempt to subcategorize the
industry.
To arrive at a subcategorization scheme, the Agency reviewed the
five major printing processes (letterpress, lithography, gravure,
flexography, and screen) and the products manufactured through
the application of these processes. EPA determined that each of
the five major printing processes involves some combination of
eight basic manufacturing steps (process operations). The Agency
established a preliminary subcategorization scheme based on these
process operations. This scheme involves use of a building block
approach; it accounts for the fact that several process
operations can be employed at any given plant. The eight
subcategories are:
1. Art and Copy Preparation and Composition
Art and copy preparation and composition includes all work
related to the preparation and assembly of copy prior to the
development of transparencies and all work related to
assembling finished transparencies for use in plate
preparation. Camera work, copy layout, transparency
stripping, and paste-up preparation are some examples. No
water is used in these operations.
2. Photoprocessing
Photoprocessing operations are employed at printing plants
to produce transparencies. In printing, transparencies are
the templates from which the images on printing plates are
created. Processing of exposed film involves contacting the
film with a developing solution, usually hydroquinone, which
reduces the exposed silver halides to elemental silver. A
fixing solution, which usually contains ammonium
thiosulfate, is applied to dissolve the unexposed silver
salts. Finally, the film is washed with water and dried.
53
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Retouching and dot etching of finished transparancies are
also considered photoprocessing operations.
3. Nonmetallic Platemakinq
Nonmetallic platemaking is the developing of a photographic
image on the light-sensitive coatings of printing plates or
screens. The basic steps involved in nonmetallic
platemaking include exposing a plate or screen covered with
a light-sensitive coating to a light source through a
transparency, removing the unexposed areas with solvents or
other developing solutions, rinsing with aqueous solutions,
and drying. (Platemaking operations which involve chemical
etching of metal surfaces are not nonmetallic platemaking
operations. In addition, the process of electroplating
printing plates is not considered a nonmetallic platemaking
operation.)
4. Metallic Platemakinq
Metallic platemaking is the creation of an image on a
metallic surface by any means except gravure cylinder
preparation. Etching, electroplating, engraving, and
casting of metal surfaces are metallic platemaking
operations.
5. Gravure Cylinder Preparation
Gravure cylinder preparation is the pre-press preparation of
cylinders or wrap-around metallic plates for use in gravure
printing. This includes cleaning and rinsing of cylinders,
copper and chrome plating of cylinders, grinding or
polishing of cylinders, transfer of photographic images to
cylinders, and etching, staging, and re-etching of
cylinders.
6. Pressroom (Nonwater-Based Inks)
Plants where products are printed with solvent-based inks
are included in the pressroom (nonwater-based inks)
subcategory. In a typical solvent-based ink formulation,
resins, lacquers, clays, and pigments are dispersed in an
oily solvent. Presses are cleaned with rags and solvents
are used to aid the cleaning process. Sources of wastewater
from these operations include press cleanup, lithographic
fountain solutions, and air pollution solvent recovery
systems.
54
-------
7. Pressroom (Water-Based Inks)
Plants where products are printed with water-based inks are
included in the pressroom (water-based inks) subcategory.
The inks are used primarily in flexographic printing on
absorbent paper stocks such as kraft or lightweight paper.
Typical constituents of water-based flexographic inks
include pigments and binders such as ammonia or amine
solubilized protein, casein, shellac, and acrylic
copolymers. Small quantities of water are used to clean the
presses after a run.
8. Finishing and Binding Operations
Finishing and binding operations include lacquering,
varnishing, laminating, flocking, die cutting, embossing, or
otherwise preparing printed material for delivery to a
customer. In recent years, most finishing operations have
become highly automated. During the binding process, solid
wastes are produced from paper cutting and trimming.
However, little or no wastewater is generated in any
finishing or binding operation.
The Agency conducted a program of sampling and analyzing raw and
treated printing and publishing plant effluents, as discussed in
Section II. The results of this program indicate that the amount
and toxicity of the toxic pollutants contained in the raw
wastewater discharges from the photoprocessing, nonmetallic
platemaking, pressroom (nonwater-based inks), and pressroom
(water-based inks) subcategories do not justify developing
national regulations. Art and copy preparation and composition
do not involve the use of water. No significant amount of
wastewater is discharged as the result of any finishing or
binding operation. Therefore, the Agency excluded these six
subcategories from national regulations under the provisions of
Paragraph 8(a)(iv) of the Settlement Agreement. (.1 ) (2)
The information and data gathered to date regarding the gravure
cylinder preparation and metallic platemaking subcategories were
not sufficient to make regulatory decisions; however, the data do
show that further study of these subcategories is warranted and
that these operations are similar to certain metal finishing
processes. Therefore, gravure cylinder preparation and metallic
platemaking will be further studied in the second phase of the
rulemaking effort for the metal finishing point source category.
Had the Agency decided to develop uniform national regulations
for the printing and publishing point source category, analyses
would have been performed to determine the effect of plant size,
55
-------
age of facilities, geographical location, and raw material usage
on wastewater characteristics. In addition, the cost of control
and treatment systems would have been considered in an economic
impact analysis. This subcategorization scheme might have been
revised had these factors been taken into account and should be
considered a preliminary subcategorization of the printing and
publishing point source category.
56
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SECTION V
WASTEWATER CHARACTERISTICS
INTRODUCTION
In this section, information is presented on the raw wastewater
characteristics of plants in the photoprocessing, nonmetallic
platemaking, and pressroom subcategories. Raw wastewater data
are presented for toxic pollutants and, where available, for such
traditional pollutants as COD, oil and grease, and BOD5.
The term "raw wastewater" refers to the liquid effluent from a
printing process or processes prior to any form of wastewater
treatment. Process steps designed primarily to recover materials
from a wastewater stream (i.e., silver recovery) are considered
to be in-plant controls. Wastewater data were obtained from
screening and verification sampling at printing plants.
Representatives of some plants, municipal sewer districts, and
state and federal agencies also supplied historical data which is
contained in the Appendix. Long-term data were, in general, not
available. Therefore, data from screening and verification
sampling are emphasized because sampling techniques, individual
plant operations, and waste stream components are known and can
be documented. The Agency could not identify standard production
indicators which could be used to calculate raw wasteloads on a
mass discharge per unit of production basis.
GENERAL CHARACTERISTICS
The major sources of process wastewater in the printing industry,
include (a) photoprocessing, (b) platemaking, and (c) pressroom
operations. In general, these processes are not performed on a
continuous basis. Film processing rarely occurs on all three
shifts of a three-shift operation. Platemaking operations may
only be employed a limited number of hours each day or week.
Length of pressrun varies with the nature and volume of the
material being printed. Thus, wastewater is not generated
continuously and its constituents vary depending on which
processes are in operation at a particular time.
At the majority of printing plants, process wastewater is not
segregated from nonprocess streams such as noncontact cooling
water or sanitary wastes. In addition, process waste streams
generally contain wastewater from more than one subcategory
operation.
57
-------
The volume of wastewater discharged from printing plants is low
compared to other industries. A discharge of 76,000 liters/day
(20,000 gpd) is a very large flow in this industry and is
extremely rare; at most plants fewer than 190 liters/day (50 gpd)
of wastewater are discharged.
PHOTOGRAPHIC PROCESSING WASTEWATER
As reported in Section III, film processing involves applying a
developer solution to the film, contacting the film with a fixing
solution, and washing the film in water to remove excess fix. In
recent years, much film processing has been done automatically
using film processing equipment rather than manually in sinks and
trays.
Process wastewater includes spent fixing and developing solutions
and rinse water. The wastewater contains hydroquinone and other
developers, sulfates, sulfites, acetic acid, and soluble silver
salts of thiosulfates. Most automatic film processors are
equipped with electrolytic or metallic replacement silver
recovery units to reclaim silver before discharge. In the
metallic replacement system, the silver content is reduced by
substituting other metals for silver. In most cases, iron, in
the form of steel wool, is substituted; however, in some cases
water soluble sulfur compounds of zinc are substituted for the
silver. Developer and fix consumption varies from less than 4
liters per week (1 gal/wk) in small shops to more than 380
liters/wk (100 gal/wk) in large establishments. Most film
processing machines are designed such that the rinse water runs
the entire time the machine is on. Rinse water flow varies from
4 to 15 liters/minute (1 to 4 gal/minute) per processor, and
usually provides considerable dilution of the discharged
developing and fixing solution. Some film processors have been
equipped with solenoid valves which allow the rinse water to flow
only when film is in the processor.
At a small plant, only one automatic film processor may be
operated for 8 hours or less per day; at a large plant, more than
10 processors may be operated for two or more shifts per day.
Thus, wastewater volume varies considerably with plant size from
less than 190 liters/day (50 gal/day) to more than 38,000
liters/day (10,000 gal/day).
PLATEMAKING WASTEWATER
Unlike photoprocessing, platemaking methods depend on the
printing process (lithography, letterpress, gravure, flexography,
or screen). Alternate platemaking procedures exist for each
printing process. The number of plates produced and, hence, the
58
-------
volume of wastewater generated vary with level of production and
length of press run. Generally, platemaking operations produce
less wastewater than photographic operations. However, the
wastewater is more likely to contain heavy metals and other
contaminants because of the acids, salts, and solvents used to
etch or develop the metal, plastic, and photopolymer plate
surfaces. At many of the plants visited, part or all of the
platemaking wastewaters (average volume of less than 1,900
liters/day (500 gpd)) were hauled from the plant or pretreated to
meet local effluent standards prior to discharge to publicly
owned treatment works.
PRINTING WASTEWATER
The process of transferring ink from an image carrier to paper
does not generate wastewater except in lithographic printing
where fountain solutions are replaced periodically. Typical
wastewater sources are processes other than the actual printing
such as press cleanup or activated carbon solvent recovery
systems used at gravure printing plants.
Lithographic Fountain Solutions
In lithographic printing, the ink repellance of the non-image
areas of the printing plate must be maintained chemically by
dampening the plate with a fountain solution. There are two
major dampening systems used on lithographic printing presses.
In the conventional system, the fountain solution is applied to
the plate from a rubber roller. In the Dahlgren system, the
dampening solution is applied to an ink covered roller; then the
fountain solution and ink are simultaneously applied to the
plate. Conventional fountain solutions are aqueous solutions
containing gum arabic, phosphoric acid, a bactericide, and an
etch. The etch, usually a dichromate or magnesium nitrate,
minimizes the corrosion of aluminum plates. Dahlgren dampening
solutions are similar to the conventional solutions, except that
they contain up to 30 percent isopropanol. Fountain solutions
readily accumulate ink constituents and, as a result, must be
replaced periodically. At a large lithographic printing plant,
57 to 76 liters (15 to 20 gallons) of spent fountain solutions
may be disposed of each week.
Press Cleanup
After a run, nonwater-based inks are removed from the presses
with rags and cleaning solvents. The particular solvent used
depends on the type of ink. Typical solvents include: (1)
aliphatic hydrocarbons, (2) aromatics, (3) ketones, (4)
chlorinated hydrocarbons, (5) alcohols, and (6) miscellaneous
59
-------
solvents such as ethylacetate or proprietary solvent mixtures
such as Cellosolves. Due to its low cost, kerosene is also
widely used.
