I
EPA-560/1 -75-005
ENVIRONMENTAL ASPECTS
OF CHEMICAL USE
IN PRINTING OPERATIONS
^ ^*
(SEPTEMBER 22-24, 1975, KING OF PRUSSIA, PA.)
CONFERENCE PROCEEDINGS
OFF-CE OF TOXIC SUBSTANCES
LHVIRUNMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
JANUARY 1976
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Conference Proceedings
ENVIRONMENTAL ASPECTS OF CHEMICAL USE
IN
PRINTING OPERATIONS
(September 1975, King of Prussia, Pennsylvania)
CONTRACT NO. 68-01-2928
Project Officer: Farley Fisher, Ph.D.
OFFICE OF TOXIC SUBSTANCES
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
Prepared for
OFFICE OF TOXIC SUBSTANCES
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
January 1976
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Agency, nor does mention
of trade names or commercial products constitute endorsement or
recommendation for use.
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FOREWORD
The proceedings for the conference on "Environmental Aspects of
Chemical Use in Printing Operations" is the third of three reports, each
on a different conference, to be submitted under Contract No.
68-01-2928 to the Office of Toxic Substances for the Environmental
Protection Agency. The conference was held at the Holiday Inn —
Valley Forge, King of Prussia, Pennsylvania, on 22-24 September 1975.
The objective of this conference was to cover and discuss current usage
of chemicals in the printing industry, the byproducts thereby
introduced, the known health or environmental effects from chemicals
used, and the measures undertaken or available for use in controlling
environmental contamination. More specifically, papers were presented
and discussions held which covered types of printing processes,
emissions regulations, and health hazards from printing effluents.
Dr. Farley Fisher, Chief, Early Warning Branch, Office of Toxic
Substances, Environmental Protection Agency, Washington, D.C., was
the Project officer and General Chairman of the conference.
Mr. Franklin A. Ayer, Manager, Technology and Resource Management
Department, Center for Technology Applications, Research Triangle
Institute, Research Triangle Park, North Carolina, was the Conference
Coordinator and Compiler of the proceedings.
in
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Table of Contents
Page
22 September 1975
Opening Session 1
Opening Comments 2
Farley Fisher, Ph.D., General Chairman
Overview of Printing Processes and Chemicals Used 5
Ben H. Carpenter
Garland K. Milliard
Session I: PRINTING PROCESSES AND CHEMICALS USED 32
Bohdan V. Burachinsky, Ph.D., Chairman
Session Introduction 33
Bohdan V. Burachinsky, Ph.D.
Federal Water Pollution Control Act—An Association's Response 36
Thomas J. Duff icy
Hydrocarbon Emission Regulations 45
James A. McCarthy
The Organic Emission Program of Chicago 52
George T. Czerniak
Session II: ENVIRONMENTAL IMPACT OF CHEMICALS USED 105
William D. Schaeffer, Ph.D.
Session Introduction 106
William D. Schaeffer, Ph.D.
Toxjcological Evaluation of Chemicals Used in the Printing and Printing Inks Industries 111
Kingsley Kay, Ph.D.
Potential Hazards of Organic Solvents in the Graphic Arts Industry 142
Jacqueline M. Fetsko
Angiosarcoma of the Liver Among Printers 154
John T. Herbert, M.D.
Lithography: Laboratory Evaluation of Environmental Risk 1g3
Robert L. Bohon, Ph.D.
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Table of Contents (con.)
Materials of Flexography 190
Kenneth A. Bownes
Environmental Impacts of Chemicals Used in Screen Printing Inks 198
Charles F. Call, Jr.
23 September 1975
Session II: ENVIRONMENTAL IMPACT OF CHEMICALS USED (con.) 203
William D. Schaeffer, Ph.D.