Some waste ink and solvents may be combined with other waste
streams and discharged. In most cases, however, the wastes are
small in volume—4 to 40 liters/day (1 to 10 gpd) per press—and
are usually stored in 210-liter (55-gallon) drums and hauled from
the premises. The rags used in press cleanup are usually sent to
commercial laundries for cleaning.
In pressroom operations where water-based inks are used, press
cleanup involves a water wash of the press inking system between
ink color changes. The number of times this occurs depends on
the nature of the plant business. Wastewater generated per ink
change typically varies from 40 to 230 liters (10 to 60 gallons)
per press, depending on whether an ink change involves only a
change in ink shade or a full color change. At some plants, all
press waste is contract hauled to disposal. The volume of
wastewater discharged varies from 0 to 1,900 liters/day (0 to 500
gpd). Representatives of 50 plants where water-based inks are
used responded to the data requesr. survey; only two reported
wastewater discharges of more than 190 liters/day (50 gpd).
Toxic pollutants present in these discharges are usually
components of the ink such as lead, chromium, and zinc.
Currently, the use of water-based inks ir. governed by the type of
substrate to be printed. According to industry contacts,
virtually all water-based inks are used .In flexographic printing
on kraft substrates (corrugated containers and bags or labels).
Limited use of water-based inks also occurs within SIC 2754
(gravure printing). Research is ongoing within the ink industry
to manufacture a water-based ink for use on a nonabsorbent
substrate. Advantages of water-based inks include good press
stability and printability, absence of fire hazard (although
water-based ink containing sufficient alcohol will burn),
convenience, and economy of water for cleanup. Also, these inks
do not cause the air pollution problems associated with certain
solvent-based inks, especially the volatile inks used in gravure
printing.
OTHER WASTEWATERS
Wastewater may also be generated from mixing and blending of
inks, screen reclamation in screen printing, and from gravure
solvent recovery. At plants where inks are blended or mixed,
small amounts of wastes are generated during cleanup. These
wastes may be discharged or drummed. In screen printing, screens
may be recovered after a press run by washing the screens with a
60
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caustic solution to remove the stencils. Resulting wastewater
contains stencil materials and ink constituents such as
precipitated chalk, pigments, and oil varnishes. At gravure
printing plants, air laden with volatile solvents is vented to
activated carbon beds. The beds are steam cleaned and the
solvents are recovered by decanting and, in some cases,
distilling the condensate. Wastewater from the solvent recovery
process is contaminated with water-miscible solvents.
RAW WASTEWATER DATA
When screening sampling was performed, Agency efforts to
subcategorize the printing and publishing industry had only
begun. As a result, samples of total plant effluent were
collected. Thus, most samples were composed of wastes from more
than one subcategory operation and, in many cases, included
nonprocess wastewater streams. The Agency believes that these
nonprocess wastewater streams contribute few, if any, toxic
pollutants, unless otherwise indicated. Table V-1 lists the
plants and process operations sampled.
Screening and Verification Sampling Data
Table V-2 lists the number of toxic pollutants detected in raw
wastewaters by subcategory. Tables V-3 and V-4 present available
toxic, conventional, and nonconventional pollutant data for
photoprocessing subcategory raw wastewaters. Table V-5 describes
the sampling sites at plants where photoprocessing and
nonmetallic platemaking operations are performed. Toxic
pollutant data for combined photoprocessing and nonmetallic
platemaking raw wastewaters are presented in Table V-6. Toxic
pollutant data for the pressroom (nonwater-based inks)
subcategory are presented in Table V-7. Toxic, conventional, and
nonconventional pollutant data for the pressroom (water-based
inks) subcategory are presented in Tables V-8 and V-9.
Data are reported for toxic pollutants which were detected. A
value reported as less than (<) signifies that traces of the
substance were identified. Pollutant loadings are shown in
parentheses where flow data are available. Screening sampling
data were used to determine presence or absence of toxic
pollutants.
The verification sampling results for two water-based ink plants
are summarized in Table V-8 and Table V-9. As discussed in
Section II, the use of water-based inks received additional
attention after preliminary subcategorization to determine
whether exclusion from regulation under Paragraph 8(a)(iv) of the
Settlement Agreement was justified.
61
-------
Historical Data
Historical wastewater data were obtained from plant
representatives and from local, state, and federal government
personnel. These data are presented in the Appendix.
62
-------
TABLE V-l
PRINTING PLANTS SAMPLED IN
SCREENING AND VERIFICATION PROGRAM
Plant
Code
4975
6372
9011
8190
9020
6653
9012
1303
5478
2382
7194
8038
1303
9002
5478
5478
9018
Subcategory
Photoprocessing
Combined
Photoprocessing
and
Nonmetal lie
Platemaking
Pressroom
(Nonwater-Based Inks)
Pressroom
(Water-Based Inks)
Flow, gpd
3230
6000
240003
200003
Unknown
115003
150003
200003
270003
3000
Unknown
Unknown
100
200
500
300 Average6
164 Average"
Total Toxic
Raw Waste Load
Ib/day
0.0501
0.742
<0.31
<0.33
Unknown^
<0.175
<0.163
<0.19
<0.26
<0.021
Unknown^*'*
Unknown^
<0.012
<0.02
<0.0855
<0.65
<0.92
Type of
Discharge
Indirect
Indirect
Ind irect
Direct
Indirect
Indirect
Ind irect
Indirect
Direct
Indirect
Ind irect
Indirect
Indirect
Indirect
Direct
Direct
Indirect
1 Data not reported for acid extractable, base/neutral extractable, or
pesticide fractions of screening samples collected at these plants.
2 Not including chromium used for cooling tower water treatment only.
3 Flows include nonprocess wastewater.
4 Raw waste load calculated only for plants with flow data.
^ Not including chromium (0.455 Ib) and lead (2.01 Ib) found at substantially
lower levels in subsequent verification sampling at the same plant.
6 Average of three days data from verification sampling; all other data are from
one day screening sampling.
63
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TABLE V-2
NUMBER OF TOXIC POLLUTANTS DETECTED IN SCREENING AND VERIFICATION PROGRAM1
Subcategory
Photo-
Processing
Combined Photo-
processing and
Nonraetal lie
Platemaking^
Pressroom
(Nonwater-
Based Inks)
Pressroom
(Water-Based
Inks)3
Number of
Plants Sampled
Number of Toxic
Pollutants Detected
# of VOAs
# of Acid Extractables
# of Base/Neutral
Extractables
# of Metals
# of Pesticides
and PCBs4
# of Other
15
4
2
0
8
30
11
1
3
10
27
12
0
3
10
29
7
2
5
13
0
1 (cyanide)
1 (cyanide)
1 (cyanide) 1 (cyanide)
1 All data obtained from one day screening sampling unless otherwise noted.
2 Photoprocessing and nonmetallic platemaking data combined due to nonsegregated
discharge from plants sampled.
3 Data obtained from three day verification sampling.
4 Pesticides tentatively identified by gas chromatography (electron capture) but
not confirmed by gas chromatography/mass spectrometry.
64
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TABLE V-3
AVAILABLE SCREENING SAMPLING RAW WASTE DATA
PHOTOPROCESSING SUBCATEGORY OPERATIONS AT PLANT 49751
Concentration Raw Waste Load^
Pollutant
Cadmium
Chromium
Copper
Nickel
Silver
Zinc
TOTAL3
ug/1
600
30
60
50
560
560
Ib/day
0.0162
0.00081
0.0016
0.0013
0.0151
0.0151
0.050
1 Raw wastewater is from film processing and sanitary sewage.
2 Process wastewater flow 3,230 gallons per day.
3 No data were reported for the acid extractable, base/neutral
extractable, or pesticide fractions of the screening sample collected
at this plant.
65
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TABLE V-4
SCREENING SAMPLING RAW WASTE DATA
PHOTOPROCESSING SUBCATEGORY OPERATIONS AT PLANT 63721
Toxic Pollutants
Pollutant
Methylene chloride
Chloroform
Trichloroethylene
Toluene
Phenol
p-chloro-m-creosol
Arsenic
Cadmium
Copper
Chromium^
Lead
Nickel
Silver
Zinc
Cyanide
TOTAL3
ug/1
2
11
13
5
18
12
77
10
260
36,000
14
3,600
390
9,300
840
Ib/day
0.0001
0.00055
0.00065
0.0003
0.0009
0.0006
0.0039
0.0005
0.013
1.8
0.0007
0.18
0.020
0.47
0.04
0.74
Conventional and
Nonconventional Pollutants
tng/1 Ib/day
Ammonia
TKN
T-phosphorus
COD
Suspended Solids
Dissolved Solids
Volatile Solids
Total Solids
Total Phenols
BOD5
Oil & Grease
43.0
52.3
3.14
264
6.5
758
141
764
36
24.2
18
2.15
2.62
0.16
13.21
0.33
37.93
7.06
38.23
1.8
1.21
0.9
Wastewater flow 6,000 gpd.
Chromium added as part of cooling tower water treatment program is
not used in photoprocessing. Data for chromium were not included in
daily raw waste load.
Data from one 24-hour flow proportioned composite sample.
66
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TABLE V-5
SAMPLING SITE DESCRIPTIONS FOR PLANTS IN THE PHOTOPROCESSING AND
NONMETALLIC PLATEMAKING SUBCATEGORIES
Plant 9011:
Plant 81901:
Plant 9020:
Plant 6653:
Plant 9012:
Plant 1303:
Plant 5478:
Plant 2382:
Plant 7194:
Raw wastewater from photoprocessing, nonmetallic
platemaking, and pressroom (nonwater-based inks)
operations combined with sanitary sewage.
Raw wastewater from photoprocessing, nonmetallic plate-
making, press roller washing, truck and battery washing,
and cooling tower blowdown.
Raw wastewater from photoprocessing, nonmetallic plate-
making, and pressroom (nonwater-based inks) operations
combined with sanitary sewage.
Raw wastewater from photoprocessing and nonmetallic
platemaking.
Raw wastewater from photoprocessing and nonmetallic
platemaking.
Raw wastewater from photoprocessing and nonmetallic
platemaking combined with sanitary sewage.
Raw wastewater from photoprocessing and nonmetallic
platemaking combined with pretreated pressroom (water-
based inks) effluent and sanitary sewage.
Raw wastewater from photoprocessing, nonmetallic plate-
making, and pressroom (nonwater-based inks) operations
combined with sanitary sewage.
Raw wastewater from photoprocessing, nonmetallic plate-
making, pressroom (nonwater-based inks) operations, and
cooling tower blowdown.
This plant prints with nonwater-based inks. Press rollers are
taken off the press and washed with an aqueous caustic solution.
Batteries are used as a direct current source for electroplating.
67
-------
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70
-------
TABLE V-7
TOXIC POLLUTANT SCREENING SAMPLING RAW WASTE DATA
PRESSROOM (NONWATER-BASED INKS) SUBCATEGORY
Raw Waste Data, ug/1 (Ib/day)
Plant Code
Pollutant
80381
13032
90023
Benzene
Carbon Tetrachloride
1,2-Dichloroethane
1,1,1-Trichloroethane
ND
ND
180
1,1-Dichloroe-thane 30
1,1,2,2-Tetrachloroethane ND
Bis(2-chloroethyl)ether ND
Chloroform
Ethylbenzene
Methylene Chloride
20
10
130
ND
ND
ND
ND
ND
20
(0.00002)
2600
(0.0022)
«0.000008)
2500
«0.0021)
«0. 000008)
60
(0.0001)
10
(0.00002)
10
(0.00002)
10
(0.00002)
ND
ND
ND
70
(0.0001)
260
(0.00043)
130
(0.00022)
Raw wastewater from electrotype platemaking combined with sanitary
sewage.
Drummed waste ink from lithographic printing process.
Decant from activated carbon solvent recovery of air emissions
from gravure printing presses.
ND means not detected.
71
-------
TABLE V-7
TOXIC POLLUTANT SCREENING SAMPLING RAW WASTE DATA
PRESSROOM (NONWATER-BASED INKS) SUBCATEGORY
(Continued, Page 2 of 3)
Raw Waste Data, ug/1 (Ib/day)
Plant Code
Pollutant 80381
Naphthalene ND4
Bis(2-ethylhexyl)pthalate <10
Di-n-butyl phthalate <10
Toluene <10
Trichloroethylene ND
B-endosulfan-beta^ ND
Antimony <10
Cadmium 10
Chromium 24
13032
2600
(0.0022)
ND
ND
370
(0.00031)
«0. 000008)
ND
«0. 000008)
«0. 000008)
79
(0.000066)
90023
ND
16
(0.000027)
«0. 00002)
190
(0.00032)
ND
1
(0.000002)
ND
«0. 00002)
24
(0.000040)
1 Raw wastewater from electrotype platemaking combined with sanitary
sewage.
2 Drummed waste ink from lithographic printing process.
3 Decant from activated carbon solvent recovery of air emissions
from gravure printing presses.
^ ND means not detected.
5 Pesticide tentatively identified by gas chromatography (electron
capture) but not confirmed by gas chromatography/mass spectrometry.
72
-------
TABLE V-7
TOXIC POLLUTANT SCREENING SAMPLING RAW WASTE DATA
PRESSROOM (NONWATER-BASED INKS) SUBCATEGORY
(Continued, Page 3 of 3)
Raw Waste Data, ug/1 (Ib/day)
Pollutant
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Zinc
TOTAL6
Plant Code
80381 ' 13032
57 1800
(0.0015)
40 110
(0.00009)
60 3740
(0.0031)
3.7 0.55
(0.00000046)
<10 ND4
«0. 000008)
«0. 000008)
90 86
UK7 «0.012)
90023
73
(0.00012)
200
(0.00033)
40
(0.000067)
1.9
(0.0000032)
17
(0.000028)
ND
«0. 00002)
ND
«0.002)
Flow (gallons per day)
NA8
100
200
1 Raw wastewater from electrotype platetnaking combined with sanitary
sewage.
2 Drummed waste ink from lithographic printing process.
3 Decant from activated carbon solvent recovery of air emissions
from gravure printing presses.
^ ND means not detected.
5 Pesticide tentatively identified by gas chromatography (electron
capture) but not confirmed by gas chromatography/mass spectrometry.
6 Total toxic pollutant raw waste load (Ib/day) calculated only for
plants with flow data.
' UK means unknown.
8 NA means not available.
73
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75
-------
TABLE V-9
VERIFICATION SAMPLING CONVENTIONAL
AND NONCONVENTIONAL POLLUTANT RAW WASTE DATA
PRESSROOM (WATER-BASED INKS) SUBCATEGORY1
Plant 5478 Plant 9018
Flexographic Ink Waste Gravure Ink Waste
Pollutant mg/1 (Ib/day) mg/1 (Ib/day)
Total Phenols 510 (0.0013) 18,000 (0.025)
BOD5 3,000 (8) 3,500 (4.8)
Total Solids 5,100 (13) 68,000 (91)
Total Suspended Solids 920 (2.3) 2,200 (2.6)
Total Dissolved Solids 4,200 (11) 66,000 (88)
Total Volatile Solids 3,000 (8) —2
COD 7,700 (19) 113,000 (150)
TOC 7,300 (18) 26,000 (34)
Oil and Grease 33 (0.083) 1,700 (2.7)
Average Flow (gpd) 300 164
1 Average of data obtained from three day verification sampling.
* Not analyzed.
76
-------
SECTION VI
CONTROL AND TREATMENT TECHNOLOGY
INTRODUCTION
In this section the technologies used for the control and
treatment of wastewater pollutants at printing and publishing
plants visited during the screening and verification program are
discussed. As discussed in previous sections the Agency
determined that six of the eight subcategories of the printing
and publishing point source category would be excluded from
regulation pursuant to Paragraph 8 (a)(iv) of the Settlement
Agreement. Therefore, the technical study of the art and copy
preparation and composition, finishing and binding,
photoprocessing, nonmetallic platemaking, pressroom (nonwater-
based inks), and pressroom (water-based inks) subcategories was
terminated after completion of the screening and verification
sampling programs. Also, because gravure cylinder preparation
and metallic platemaking will be addressed as part of the metal
finishing point source category, treatment system data for plants
in these subcategories are not included in this document.
Wastewater control and treatment or pretreatment technologies
used at plants visited and sampled during this study have been
emphasized in this document. One should not assume that the
control and treatment technologies discussed in this report are
the only technologies applicable to treating printing and
publishing wastewaters.
SUMMARY OF AVAILABLE DATA
General
Table VI-1 lists the types of processes and treatment systems
employed at the sampled plants. The major operations at these
plants fall into the photoprocessing, nonmetallic platemaking,
and pressroom subcategories. Two plants were direct dischargers;
the others were indirect dischargers (i.e., discharge to
municipal sewers).
Wastewater flows at plants in the industry where wastewater is
discharged were generally not continuous and ranged from 95
liters/day (25 gpd) to more than 76,000 liters/day (20,000 gpd).
Many of the wastes, especially those containing heavy metals, are
generated and treated on a batch basis. At most of the plants
visited, all or part of the pressroom effluents are contract
hauled. Some form of treatment was employed at only 418 of the
5,004 plants whose representatives responded to the Data Request
77
-------
i
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-------
Flexographic Ink Cleanup Sinks (2)
(Note: all PVC piping)
Simp Pump
H2S04 to pH 4.5 •
Aluninun Sulphate •
Johns Manville 545 Celite-
600-gal. Fiberglass®
Storage Tank
600-gal. Fiberglass®
Batch Treatment Tank
15-psi Vacuum
Paddle Mixer
5-10 min./batch
30" Dia. Trommel
Rotary Vacuum Filter
Sludge and
Paper Filter •
to Bin
Solid Waste
Filtrate to
Biological Treatment
FIGURE VI-1. METALS TREATMENT SYSTEM AT PLANT 5478
79
-------
PLANT
Conbined Waste: totals Treatment Effluent 600 gpd
Photoprocessing, (bimetallic
Platemaking and Nonprocess
Wastewater 2%00 gpd
Manhole 30000 gpd
20'
Aeration Basin
Minimum 12-hr. Detention
12'
deep
Final Clarifier
Pump
Deep Bed Sand Filter
(400 sq. ft.)
2' Sand
2' 1/2" Bock
2' 1/2" Rock
Percolated to Groundwater
FIGURE VI-2. BIOIDGICAL THEA3MENT SYSTEM AT PLANT 5478
80
-------
TABLE VI-2
TOXIC POLLUTANT REMOVAL IN BATCH METALS
TREATMENT SYSTEM AT PLANT 54781
Parameter
Chromium
Copper
Lead
Nickel
Zinc
Ethylbenzene
Benzene
Chloroform
Arsenic
Influent to
Treatment (ug/1)
109,000
4,610
482 , 000
74
10,700
1,780
190
900
33
Effluent From
Treatment (ug/1)
1,690
771
3,830
71
14,300
80
10
5
6
Percent
Remova 1
98
83
99
4
96
95
99
82
Flow = 600 gpd from water-based ink press cleaning.
81
-------
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TABLE VI-4
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT
REMOVAL IN BIOLOGICAL TREATMENT SYSTEM AT PLANT 54781
Influent to Effluent From Percent
Parameter (mg/1) Biological System Biological System Removal
COD
BOD5
TOC
NH3 as N
TKN as N
N03, N02 as N
Total Suspended Solids
Total Volatile Solids
270
130
84
21
50
0.06
160
300
35
<6.0
9.0
2.6
3.4
5.7
3.0
170
87
>95
89
88
93
98
43
1 Flow 30,000 gpd; 29,400 gpd sanitary, cooling, photoprocessing
and nonmetallic plateraaking process wastewater and 600 gpd metals
pretreatraent effluent.
83
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Survey. In many instances, respondents who reported treatment
were referring to silver recovery of photoprocessing wastes for
economic purposes. As reported in Section III, process
wastewater was discharged directly at less than 54 plants
nationwide.
Wastewater treatment systems are not employed at many small
plants. The data presented here were obtained from screening or
verification sampling at large plants. Sampling and analysis
procedures followed the Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollutants.(7)
Data are reported only for toxic pollutants which were detected
in raw or treated effluent samples and for conventional
pollutants which were analyzed.
Plant 5478
At Plant 5478, gummed labels, pricing stickers, paper bags,
plastic bags, sales slips, and boxes are printed by the
lithographic, flexographic, and letterpress processes.
Water-based inks are used in flexographic printing. Sources of
wastewater are the flexographic press cleanup, film processing,
and the lithographic and flexographic platemaking operations. A
metals treatment system and a package-type biological system are
employed at the plant. Schematics of these treatment systems are
shown in Figures VI-1 and VI-2.
Wastewater generated from cleanup of the flexographic printing
presses is batch treated for metals removal in a 2,300 liter (600
gal) fiberglass tank equipped with a paddle mixer. After the pH
is adjusted to 4.5 with sulfuric acid; alum and a filter aid are
added. (The pH adjustment is necessary to achieve optimum
coagulation and flocculation). The treated wastewater flows
through a 76-cm (30-inch) diameter vacuum filter. The filtrate
(2,300 liters/day (600 gpd)) combines with 111,000 liters/day
(29,400 gpd) of photoprocessing, platemaking, and nonprocess
wastewater to form the influent to the biological treatment
system. The biological system consists of an aeration tank and a
clarifier. The clarifier sludge is partially recycled; the
portion which is wasted is contract hauled to a landfill. The
effluent from the biological system percolates to groundwater
through a multimedia filter consisting of a 61-cm (2 foot) top
layer of sand over a 122-cm (4 foot) bed of rock. The sand
filter can be bypassed, in which case the biological treatment
system effluent flows directly to a creek.
The reductions of toxic pollutants in the metals treatment system
and in the biological system are shown in Tables VI-2 and VI-3.
84
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The reductions of conventional and nonconventional pollutants in
the biological system are shown in Table VI-4.