Gravure Industry's Environmental Program 204
Harvey F. George
Storage and Handling of Flammable and Toxic Chemicals 217
Josef F. Heller
Heavy Metal Contamination in Printing Papers 228
Robert W. Praskievicz
Processing Effluent Characteristics of Dycril Photopolymer Printing Plates 242
Ellen G. Mellinger
Platemaking and Its Effect on the Environment 253
Steven Latus
Current Status of Web Heatset Emission Control Technology 261
Joseph L. Zborovsky
Monitoring and Testing of Effluents From Letterpress and Offset Printing Operations 283
Robert D. Fremgen
Session III: IMPACT OF WASTE RECOVERY AND RECYCLING ON THE ENVIRONMENT 3°3
Robert L. King, Chairman
Session Introduction 304
Robert L. King
Monitoring of Liquid Effluents From the Government Printing Plant 305
Albert R. Materazzi, Ph.D.
Discussion of Polychlorinated Biphenyls in Waste Streams From Paper Recycling 319
Karl E. Bremer
VI
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Table of Contents (con.)
Page
Recovery of Materials Used in Letterpress and Rotogravure Plate Preparation 327
William A. Rocap, Jr.
Solvent Recovery in a Modern Rotogravure Printing Plant 344
B. Gordon Watkins, Jr.
Paul Warned, Eng. D.
24 September 1975
Session III: IMPACT OF WASTE RECOVERY RECYCLING ON THE ENVIRONMENT (con.) 357
Robert L. King, Chairman
An Economic Approach to Treatment of Liquid Wastes in Rotogravure Cylinder Preparation 358
Donald P. Manning
Recovery and Reuse of Organic Ink Solvents 367
Richard L. Marvin, Ph.D.
Session IV: IMPACT OF NEW DEVELOPMENTS AND CHEMICAL FORMULATIONS 390
Robert H. Downie, Chairman
Opening Comments 391
Farley Fisher, Ph.D.
Session Introduction 392
Robert H. Downie
UV and Other Metal-Decorating Processes 394
Elgin D. Sal lee, Ph.D.
The Application of Solventless Inks in Web and Sheetfed Offset Systems 412
William E. Rusterholz
Electricure Environmental Impact 419
Robert G. Muggli, Ph.D.
Carbonless Copying Papers 426
George Baxter, Ph. D.
Session Summation 447
Robert H. Downie
CONFERENCE SUMMATION 448
Farley Fisher, Ph. D.
VII
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Table of Contents (con.)
Page
SUBMITTED PAPERS - NOT PRESENTED AT CONFERENCE 453
Comments From a Screen Printing Ink and Pressure-Sensitive-Film Manufacturer: 454
General Formulations — Division of General Research
John M. Sommer
viii
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22 September 1975
Opening Session
Farley Fisher, Ph.D.*
General Chairman
"Chief, Early Warning Branch, Office of Toxic Substances, Environmental Protection Agency,
Washington, D.C.
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OPENING COMMENTS
Farley Fisher, Ph.D.
General Chairman
I would like to welcome you all to the opening of the conference on
Environmental Aspects of Chemical Use in Printing Operations sponsored
by the Office of Toxic Substances of the Environmental Protection Agency.
I am Farley Fisher, Chief of the Early Warning Branch of the Office of
Toxic Substances of EPA. I am going to be your general chairman here, which
means I am pretty much of a figurehead.
However, since I am largely responsible for setting up this snowball,
which has developed into this conference, let me say just a few words about
why we decided to hold this conference and what we hope to accomplish.
The mission of the Early Warning Branch in EPA basically is to iden-
tify potential and environmental problems and to try to achieve some sort of
study and, if possible, some sort of resolution of those problems before
the matter becomes one of general concern and has to be settled in an arena
where speed is of the essence, where frequently, rational thought and care-
ful consideration get sacrificed in order for things to be done rapidly.
As part of our attempt to accomplish this, we thought, about 2 years
ago, that it might be nice to look at a few industries where people seemed to
have the feeling there were a lot of things going on, but nobody really knew
what. The idea was to find out exactly what the problems are or if business
is just a lot of rumor mongering and in fact, the problems are not nearly as
severe as many uninformed people seem to think they are. Accordingly, we
set up a series of conferences, which we hope will be a continuing series.
We invited people who are knowledgeable, who have things to say, to come to a
public forum which would be organized in such a way that all persons,
including those not on the program, would have an opportunity to contribute
what they could so that we could get a reasonably good picture of exactly
what the situation in question is.
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Somewhere along the line we abandoned the notion of holding conferences
by industries and felt that it would make more sense to do it in terms of a
series of processes without necessarily identifying them with industries,
even though in many cases the correspondence would be rather close. Conse-
quently, this conference is on printing processes. We hope to discuss any
printing operation, regardless of the type of industry to which it is nomin-
ally attached.
This is the third conference in the series. I think the series has
been successful at what we hoped it to do. These conferences have shown
that they can, in fact, stimulate a lot of good discussion and stimulate
people to do some thinking about things they might not otherwise have
considered.
It is inevitable when you hold a meeting for a general audience
that many of the people find some of the matter presented rather elementary
while others consider it quite new and interesting. I anticipate that most
of you, at one time or another, will feel bored by the presentation on the
grounds that you have heard it before. But I also think very strongly that
every one of you will find a great number of papers that will in fact tell
you things that you did not know before. I certainly hope every one of you
goes away from here knowing something you did not know when you came.
I want to make it clear that this is not a witch hunt. This is not
an attempt to put the printing industry behind the eight ball. There
are no regulatory actions which are expected to stem, in a direct sense,
from this conference.
I want to encourage everybody to be open and candid in what ttay ke. n
htrvB to say because I think that is the only way we are going to accomplish
what we are here to do.
The emphasis in this conference is on the environmental aspects: the
external environment, including air and water pollution, waste-disposal
problems, and matters of this nature. We realize that it is very difficult
if not impossible, to separate the environmental concerns from what you might
call microenvironmental concerns, the occupational setting, and some of the
papers today will in fact deal with occupational studies. We consider this
quite appropriate. However, it is my hope that we do not allow this to turn
into a conference on industrial hygiene. The idea of the conference is to
discuss the environmental aspects of chemical uses.
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Mr. Frank Ayer, who is standing by the door there, is the conference
coordinator from Research Triangle Institute. He and his staff are available
to help you with your problems. If you have any questions, please seek him
out. You will notice he already has grey hair, so you are not going to hurt
that too much more.
We are trying something a little bit different on this conference from
what we have done in the past. Because this is a general audience and we
realize that the industry itself is broken into some rather specialized com-
ponents, we are going to start with a brief review of practice in printing
operations. This review is based on a technical study, which was performed
by RTI as a planning step in designing this conference. In the past, we
have not presented the results of this study at the conference itself, but
we have found that this frequently meant that speakers who really wanted to
talk at a technical level had to go back and give a primer to much of the
audience about what they had to say. This study, I realize is going to be
old news to those of you who are experts in the field, but we hope, by
presenting it, to bring some of the nonexpert audience up to a level that
will permit the other speakers to launch right into technical material.
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OVERVIEW OF PRINTING PROCESSES
AND CHEMICALS USED
Ben H. Carpenter and Garland K. Milliard*
Abe tract
This overview of the use of chemicals in the printing industry identifies
potentially detrimental effects on the environment or upon health that merit
further investigation. The size and diversity of the industry presents a
major problem in the study of the environmental aspects of chemical usage
therein. As a prerequisite, therefore, -tine industry is categorized, in
logical fashion, into major printing processes, subprocesses, and supporting
processes. For these categories, the current status of utilization by the
industry as well as the projected status is estimated. Within these categories,
different types of printing operations are discussed, along with their prod-
ucts, in terms of the chemical usage and the possibility of air pollution,
water contamination, solid waste, and odor generation. The aim is to indi-
cate the scope of potential problems and their relative magnitude within
the industry. New inks and processes are reviewed to show their potential
roles and impacts on the environment.