Plant 8190
Magazines, comic books, and commercial publications are printed
and bound at plant 8190. Photoprocessing and platemaking
operations are performed in conjunction with letterpress and
lithographic printing. Products are bound with hot melt glues by
the "perfect binding" process. Water is not used in the binding
process.
Pressroom effluents, including cleanup and waste ink are stored
in a 5,700 liter (1,500 gal) tank. Twice a month, the tank is
emptied and its contents are hauled from the plant by a licensed
scavenger. Sanitary and cooling wastewaters are segregated from
process wastewater and discharged to a municipal sewer.
Approximately 148,000 liters/day (39,000 gpd) of wastewater from
photoprocessing, platemaking, press roller washing, truck
washing, battery washing2, and cooling tower blowdown is pumped
to the treatment system illustrated in Figure VI-3. Fix solution
used in photoprocessing operations flows through a three-stage
silver recovery unit prior to entering the treatment system. The
cooling water contains the following additives: a phosphate ester
or hydrochloric acid, sodium nitrate, and biocides. Phosphate
esters and hydrochloric acid are used to prevent scaling; sodium
nitrate prevents corrosion/ and biocides control algae.
Flocculants are added to the wastewater in the combination flash
mix and flocculation tank. The next step in the treatment
process is a flotation-clarifier unit which provides both
settling and flotation of floe. Flotation is assisted by bubble
aeration. The sludge from the clarifier is pumped to one of two
interconnected settling basins, each of which is approximately
0.506 hectares (1.25 acres) in area and has a volume of
approximately 4.9 million liters (1.3 million gal). Supernatant
from the settling ponds may be recirculated to the flash-mix and
flocculation tank. Sludge is periodically removed by dredging
and deposited in a landfill (at the time of the visit, the east
pond had recently been cleaned and was not in operation). The
clarifier effluent flows through a garnet filter bed followed by
an alumina filter bed, and then enters an aerated tank. Filter
backwash, which occurs for 15 minutes at the rate of 150
2Batteries are used as a direct current source in electroplating
operations.
85
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liters/minute (40 gpm) once every 6 hours, is pumped to the
settling basin. The final treatment step consists of an
activated carbon system which receives a flow of approximately 76
liters/minute (20 gpm). Carbon is thermally regenerated on site
about twice monthly. Treated effluent is discharged into a
creek. Wastewater characteristics and treatment efficiencies are
shown in Table VI-5.
Plants 6653 and 9012
The same newspaper is printed by the offset lithographic process
at plants 6653 and 9012. These establishments are two
manufacturing locations of a large newspaper publishing company.
Process wastewater is generated from photoprocessing operations
and from platemaking operations in which automatic plant
processors are employed. Wastewater is handled in the same
manner at both plants. Effluents are filtered through 61-cm
(2-foot) diameter, 91-cm (3-foot) deep limestone filters prior to
discharge to a municipal sewer. The filters are used for pH
adjustment. The influent and effluent characteristics for the
filter at each plant are presented in Tables VI-6 and VI-7.
Plant 5430
Textbooks, encyclopedias, and other books are printed at plant
5430. Photoprocessing, nonmetallic platemaking, ink blending,
finishing, and binding operations are performed in conjunction
with lithographic and letterpress printing. Spent solvents,
waste glues, varnishes, laquers, and oils are drummed and
contract hauled from the premises to a landfill. Hot water,
steam, and a biodegradable detergent are used to launder 182-kg
(400 pound) batches of ink rags. As much as 1,140 kg (2,500
pounds) of rags are washed during one shift. Wastewaters from
photoprocessing, nonmetallic platemaking, and rag laundering are
treated in the system illustrated in Figure VI-4.
Acidic wastewater (pH 2-4) from ink blending, photoprocessing,
and nonmetallic platemaking and alkaline wastewater (pH 9-11)
from rag laundering are segregated and stored in 38,000 liter
(10,000 gal) holding tanks. When sufficient volumes are
accumulated, 3,800 liters (1,000 gal) of the acidic wastewater
are combined with 7,600 liters (2,000 gal) of the alkaline
wastewater in a 13,000 liter (3,500 gal) reactor equipped with a
two-speed paddle mixer. Hexavalent chromium is reduced with
sodium metabisulfite. The progress of this reaction is monitored
with an oxidation reduction potential meter. Metals
precipitation is accomplished by adding sufficient caustic soda
to raise the pH to 10. Jar tests are performed to determine
optimum conditions for flocculation, and cationic or anionic
86
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polymer flocculants are added as appropriate. The reduction,
precipitation, and flocculation reactions may be controlled
manually or automatically. The reactions take from 1 to 2 hours
but settling time may vary from 4 to 20 hours.
After settling, sludge and supernatant are pumped to further
treatment. Sludge (two to three precent solids) is collected in
a holding tank and then concentrated by centrifuging. The sludge
cake (13 to 20 percent solids) is hauled to a landfill and the
centrate is discharged to the sewer, or recycled to the sludge
holding tank. Reactor supernatant is filtered by a fabric filter
and then metered to the sewer from a 19,000-liter (5,000-gal)
holding tank. Batches which contain unsatisfactory levels of
suspended solids are recycled to the reactor. Filtered solids
are hauled to a landfill. The reduction of toxic pollutants in
the reactor is shown in Table VI-8.
87
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UDIV[CO
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-------
TABLE VI-5
REDUCTION OF TOXIC, CONVENTIONAL, AND NONCONVENTIONAL POLLUTANTS
IN PHYSICAL/CHEMICAL TREATMENT SYSTEM AT PLANT 81901
Pollutant
Chromium (ug/1)
Copper (ug/1)
Lead (ug/1)
Silver (ug/1)
Zinc (ug/1)
BOD5 (mg/1)
COD (mg/1)
TOG (mg/1)
NH3 as N (mg/1)
TKN as N (mg/1)
Total Suspended Solids
(mg/1)
Total Volatile Solids
(mg/1)
Raw
Wastewater
1,190
52
46.1
8.5
395
570
2,700
560
8.4
1.2
40
360
Treated
Effluent
75
12
7.5
0.5
28
<6.0
31
9.0
0.4
0.7
4.0
50
Percent
Removal
94
77
84
94
93
>98
99
98
95
42
90
86
approximately 39,000 gpd. Chromium is added as part of
cooling water treatment program. Raw wastewater does not include
contract hauled pressroom effluent.
89
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TABLE VI-6
REDUCTION OF TOXIC POLLUTANTS IN
LIMESTONE FILTER AT PLANT 66531>2
Parameter
PH3
Cadmium
Chromium
Copper
Lead
Silver
Zinc
Mercury
Influent
(ug/1)
8.4
70.5
281
180
22.4
51.3
553
11
Effluent
(ug/1)
9.1
1.25
11
39
0.6
29.8
—
2.1
Percent
Removal
98
96
78
97
42
81
Wastewater flow is estimated to be 11,500 gpd.
No toxic organic pollutants were detected in either of the
screening samples collected.
pH readings from grab samples collected October 13, 1977.
: Not analyzed.
90
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TABLE VI-7
REDUCTION OF TOXIC POLLUTANTS
IN LIMESTONE FILTER AT PLANT 90121'2
Parameter
PH3
Cadmium
Cyanide
Zinc
Mercury
Influent
(ug/1)
8.8
319
560
35.4
3.3
Effluent
(ug/1)
9.3
8.52
120
40
1.7
Percent
Removal
97
79
48
1 No flow data available.
2 No toxic organic pollutants were detected in either of the
screening samples collected.
3 pH reading from grab samples collected October 13, 1977.
91
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-------
TABLE VI-8
REDUCTION OF TOXIC POLLUTANTS IN
METALS TREATMENT SYSTEM AT PLANT 5430
Parameter
Bis ( 2-ethylhexyl ) phthalat e
Phenol
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Cadmium
Chromium
Copper
Lead
Zinc
Blended Raw
Wastewater
(ug/1)
9,800
500
200
800
89
50
13,755
20,950
4,200
220,000
Reactor
Effluent
(ug/1)
<10
500
<10
<10
<10
13
3,413
692
36
685
Percent
Removal
>99
0
>95
>99
>89
74
75
97
99
>99
A maximum of four 3,500 gallon batches are treated per day.
93
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SECTION VII
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE (BAT),
NEW SOURCE PERFORMANCE STANDARDS (NSPS), AND
PRETREATMENT STANDARDS FOR NEW AND EXISTING SOURCES (PSNS AND PSES)
INTRODUCTION
The Agency has excluded the six printing and publishing
subcategories which are the main subject of this document from
national regulations under the provisions of Paragraph 8 (a)(iv)
of the Settlement Agreement. (1)(2) This section summarizes
information and data which support the Agency's decision.
Art and copy preparation and composition operations do not
involve the use of water and finishing and binding operations are
essentially dry processes. Total toxic pollutant raw waste loads
from plants in the remaining four subcategories are less than 1.2
pounds per day per plant. EPA estimates that there are 56,000
printing and publishing manufacturing establishments at which at
least one, but usually several, process operations are employed.
The results of the data request survey indicate that the median
wastewater discharge volume at these plants is between 98 and 190
liters per day (26 and 50 gallons per day). Based on NPDES
permit information, there are less than 54 printing and
publishing plants nationwide where process wastewater is
discharged directly to navigable waters. At all other plants,
wastewaters are either not discharged or are discharged to
publicly owned treatment works.
ART AND COPY PREPARATION AND COMPOSITION SUBCATEGORY
Decision Not to Establish National Regulations
Based on an extrapolation of the results of the data request
survey, there are approximately 32,000 plants where art and copy
preparation and composition operations are performed. No water
is used in these operations. Therefore, BAT, NSPS, PSNS, and
PSES regulations will not be established for this subcategory,
under the authority of Paragraph 8 (a)(iv) of the Settlement
Agreement.
95
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PHOTOPROCESSING (PRINTING AND/OR PUBLISHING FACILITIES ENGAGED IN
INTERNAL PHOTOPROCESSING OPERATIONS) AND NONMETALLIC PLATEMAKING
SUBCATEGORIES
Decision Not to Establish National Regulations
Discharge of heavy metals and other toxic pollutants may occur
from plants in the photoprocessing and nonmetallic platemaking
subcategories. While potential exists for discharge, the amount
and toxicity of the pollutants contained in the raw wastewater
discharges do not justify developing national regulations.
Therefore, BAT, NSPS, PSNS, and PSES regulations will not be
established for these subcategories, under the authority of
Paragraph 8 (a)(iv) of the Settlement Agreement.
Data Evaluation
Except in two instances, it was not possible to segregate
photoprocessing and nonmetallic platemaking waste streams in the
screening sampling program; therefore, the decision not to
regulate these subcategories is based on the combined raw waste
loads from both processes.
Table VII-1 summarizes the screening sampling data obtained at
seven large facilities where photoprocessing and nonmetallic
platemaking operations are performed. The discharge volumes at
these seven large plants ranged between 11,000 and 100,000 liters
(3,000 and 27,000 gallons) per day. The pollutant loadings at
these plants are expected to be significantly greater than at
smaller facilities which make up the majority of the plants in
these subcategories. The greatest total discharge of toxic
pollutants from any individual plant was less than 0.150
kilograms (0.329 pounds) per day.
Photoprocessing Subcategory Plant Profile
Based on an extrapolation of the results of the data request
survey, there are approximately 41,000 plants where
photoprocesssing operations are performed. At over 99 percent of
these facilities process wastewater is either discharged to
publicly owned treatment works or not discharged.
Nonmetallic Platemaking Subcategory Plant Profile
Based on an extrapolation of the results of the data request
survey, there are approximately 43,000 plants where nonmetallic
platemaking operations are performed. At over 99 percent of
96
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TABLE VII-1
TOXIC POLLUTANT RAW WASTE LOADS FROM PHOTOPROCESSING
AND NONMETALLIC'PLATEMAKING OPERATIONS
Plant Code
Pesticides^
(Ib/day)
Organics
(Ib/day)
Metals and
Cyanide
(Ib/day)
Total Toxic
Pollutants
(Ib/day)
9011 81901
ND3 0.005
<0.108 <0.222
<0.201 <0.102
<0.310 <0.329
6653 9012 1303 5478 2382
ND ND <0.001 ND <0.002
<0.059 <0.037 <0.092 ND MR4
0.116 <0.126 <0.097 <0.260 <0.017
<0.175 <0.163 <0.190 <0.260 <0.020
* Chromium added as part of cooling tower water treatment program at
Plant 8190 and is not used in photoprocessing or nonmetallic
platemaking. Data for chromium were not included in the raw waste
load for this plant.
2 Pesticides tentatively identified by gas chromatography (electron
capture) but not confirmed by gas chromatography/mass spectroscopy.
-' ND means not detected.
4 NR means not reported.
97
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these facilities process wastewater is either discharged to
publicly owned treatment works or not discharged.
PRESSROOM (NONWATER-BASED INKS) SUBCATEGORY
Decision Not to Establish National Regulations
Discharge of heavy metals and other toxic pollutants may occur
from plants in the pressroom (nonwater-based inks) subcategory.
While the potential exists for discharge, the amount and toxicity
of the pollutants contained in the raw wastewater discharges do
not justify developing national regulations. Therefore, BAT,
NSPS, PSNS, and PSES regulations will not be established for this
subcategory, under the authority of Paragraph 8 (a)(iv) of the
Settlement Agreement.
Data Evaluation
Table VI1-2 summarizes screening sampling data obtained at two
large facilities where pressroom (nonwater-based inks) operations
are performed. The discharge volumes at these plants were 400
and 800 liters (100 and 200 gallons) per day. The total
discharge of toxic pollutants from each plant was less than
0.0054 kilograms (0.012 pounds) per day. Because of the value of
solvents used in nonwater-based inks, waste inks are drummed and
collected by waste scavengers at the majority of the plants in
this subcategory.
Pressroom (Nonwater-Based Inks) Subcategory Plant Profile
Based on an extrapolation of the results of the data request
survey, there are approximately 46,000 plants where pressroom
(nonwater-based inks) operations are performed. At over 99
percent of these facilities process wastewater is either
discharged to publicly owned treatment works or not discharged.
PRESSROOM (WATER-BASED INKS) SUBCATEGORY
Decision Not to Establish National Regulations
Discharge of heavy metals and other toxic pollutants may occur
from plants in the pressroom (water-based inks) subcategory.
While the potential exists for discharge, the amount and toxicity
of the pollutants contained in the raw wastewater discharges does
not justify developing national regulations. Therefore, BAT,
NSPS, PSNS, and PSES regulations will not be established for this
subcategory, under the authority of Paragraph 8(a)(iv) of the
Settlement Agreement.
98
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TABLE VII-2
TOXIC POLLUTANT RAW WASTE LOADS FROM PRESSROOM
(NONWATER-BASED INKS) OPERATIONS
Plant Code
1303 9002
Pesticides (Ib/day)1 ND2 <0.000002
Organics (Ib/day) <0.0070 <0.0013
Metals and Cyanide (Ib/day) <0.0050 <0.00070
Total Toxic Pollutants (Ib/day) <0.0120 <0.0021
1 Pesticides tentatively identified by gas chromatography (electron
capture) but not confirmed by gas chromatography/mass spectroscopy,
2 ND means not detected.
99
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Data Evaluation
Table VII-3 summarizes the verification sampling data obtained at
two large facilities where pressroom (water-based inks)
operations are performed. Discharge volumes at these large
plants ranged between 621 and 1900 liters per day (164 and 500
gallons per day). The typical discharge volume at pressroom
(water-based inks) plants where wastewater is discharged is less
than 200 liters (50 gallons) per day. Therefore, the pollutant
loadings at the sampled plants are expected to be significantly
greater than at smaller establishments which make up the vast
majority of the plants in this subcategory. The average
discharge of total toxic pollutants determined from screening and
verification sampling at the two facilities was less than 0.545
kilograms (1.2 pounds) per day per plant.
Pressroom (Water-Based Inks) Subcateqory Plant Profile
Based on an extrapolation of the results of our data request
survey, there are approximately 600 plants where pressroom
(water-based inks) operations are performed. EPA estimates that
process wastewater is generated at only half of these plants and
that more than 95 percent of the generated wastewater is not
discharged or is discharged to publicly owned treatment works.
FINISHING AND BINDING OPERATIONS SUBCATEGORY
Decision Not t£ Establish National Regulations
Based on an extrapolation of the results of the data request
survey, there are approximately 6,000 plants where finishing and
binding operations are performed. Finishing and binding
operations are dry processes, with the possible exception of
small amounts of wastewater generated from infrequent cleanup
operations. However, in most cases, this waste is hauled away.
Because these are essentially dry operations, BAT, NSPS, PSNS,
and PSES regulations will not be established for this
subcategory, under the authority of Paragraph 8 (a)(iv) of the
Settlement Agreement.
100
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TABLE VI1-3
TOXIC POLLUTANT RAW WASTE LOADS FROM PRESSROOM
(WATER-BASED INKS) OPERATIONS
Pesticides (Ib/day)^
Organics (Ib/day)
Metals and Cyanide
5478
Screening^ > •
0. 000004
0.017
<2.58
Plant Code
5478
2 Verif ication^
ND5
0.018
<0.620
9018
Verification-^
ND
0.004
<0.910
(Ib/day)
Total Toxic Pollutants
(Ib/day)
<2.606
<0.6386
<0.914
1 Data from one day screening sampling.
2 Total toxic pollutant raw waste load at Plant 5478 was 0.085 Ib/day
(during screening) if chromium and lead are not included in the
total. Both chromium and lead were found at substantially lower
levels during subsequent verification sampling at this plant.
3 Average of data from three day verification sampling.
^ Pesticides tentatively identified by gas chromatography (electron
capture) but not confirmed by gas chromatography/mass spectrometry.
5 ND means not detected.
" The average total toxic pollutant raw waste load from Plant 5478
is <1.2 Ib/day. This loading was determined by averaging the data
from the one day of screening sampling and the three days of
verification sampling.
101
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SECTION VIII
ACKNOWLEDGEMENTS
The U.S. Environmental Protection Agency (EPA) wishes to
acknowledge the contributions to this project by Environmental
Science and Engineering, Inc., of Gainesville, Florida. Mr. John
D. Crane, P.E., and Mr. Bevin A. Beaudet, P.E., were the Project
Directors. Mr. Edward M. Kellar, Project Manager, and Ms.
Patricia H. Markey, Project Manager, were the key contributors to
the technical study and the drafting of the initial report on
which this document is based. Other personnel of Environmental
Science and Engineering, Inc. and its subcontractors who
contributed to the project are Mr. Dean Williamson, John J.
Mousa, Ph.D., Ms. Suzanne E. Albrecht, Ms. Patricia L. McGhee,
Mrs. Elizabeth A. Brunetti, Ms. Kathleen R. Crase, Ms. Linda J.
Harding, and J.R. Silver, Ph.D., Consultant of the Rochester
Institute of Technology.
The Agency also acknowledges the contributions of E.H. Richardson
and Associates (EHRA) of Dover, Delaware, for field sampling and
analytical efforts during the project. Dr. Thomas A. Dean
directed this effort for EHRA.
EPA wishes to express its appreciation to the plant managers,
engineers, and other representatives of the industry whose
cooperation in information gathering efforts and assistance in
site visitations made the completion of this project possible.
The efforts of several printing and publishing industry trade
associations, particularly the Printing Industries of Connecticut
(PIC), the Graphic Arts Technical Foundation (GATF), the Gravure
Research Institute (GRI), and the American Newspaper Publishers
Association (ANPA), had a significant positive impact on this
project. Special acknowledgement is due to the Industry
Environmental Conservation Board Ad-Hoc Water Committee.
Individuals who particularly deserve mention are Dr. William 0.
Schaeffer, Director of Research, GATF, who served as committee
chairman, Ms. Mary Pat David of GATF, Dr. Stephen S. Blechanzyck
of R. R. Donnelly and Sons, Dr. Lewis E. Allen of Eastman Kodak
Company, and Mr. Harvey F. George of GRI.
Mr. Mark Mjoness, Mr. Carl Kassebaum, and Mr. David Alexander
served as EPA Effluent Guidelines Division (EGD) Project Officers
during the various phases of this study. Their coordination of
the technical studies was indispensable to this project. Mr.
Robert W. Dellinger of EGD reviewed drafts of this document and
made major contributions. Ms. Gail Cooper of EPA's Office of
103
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General Counsel and Mr. John E. Riley, Mr. Jeffery D. Denit, and
Mr. Robert B. Schaffer of EGD made significant contributions.
Mrs. Glenda Colvin, Mrs. Glenda Nesby, Ms. Carol Swann, and Mrs.
Pearl Smith of EGD are recognized for their patience and
invaluable assistance.
104
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SECTION IX
REFERENCES
REFERENCES CITED IN TEXT
1 . Natural Resources Defense Council, Inc., e£ al. v. Train,
United States District Court for the District of Columbia,
(8 ERC 2120), June 7, 1976.
2. Natural Resources Defense Council, Inc., et al. v. Costle,
United States District Court for the District of Columbia,
(12 ERC 1833), March 9, 1979.
3. Standard Industrial Classification Manual, Office of
Management and Budget, Washington, D.C., 1972.
4. U.S. Environmental Protection Agency, Draft Development
Document for Paint and Ink Formulation and Printing,
National Field Investigations Center, Denver, Colorado,
1974.
5. U.S. Environmental Protection Agency, Environmental Aspects
of_ Chemical Use jjn Printing Operations, Conference
Proceedings, Office of Toxic Substances, EPA 560/1-75-005,
Washington, D.C., January 1976.
6. Dun and Bradstreet, Inc., Middle Market Directory, 1977, New
York, New York, 1976.
7. U.S. Environmental Protection Agency, Sampling and Analysis
Procedures for Screening of Industrial Effluents for
Priority Pollutants, Cincinnati, Ohio, April 1977.
8. U.S. Environmental Protection Agency, Guidance Document for
the Control of. Water Pollution ir\ the Photographic
Processing Industry, EPA 440/1-81/082-9, Washington, D.C.,
April 1981.