INTRODUCTION
The printing industry applies inks, coatings and varnishes, and sol-
vents to papers, textiles, metals, wood, and plastic materials. Press op-
erations themselves involve emissions to the air. Water use is minimal
unless water-base inks are used. Supporting processes (composition, photog-
raphy, and platemaking), however, involve water contamination, including
contamination with metallic salts. The amount of solid waste from printing
operations varies widely, and depends upon the size of the plant. Both
printing operations and supporting processes involve odors to some extent.
*Ben H. Carpenter, Senior Engineer, Research Triangle Institute,
Research Triangle Park, North Carolina; Garland K. Milliard, Consultant,
Engineering Department, North Carolina State University, Raleigh, North
Carolina.
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Odors arise where chemical solvents are evaporated and where chemically
reactive inks are exposed to heat.
Five printing processes have been assessed in a recent survey as
sources of organic chemical emissions: lithography, letterpress, gravure,
flexography, and screen printing (ref. 1). Heat set inks used in lithog-
raphy and letterpress generally contain 30 to 40 percent solvents. At
least half of this solvent is removed in dryers. Gravure and flexographic
inks contain up to 60 percent low-boiling solvent, most of which is re-
moved in drying. The major source of emissions in metal decorating (by
lithography and screen printing) is the protective coatings put under and
over the ink, rather than the ink itself. Many types of inks and paints
are used in screen process printing. This process has the smallest total
production of paper substrates, but is applied extensively in textile print-
ing. It is definitely a process to study in terms of pollution and health
hazards.
The industry prepares image transfer materials, using photographic
typesetting and other processes, from which organic compounds, metallic
residues, and scrap can be wasted to the air or to water, or to solids
disposition.
PRINTING PROCESSES AND AIR POLLUTION
The status, the products, and the chemical usages of the major printing
processes are given in appendix A, which also includes these characteristics
of the supporting processes. The pollution potential of each of these op-
erations depends upon the nature of the process employed. Printing opera-
tions themselves tend to result in emissions of ink solvents and chemicals,
some odor generation, and some solid wastes.
Offset lithography transfers ink from an image area, which is essen-
tially at the same level as the nonimage area. The nonimage area is wet
by water and the image area is wet by ink only. Water is transferred to
the plate first, followed by the ink.
This process customarily employs curved metal plates mounted on a
cylinder press. Water used to dampen the plates may contain 15 to 30 per-
cent isopropanol. (If the Dalgren dampening system is used, isopropanol is
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required.) Ink is transferred to the plate, then from the image to a
rubber surface on the blanket cylinder, which transfers the ink to the pa-
per. When a web or continuous roll of paper is used, this process is com-
monly called "web offset."
Figure 1 shows a web offset publication process flow chart in which a
38-inch wide web enters the press at 1,000 feet per minute. With blanket-
to-blanket press configuration, the paper is fed between two blankets and
two different images are printed simultaneously on the two sides of the
sheet. The web passes through several printing units to complete the print-
ing of complete images on both sides, and then it enters the dryer. Leaving
the dryer, the paper passes over chill rolls and is then ready for cutting,
folding, and finishing. The system exhausts 1,500 to 3,500 standard cubic
feet per minute (scfm) of air; it circulates 6,000 to 10,000 scfm through
the dryer.
Other configurations are possible. When the paper is printed on only
one side, the dryer exhaust rate may be up to 30 percent less than when
both sides are printed. A tunnel (floater) dryer is the only type for use
when both sides of the web are printed simultaneously. A steam drum dryer
is not applicable because of the problem of wet ink contact with the steam
drum surface.
Optional additions to the drying process, for emissions control, are
shown with dotted lines. While exhaust from the chill rolls is shown
entering the dryer exhaust, it could probably be added to the dryer recycle
as part of the makeup air, or simply be exhausted without any correction.