9. U.S. Bureau of the Census, 1972 Census of. Manufactures;
Commercial Printing and Manifold Business Forms, Social and
Economic Statistics Administration, MC72(2)-27B, Washington,
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10. U.S. Bureau of the Census, 1972 Census of. Manufactures;
Converted Paper and Paperboard Products, Except Containers
and Boxes, Social and Economic Statistics Administration,
MC72(2)-26B, Washington, D.C., 1975.
105
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11. U.S. Bureau of the Census, 1972 Census of Manufactures;
Greeting Cards; Bookbinding; Printing Trade Servides, Social
and Economic Statistics Administration, MC72(2)-27C,
Washington, D.C., 1974.
12. U.S. Bureau of the Census, 1972 Census of Manufactures;
Chemical Products, Social and Economic Statistics
Administration, MC72(2)-28H, Washington, D.C., 1974.
13. U.S. Bureau of the Census, 1972 Census of Manufactures;
Newspapers, Periodicals, Books, and Miscellaneous
Publishing, Social and Economic Statistics Administration,
MC72(2)-27A, Washington, B.C., 1974.
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1977.
15. American Newspaper Publishers Association, "An Overall Look
at DiLitho", ANPA Research Institute Bulletin 1258, April 6,
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21. American Newspaper Publishers Association, "Specification
Data - 1975", ANPA Research Institute Bulletin, 1976.
106
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22. American Newspaper Publishers Association, "Paste-up to
Press Workshop", ANPA Research Institute Bulletin 1243,
November 3,1976.
23. American Newspaper Publishers Association, "Printing
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24. American Newspaper Publishers Association, "Systems to
Satellites", ANPA Research Institute Bulletin 1240, October
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25. Anderson, A., "Ink Chemistry and a Review of Sheet Fed Ink
Curing", Society of Manufacturing Engineers Technical Paper,
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26. Ayers, G.L., "How Processor Waste Loads Can Be Minimized",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
27. Bard, C.C., J.J. Murphy, D.L. Stone, and C.J. Terhaar,
"Silver in Photoprocessing Effluents", Journal Water
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389-394, February, 1976.
28. Barnhart, E.L., "Basic Elements of Waste Treatment",
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29. Barnhart, E.L., "Biological Waste Treatment of
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Environment, New York, New York, June 6, 1974.
30. Bassemer, R.W., "Avoiding Solvent Emissions-Solventless
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31. Bassemer, R.W., "Ultraviolet Ink Chemistry-Paper and Paper-
board", Society of Manufacturing Engineers Technical Paper,
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32. Battelle Laboratories, "An Investigation of Techniques for
Removal of Cyanide from Electroplating Wastes", Columbus,
Ohio, November 1971.
107
-------
33. Bober, T.W. and A.C. Cooley, "The Filter Press for the
Filtration of Insoluble Photographic Processing Wastes",
Reproduced from Photographic Science and Engineering, Volume
16, Number 2, March-April, 1972, as Eastman Kodak
Publication J-45, Rochester, New York, 1972.
34. Bober, T.W. and T.J. Dagon, "The Regeneration of
Ferricyanide Bleach Using Ozone", Reproduced from Image
Technology, Volume 14, Number 4, June-July, 1972, and Volume
14, Number 5, August-September, 1972, as Eastman Kodak
Company Publication J-42, Rochester, New York, 1972.
35. Bober, T.W. and T.J. Dagon, "Ozonation of Photographic
Processing Wastes", Journal Water Pollution Control
Federation, Volume 47, Number 8, Pages 2114-2129, 1975.
36. Bond, R.G., C.P. Straub, and R. Prober, Editors, Handbook of.
Environmental Control, CRC Press, Inc., Cleveland, Ohio,
1974.
37. Book Manufacturers' Institute, Inc., 1977 Membership
Directory, Ridgefield, Connecticut.
38. Booz Allen Applied Research, Inc., "A Study of Hazardous
Waste Materials, Hazardous Effects and Disposal Methods",
Volumes I-III, Bethesda, Maryland, July 1973.
39. Bruno, M.H., "Technology: 1976", Inland Printer/American
Lithographer, Volume 176, Number 4, Pages 35-39, January
1976.
40. Carlick, D.J., "Ultraviolet Curing of Inks", Modern
Packaging, Volume 45, Number 12, pages 64-67, 1972.
41. Commodity Research Bureau, Inc., Commodity Yearbook, 1976,
New York, New York, 1976.
42. Cooley, A.C., "Reuse and Recovery of Processing Chemicals",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
43. Dagon, T.J., "The Biological Treatment of Photographic
Processing Effluents", Eastman Kodak Publication J-46,
Rochester, New York, 1972.
44. Dagon, T.J., "Biological Treatment of Photo Processing
Effluents", Journal Water Pollution Control Federation,
Volume 45, Number 10, October, 1973.
108
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45. Dagon, T.J., "Specific Applications of Photographic
Processing Effluent Treatment", National Association of
Photographic Manufacturers Seminar, Photoprocessing and the
Environment, New York, New York, June 6, 1974.
46. Daignault, L.G., "Pollution Control in the Photoprocessing
Industry Through Regeneration and Reuse", Journal of Applied
Photographic Engineering, Volume 3, Number 2, Spring 1977.
47. Duff icy, T.J., "The Federal Water Pollution Control Act of
1972-1ts Effect on Photographic Processing Operations",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
48. Dunn, J.E. and J.M. Weir, "Cancer Experience of Several
Occupational Groups Followed Prospectively", American
Journal o_f_ Public Health, Volume 55, Number 9, Pages
1367-1375, September 1965.
49. Eastman Kodak Company, "Glossary of Terms/Index", Eastman
Kodak Publication No. J-48, Rochester, New York, 1975.
50. Eastman Kodak Company, "Recovering Silver from Photographic
Materials", Eastman Kodak Publication No. J-10, Rochester,
New York, 1972.
51. Eastman Kodak Company, "Regeneration of Kodak EA-5 Bleach
and Replenisher", Rochester, New York, 1972.
52. Eastman Kodak Company, "BOD5 and COD", Eastman Kodak
Publication No. J-41, Rochester, New York, 1973.
53. Eastman Kodak Company, "Disposal of Photographic Processing
Effluents and Solutions", Eastman Kodak Publication No.
J-28, Rochester, New York, 1973.
54. Eastman Kodak Company, "A Simple Waste Treatment System for
Small Volumes of Photographic-Processing Wastes", Eastman
Kodak Publication No. J-43, Rochester, New York, 1974.
55. Eastman Kodak Company, "Chemical Composition of Photographic
Processing Solutions", Eastman Kodak Publication No. J-47,
Rochester, New York, 1975.
56. Eastman Kodak Company, "American National Standard on
Photographic Processing Effluents", Eastman Kodak
Publication No. J-49, Rochester, New York, 1975.
109
-------
57. Eastman Kodak Company, "Disposal of Photographic-Processing
Solutions for the Small User", Eastman Kodak Publication No.
J-52, Rochester, New York, 1976.
58. Eastman Kodak Company, "Silver Recovery with the Kodak
Chemical Recovery Cartridge, Type P", Rochester, New York,
1976.
59. Eastman Kodak Company, "Potential Silver Yield From Kodak
Photographic Products", Eastman Kodak Publication No. J-10A,
Rochester, New York, 1977.
60. Eastman Kodak Company, "Silver Recovery with the Kodak
Chemical Recovery Cartridge, Type 3", Eastman Kodak
Publication No. J-9A, Rochester, New York, 1977.
61. Eastman Kodak Company, "Water Conservation in Photographic
Processing", Eastman Kodak Publication No. S-39, Rochester,
New York, 1977.
62. Eaton, G.T., Photographic Chemistry, Morgan & Morgan, Inc.,
Publishers, Hastings-on-Hudson, New York, 1957.
63. "An Electrostatic Precipitator Solves Web Printer Pollution
Problems", Inland Printer/American Lithographer, Volume 177,
Number 11, Pages 55-56, August 1976.
64. Elsheikh, A., A. Yassen, and A.A. Aal, "A Survey on Lead
Absorption and Intoxication in Workers of a Printing Plant",
Journal of the Egyptian Medical Associaton, Volume 48, Pages
508-513, 1965.
65. R.E. Kirk and D.F. Othmer, Encyclopedia of Chemical
Technology, 2nd Edition, Wiley-Interscience, 1963-1970.
66. Evans, J.C.W., "Environmental Improvements and Protection
Developments Reviewed", Pulp and Paper, Volume 50, Number
14, Pages 139-141, 1976.
67. Falcone, J.S. and R.W. Spencer, "Silicates Expand Role in
Waste Treatment, Bleaching, Deinking", Pulp and Paper,
Volume 49, Number 14, Pages 114-117, December 1975.
68. Ferguson, T.L., et a1., "Determination of Incinerator
Operating Conditions Necessary for Safe Disposal of
Pesticides", U.S. Environmental Protection Agency, Office of
Research and Development, EPA-600/2-75-041, Cincinnati,
Ohio, December 1975.
110
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69. Florida Chamber of Commerce, Directory of Florida
Industries, Tallahassee, Florida, 1976.
70. Fremgen, R.D., Monitoring and Testing of. Effluents from
Letterpress and Offset Printing Operations, Dayton Press,
Inc., September 10, 1975.
71. Fulweiler, S.B., "The Nature of Photographic Processing",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
72. Gadomski, R.R., M.P. David, and G.A. Blahut, "Evaluations of
Emissions and Control Technologies in the Graphic Arts
Industries", Final Technical Report, Graphic Arts Technical
Foundation, Pittsburgh, Pennsylvania, August 1970.
73. Gale Research Company, Encyclopedia of_ Associations, 10th
Edition, Volume I., National Organizations of U.S., Detroit,
Michigan, 1976.
74. Carver, S.R., and R.W. Klippel, "Multiple Reuse of Photo
Processing Wastewaters Using Reverse Osmosis, Brine
Reclamation and Cooling Tower Application", Proceedings of
the Seventh Mid-Atlantic Industrial Waste Conference, Drexel
University, Philadelphia, Pennsylvania, November 12-14,
1974.
75. Gove, G.W. and J.J. McKeown, "Current Status of Paper
Reprocessing Effluent Characteristics and Disposal
Practices", TAPPI, Volume 58, Number 11, Pages 121-126,
1975.
76. Graphic Arts Technical Foundation, Inc., Environmental
Control Report, Pittsburgh, Pennsylvania, July 1971,
September 1971, December 1971, March 1972, June 1973, April
1974, and August 1974.
77. Graphic Arts Technical Foundation, Inc., Handbook for
Graphic Communications, Pittsburgh, Pennsylvania, 1972.
78. Hanson, J.P., "Brown Recycles Deinking Water on Tissue-Grade
Products", Pulp and Paper, Volume 5, Number 11, Pages
136-138, 1977.
79. Hartsuch, P.J., Chemistry of_ Lithography, Lithographic
Technical Foundation, Inc., New York, New York, 1961.
Ill
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80. Hartsuch, P. J., Chemistry of Lithography, Graphic Arts
Technical Foundation, Pittsburgh, Pennsylvania, 1975.
81. Harvin, R.L., "A Modern Design Solvent Recovery Plant",
American Institute of Chemical Engineers Symposium Series -
Air Pollution and Its Control, Volume 68, Number 126, New
York, New York, 1972.
82. Hellberg, E.V., "Deinking to Original Brightness?", Pulp and
Paper, Volume 51, Number 1, Pages 139-141, January, 1977.
83. Huang, J.C. and J.T. Garrett, "Effects of Polyelectrolytes
and Clay", Water and Sewage Works, Volume 124, Number 3,
Pages 64-68, March 1977.
84. Idaho Department of Commerce and Development, Manufacturing
Directory of Idaho - 1973, Boise, Idaho, 1973.
85. Imbelli, C., W.B. Pressman, and H. Radiloff, "The Industrial
Wastes Control Program in New York City", Journal Water
Pollution Control Federation, Volume 40, Number 12, Pages
1981-2012, December 1968.
86. International Paper Company, Pocket Pal - A Graphic Arts
Production Handbook, Twelfth Edition, March, 1979.
87. Iowa Division of Commerce, Directory of Iowa Manufactures,
1973 - 1974, Des Moines, Iowa, 1973.
88. Jaffe, E., "A New Letterpress Process", TAPPI, Volume 57,
Number 4, Pages 81-82, April 1974.
89. Jezuit, L.J., "UV Drying and Sheet Fed Offset Printing:
Marriage or Mirage", Society of Manufacturing Engineers
Technical Paper, FC74-514, 1974.
90. Jordan, J.W., Remarks Presented at the National Association
of Photographic Manufacturers Seminar, Photoprocessing and
the Environment, Chicago, Illinois, June 14, 1974.
91. Kansas Department of Economic Development, 1972-1973
Directory of Kansas Manufactures and Products, Topeka,
Kansas, 1972.
92. Karch, R.R. and E.J. Buber, Graphic Arts Procedures,
American Technical Society, Chicago, Illinois, 1973.
112
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93. Kehoe, R.A., "Note on Studies of the Lead Hazards in Certain
Phases of Printing", Journal of_ Industrial Hygiene and
Toxicology, Volume 23, Number 4, Pages 159-162, 1941.
94. Kincaid, R.B., "Characteristics of a New Printing Process
Using Dry Plates", TAPPI, Volume 55, Number 12, Pages 1676-
1677, December 1972.
95. Klein, L.A., M. Lang, N. Nash, and S.L. Kirschner, "Sources
of Metals in New York City Wastewater", Journal Water
Pollution Control Federation, Volume 46, Number 12, Pages
2653-2662, December 1974.
96. Ling, J.T., "Pollution Prevention Pays: 3M Resource
Conservation Program Attacks Pollution at Its Sources",
Pollution Engineering, Volume 9, Number 5, Pages 30-34, May
1977.
97. Merle, R.L., M.C. Young, and G.R. Love, "Design and
Operation of a Suspension Fired Industrial Solid Waste
Disposal System for Kodak Park", Rochester, New York, 1976.
98. Mount Sinai School of Medicine of the City University of New
York, Plant Visit to Government Printing Office, Washington,
D.C., November 21, 1975.
99. Mount Sinai School of Medicine of the City University of New
York, Plant Visit to W.F. Hall Printing Co., Chicago,
Illinois, Nobember 20, 1975.
100. Mount Sinai School of Medicine of the City University of New
York, Plant Visit to Regensteiner Publishing Enterprises,
Chicago, Illinois, January 7, 1976.
101. Metzner, A.V., "Removing Soluble Metals from Wastewater",
Water and Sewage Works, Volume 124, Number 4, April 1977.
102. Mitchell, C., "HVAC 'Aids in Recovery at Meredith/Burda",
Inland Printer/American Lithographer, Volume 174, Number 1,
Pages 74-75, October 1974.
103. Moody's Investors Service, Inc., Moody's OTC Industrial
Manual, New York, New York, 1976.
104. Moss, E., T.S. Scott, and G.R.C. Atherley, "Mortality of
Newspaper Workers from Lung Cancer and Bronchitis, 1952-
1966", British Journal of_ Industrial Medicine, 1972.
113
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105. National Association of Photographic Manufacturers, Inc.,
"Photoprocessing and the Environment-Questions and Answers",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
106. National Association of Photographic Manufacturers, Inc.,
"Characteristics of Photographic Processing Effluents",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
107. National Institute for Occupational Safety and Health,
Health and Safety Guide for the Printing Industry, 1975.
108. Naval Education and Training Command, Lithographer 3_ and 2^,
Washington, D.C., 1975.
109. Oklahoma Industrial Development and Park Department,
Oklahoma Directory of Manufactures and Products - 1972,
Oklahoma City, Oklahoma, 1972.
110. Oregon Department of Economic Development, Directory of_
Oregon Manufactures 1976 - 1977, Portland, Oregon, 1976.
111. Ottinger, R. S., et al., "Recommended Methods of Reduction,
Neutralization, Recovery, or Disposal of Hazardous Waste",
TRW Systems Group, Redondo Beach, California, Volume I (NTIS
PB-224 580), Volume II (NTIS PB-224 581), Volume III (NTIS
PB-224 582), Volume IV (NTIS PB-224 583), Volume XVI (NTIS
PB-224 595), August 1973.
112. "Photomechanics: What's Happening Right Now in
Platemaking", Inland Printer/American Lithographer, Volume
177, Number 12, Pages 41-45, 1976.
113..Powers, P.W., "How to Dispose of Toxic Substances and
Industrial Wastes", Environmental Technology Handbook 4_,
Noyes Data Corporation, Park Ridge, New Jersey, 1976.
114. Regna, E.A., Remarks Presented at the National Association
of Photographic Manufacturers Seminar, Photoprocessing and
the Environment, New York, New York, June 6, 1974.
115. Rhode Island Development Council, Rhode Island Directory of
Manufactures - 1973, Providence, Rhode Island, 1973.
114
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116. Rice, B. and R. van Soest, "Practical Experience of a New
Effluent Plant One Year After Startup", TAPPI, Volume 58,
Number 10, Pages 104-107, October 1975.
117. Sanai, G.H., N. Ziai, and A. Ghasemi, "Lead Intoxication in
Printing Houses", Bulletin of Environmental Contamination
and Toxicology, Volume 14, Number 5, 1975.
118. Schaeffer, D.J., et al., "Relationship Between BOD5 and
Fats, Oils and Greases", Water and Sewage Works, Volume 124,
Number 3, Pages 82-83, 1977.
119. Schwer, R.F., "A Systematic Approach to Handling Wastewater
Discharges", National Association of Photographic
Manufacturers Seminar, Photoprocessing and the Environment,
New York, New York, June 6, 1974.
120. Shreve, R.N., Chemical Process Industries, 3rd Edition,
McGraw-Hill Book Company, New York, New York, 1967.
121. Sloan, C.T., "How to Handle Spent Plating Solutions",
Industrial Wastes, Volume 20, Number 6, Page 34,
November/December 1 974.
122. Smith, K.M., "Establishing Photoprocessing Effluent Loads",
National Association of Photographic Manufacturers Seminar,
Photoprocessing and the Environment, New York, New York,
June 6, 1974.
123. "A Solution to Fountain Solution Problems: pH Control",
Inland Printer/American Lithographer, Volume 176, Number 5,
Pages 74E- 74F, February 1976.
124. Sorg, T.J., "Solid Waste Management in the Printing and
Publishing Industry", Proceedings of the 26th Industrial
Waste Conference, Part Two, Engineering Bulletin of Purdue
University, Engineering Extension Series No. 140, May 4-6,
1971 .
125. Standard and Poors Corporation, Standard and Poors Register
of Corporations, Directors, and Executives, New York, New
York, 1976.
126. Strauss, V., The Printing Industry, Printing Industries of
America, Inc., Washington, D.C., 1967.
127. Teigen, K., Graphic Arts, an Introduction, Management
Development Institute Publications, Division of Information
Industries, Inc., Wayne, Pennsylvania, 1968.
115
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128. Thoma, P.J., "How New Developments in the Printing Field
Affect Paper-makers", TAPPI, Volume 58, Number 6, Pages 56-
58, June 1975.
129. Thomas, M.J. and T.L. Theis, "Colloid Chemical Properties of
Chrome Hydroxides Applied to Metal Finishing Wastes",
Proceedings of the Seventh Mid-Atlantic Industrial Waste
Conference, Drexel University, Philadelphia, Pennsylvania,
November 12-14, 1974.
130. Turnbull, A.T. and R.N. Baird, The Graphics of_
Communication, Typography-Layout-Desiqn, 2nd Edition, Holt,
Rinehart, and Winston, Inc., New York, New York, 1968.
131. U.S. Department of Commerce, Printing and Publishing,
Quarterly Industry Report, July/October 1973.
132. U.S. Department of Commerce, Printing and Publishing,
Quarterly Industry Report, Fall 1976.
133. University of Colorado, School of Business, Directory of
Colorado Manufactures, 1973 - 1974, Boulder, Colorado, 1973.
134. University of New Mexico, 1974 - 1971 Directory o_f
Manufacturing and Mining, Sante Fe, New Mexico, 1974.
135. U.S. Environmental Protection Agency, Development Document
for Effluent Limitations Guidelines and New Source
Performance Standards for the Oil Base Solvent Wash
Subcategories of the Paint Formulating and the Ink
Formulating Point Source Category, EPA 440/1-75/050-a Group
II, Washington, D.C., July 1975.
136. U.S. Environmental Protection Agency, Development Document
for Interim Final Effluent Limitations Guidelines and
Proposed New Source Performance Standards for the
Photographic Processing Subcategory of the Photographic
Point Source Category, EPA 440/1-76/0601, Group II,
Washington, D.C., July 1976.
137. Utah Department of Employment Security, 1975 - 1976
Directory of Utah Manufactures, Salt Lake City, Utah, 1975.
138. "UV Cure Cuts Pollution, Energy Use", Environmental Science
& Technology, Volume 76, Number 6, Page 502, 1973.
139. Vincent, K.D, "The Utilization of Photopolmyer Inks to Print
on Thin Plastic Film by Offset Lithography", Society of
Manufacturing Engineers Technical Paper, FC74-529.
116
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140. Walsh, J.J., "A Review of the Graphic Arts Industry",
Institute of Electrical and Electronic Engineers,
Transactions on Aerospace and Electronic Systems, Volume
AES-6, Number 4, Pages 422-431, July 1970.
141. Welling, L.J. and W.C. Vreeland, "Coating Reclaim at
Consolidated Papers, Inc., Wisconsin Rapids Division",
TAPPI, Volume 58, Number 9, Pages 105-107, 1975.
142. Wells, A.M., "Printing Inks - Recent Developments", Noyes
Data Corporation, Park Ridge, New Jersey, 1976.
143. West, L.E., "In Support of Clean Water-Disposing of
Effluents from Film Processing", Eastman Kodak Publication
No. J-44, Rochester, New York, 1974.
144. West Virginia Department of Commerce, West Virginia
Manufacturing Directory, 1974, Charleston, West Virginia,
1974.
145. Zehnpfennig, R.G., "Possible Toxic Effects of Cyanates,
Thiocyanates, Ferricyanides, Ferrocyanides, and Chromates
Discharged to Surface Water", Proceedings of the 22nd
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of Purdue University, Engineering Extension Series No. 129,
May 2-4, 1967.
117
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SECTION X
GLOSSARY
Art and Copy - Material to be reproduced in quantity.
Manuscripts are examples of line copy. Photographs and full
color artwork are termed continuous tone.
Binder - The film forming component of an ink.
Carbon Tissue - A light-sensitive emulsion on a paper backing
used in gravure cylinder preparation. (see resist)
t
Cellosolve - Union Carbide Corporation Trademark for mono and
dialkyl ethers of ethylene glycol and their derivatives.
Composition - The process of preparing original type or
manuscripts for platemaking operations.
Continuous Tone - An image which is composed of a continuous
range of overlapping tones.
Deep-Etch Plate - A type of lithographic printing plate on which
the image areas are slightly below the surface of the plate.
Diazonium Resin - A light-sensitive coating used on short-run
lithographic printing plates.
Direct Discharger - A plant where treated or untreated process
wastewater is released from its site or property, generally into
a receiving water, but not into a publicly owned treatment works.
Dot Etching - Chemically reducing the size of the dots on a
halftone image to increase or reduce (depending on whether the
respective image is a positive or a negative) local color.
Drier - A salt of cobalt, manganese, lead, or another metal used
to catalyze the oxidation of the binding vehicle in certain inks.
Etch - The process of forming an image on a printing plate or
cylinder by the action of an acid or an electrolyte. Also a
chemical used in lithographic fountain solutions to prevent
corrosion of the aluminum backings on printing plates.
Evaporation of Wastewater - A disposal method in which natural or
induced head causes evaporation of wastewater.
Expose - To submit a photographic emulsion to light.
119
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Fixing - Chemical action which renders photographic images
permanent and insensitive to further exposure.
Fountain Solution - See Lithographic Fountain Solution.
Gelatin - A medium which serves to hold light-sensitive materials
in suspension.
Gum Arabic - An exudation of the acacia plant. When applied to
lithographic printing plates, gum arabic makes the non-image
areas repel greasy inks.
Halftone - An image, composed of a series of minute dots,
produced by exposing a photographic emulsion to the subject
through a fine screen. This is the type of image on
lithographic, letterpress, flexographic, and halftone gravure
cylinders. The ink density on these printing plates and
cylinders is constant; tonal variations in the products are the
result of varing dot sizes on the plates.
Indirect Discharger - A plant where treated or untreated process
wastewater is released from its site or property to a publicly
owned treatment works.
In-house Printing - A printing operation which produces goods or
services solely for a parent organization (or one or more of its
divisions) primarily engaged in a business other than printing or
publishing.
Intaglio - An engraved image.
Lacquer - In platemaking, an ink receptive coating. Also a clear
glossy protective coating applied to printed products.
Layout - A model of the finished printed product.
Landfill - A solid waste land disposal technique in. which waste
is placed in an excavation and covered with earth. Wastewaters
and sludges may also be disposed of by this method.
Land Disposal - A wastewater disposal technique such as spray
irrigation or evaporation ponds.
Light-Sensitive Material - A material which reacts to form a
latent image upon exposure to light.
Lithographic Fountain Solution - An aqueous solution used on
lighographic printing plates to keep the non-image areas free of
ink.
120
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Negative - An image on printing plates or transparencies in which
the light and dark values are reversed from the subject.
Negatives are used chiefly for making positives.
Noncontact Cooling Water - Water which is used for cooling
purposes but which has no direct contact with and is no way
contaminated by (temperature change excepted) the manufacturing
process or contaminated wastewaters.
Nonprocess Wastewater - Wastewater which is not contaminated by
the process or related materials. Examples of nonprocess
wastewater include boiler blowdown, noncontact cooling water,
sanitary sewage, and storm water.
NPDES (National Pollutant Discharge Elimination System) Permit -
A permit issued by EPA or an approved state program to point
sources which discharge to public waters. The permit specifies
certain conditions which the permittee must attain in order to
continue its effluent discharge.
Perfect Binding - A book binding, widely used on paperback books,
which consists primarily of a flexible adhesive.
Pigment - A solid with desirable color properties. Colloidal
suspensions of such solids in an ink give the ink its
characteristic color.
Positive - An image on printed material, printing plates, or
transparencies showing the light and dark values as they are in
the subject.
Potassium Alum - Aluminum Potassium Sulfate-Al2(S04)3 . K2(S04) .
24H20
Presensitized Plate - A lithographic printing plate which is
supplied to the printer covered with a light-sensitive coating.
(See wipe-on plate)
Process Wastewater - Any used water which results from or has had
contact with printing or allied processes, including any water
for which there is a reasonable possibility of contamination from
the process or from raw material - intermediate product -final
product storage and handling, transportation, processing, or
cleaning operations. Examples of process wastewater include
wastewater generated by photoprocessing, engraving and etching,
platemaking, equipment and plant cleanup, etc. Cooling water,
sanitary wastewater, storm water and boiler blowdown are not
considered process wastewater if they have no contact with the
process.
121
-------
Proof - Printed material which is checked for errors prior to
full scale production.
Publicly Owned Treatment Works - Wastewater collection and
treatment facilities owned and operated by a public body such as
a municipality or county.
Resist - A light-sensitive coating used on printing plates,
cylinders, or screens which hardens upon exposure to light and
serves to prevent etching of the hardened areas during subsequent
processing with etching solutions.
Retouching - Chemically correcting the tone values on finished
transparencies.
Sanitary Sewage - Liquid waste resulting from bathrooms, drinking
fountains, etc., which is totally independent of the
manufacturing process.
Stripping - The positioning of transparencies in platemaking
operations.
Spray Irrigation - The transport ot wastewater or sludge to a
distribution system from which it is sprayed over an area of
land. The liquid percolates into the soil or evaporates. None
of the sludge or wastewater runs off the irrigated area.
Thermography - A variation of the letterpress or lithographic
processes. Printed material is dusted with a proprietary powder
and heated as it comes off the printing press. The ink swells as
it dries creating a raised image on the product.
Transparency - A partially transparent copy such as a photo-
graphic film. In platemaking operations, light is passed through
or reflected from the transparency, thereby exposing and forming
an image on the light-sensitive coating of a printing plate.
Varnish - A vehicle used in printing inks. Also the term for
certain coatings used on printed products for durability and
appearance. In addition, an acid resistant coating used in
gravure platemaking.
Wastewater - Water for which a facility has no further use and
which must be disposed.
Wax - A component of some printing inks and a coating used on
printed material which prevents products from sticking together.
Wipe-On Plate - A lithographic printing plate which is covered
with a light-sensitive coating by the printer.
122
-------
APPENDIX - HISTORICAL RAW WASTEWATER DATA
HISTORICAL DATA FROM PLANTS VISITED AND/OR SAMPLED
Representatives of five plants which were visited by Agency
representatives during this study provided historical raw
wastewater data. The data for Plants 8190 and 5430 are shown in
Tables A-l and A-2. These plants are discussed in Section VI. A
brief summary of the processes employed and the sources of
wastewater at the remaining three plants is presented below.
Plant 5247
At plant 5247, six film processing machines are used in the
production of positive and negative screened transparencies. The
transparencies are sold to printing establishments where they are
used to manufacture printing plates.
City water is filtered and treated with zeolite water softeners
prior to use in photoprocessing operations. This is necessary to
avoid damage to the film. Developer consumption ranges between 8
and 45 liters/day (2 and 12 gpd) per machine depending on the
size and quantity of transparencies developed. Fixing solution
flows continuously at a constant rate of approximately 0.50
liter/minute (0.13 gpm). Used fixing solution flows through a
silver recovery unit and the desilvered fixing solution is
partially recycled. Rinse water flow is regulated at
approximately 8 liters/minute (2 gpm). The rinse water flows
only when film is being processed. Waste fix, developer, and
rinse water flow through a proportional chlorinator. The
chlorinator effluent is combined with sanitary sewage and
discharged. The combined sanitary sewage and process wastewater
volume ranges between 19,000 and 26,000 liters/day (5,000 to
7,000 gpd). Available raw wastewater data are presented in Table
A-3.
Plant 9010
Plant 9010 is a large, fully integrated offset lithographic
WP Q
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and developed by a deep-etch plate processing machine. Zinc
printing plates are also produced by a chemical etching process.
Process wastewater sources include: film processing, deep-etch
platemaking, zinc etching wastes, spent fountain solutions, and
oily wastes from the printing presses. Total process and
nonprocess wastewater volume is estimated to be 151,000
liters/day (40,000 gpd). Raw wastewater data are presented in
Table A-4.
Plant 8301
Over 500 people are employed to produce greeting cards at Plant
8301. Finishing and binding are the major plant operations; less
than ten percent of the cards produced are actually printed at
the plant. These finishing and binding operations include
gluing, die cutting, embossing, foil stamping, and other
decorative processes. Products are printed by the sheet-fed and
web-fed lithographic, thermographic, and flexographic methods.
Process wastewater is generated in platemaking and, to a small
extent, in cleanup operations. Process and sanitary wastewaters
are combined and discharged to a municipal sewer. Noncontact
wastewaters flow directly to a storm sewer. Table A-5 presents
pollutant data for combined process and sanitary wastewater.
HISTORICAL DATA FROM PLANTS NOT VISITED AND/OR SAMPLED
Tables A-6 through A-ll present historical raw wastewater data
for 44 plants which were not visited. The data were obtained
from plant representatives or from local, state, and federal
authorities. These tables are organized by printing process
rather than by subcategory. Wastewater streams and sample type
are documented to the extent that the information was available.
-------
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TABLE A-2
HISTORICAL RAW WASTEWATER DATA FOR PLANT 54301
TOXIC AND CONVENTIONAL POLLUTANTS
Concentrations, mg/1
Wastewater Flow
Stream (gpd) pH Cu Cr Zn TSS BOD5 COD
Photographic
Department 1,155 2.6 174 100 4,750 29 32,000 64,100
Press
Circulators 300 4.1 15.9 400 100 111 70,000 375,000
Rag
Laundry 8,000 10.1 3.44 1.60 4.65 737 1,130 5,860
Total Flow 9,455
Data from consultant report, September 1975. Sample type unknown.
126
-------
TABLE A-3
HISTORICAL RAW WASTEWATER DATA FOR PLANT 52471.2
Concentration
Wastewater Stream Parameter mg/1
Fix, Developer, and Acetate as Acetic Acid 40
Rinse Water Aluminum 0.04
Ethylene Diamine <10
Ethylene Glycol < 1.5
Formaldehyde < 1.5
Hydroquinone <10
Total Phosphate as P04 1.76
Sulfite as 803 365
Thiosulfate as ^8203 2,075
BOD5 440
COD 2,756
Ammonia as N 159
Borate as B <0.10
Silver 31.746
Total Phenols 0.168
Total Suspended Solids 2
1 Analysis provided by plant consultant, October 1976.
2 Grab sample taken before silver recovery unit.
127
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