More information and data are needed to determine whether chill-roll ven-
tilation air needs treatment to eliminate emissions.
The web offset process, when used to print newspapers and business
forms, does not usually employ dryers and air pollution control equipment.
Emissions are thought to be low because the inks contain very little solvent,
porous paper is generally used, and the coverage is much less with text
than with pictorial process color work. The total consumption of ink and
its associated solvents in newspaper printing has not been separately tab-
ulated. (Census figures exclude a substantial quantity of captive ink
made by large printers for their own use.) Nor is there much data on
actual emissions.
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(Optional equipment shown dotted; letterpress and offset
incineration systems are interchangeable.)
Figure 1. Web offset publication.
8
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Sheetfed lithography uses either coated or uncoated paper, and applies
low solvent, oxidative-drying inks. Isopropanol is commonly used in foun-
tain solutions. Ink usage is much less than in web offset publication
because of the lower feed rate and also because usually only one side is
printed.
Letterpress printing transfers ink directly to the paper from the
image surface, which is raised slightly above the rest of the plate.
In letterpress newspaper printing, the image is transferred to a mat
which can be curved to make a cylinder plate. No dampening solution is
used in this process. Washup solvents are, however, used on the press.
All other air and organic emissions are from the dryer unless an incinera-
tor is used, in which case the only exhaust is from the incinerator. In a
few cases, a catalytic incinerator has been installed in a recycle line for
the dryer. This has not necessarily eliminated the need for another incin-
erator for the exhaust gases.
Letterpress newspaper printing tends to emit relatively inert ink mist
and paper dust. The amounts are claimed to be noticeable only in very
large installations and can presumably be controlled by an air conditioning
system; that is, by moderate filtration of the air. Filters are sometimes
placed in ducts located over the presses to remove some of the ink mist and
paper dust.
Letterpress publication printing uses different inks for color repro-
duction, etc. Also, different papers are used, and the inks are not dried
by absorption alone. These differences lead to different problems in emis-
sion control.
Sheetfed letterpresses tend to use more ink than sheetfed offset
presses, because the letterpress ink film is two to three times as thick as
the lithographic ink film.
Metal decorating processes transfer the image by lithography or screen
to a dried (usually vinyl) lacquer undercoat applied to the metal sheets.
Several colors may be applied. After printing, a trailer roller coater
puts a varnish coating over the wet ink, and the sheet is dried again. For
bottle caps, a thick coating of varnish is put on the outer side and dried.
Sheets leaving the 300° F drying ovens may still have 7 to 10 percent
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solvents (ref. 2). Coating thickness and solvent content influence the per-
cent solvent in the oven exhaust. Exhaust rates are usually set to limit
solvents from 10 to 25 percent of the lower explosive limit. Since the
inks themselves contain little solvent, the emissions from lithographic
metal decorating are small compared to those from coating application and
drying. Solvent is not always exhausted from the roller coating area.
Flexographv. like letterpress, transfers ink directly from the plate
to the paper or substrate. The plate image area is raised above the rest
of the surface. It is made of rubber, however, and alcohol-base inks are
used; these characterize the process as flexography. Most flexographic
inks contain about 55 percent organic solvent. There are, however, three
types of inks: solvent inks, steam set inks, and water-base inks. When
solvent inks are used, the product may be steam drum dried or air dried at
140° F, and then passed over chill rolls. It is assumed that more solvent
is driven out in the dryer than at the inking area, but the ratio is not
known. About 90 percent of the applied solvent is believed to be driven
out during and after printing. The remaining 10 percent of the original
solvent would evaporate slowly from the solidified vehicle resins on the
cool web.
Steam set inks, employed in the "water flexo" or "steam set flexo"
process, are low-volatility inks of a paste consistency, which are gelled
by water or steam. The vehicles generally consist of a glycol type solvent
almost saturated with a resin. The addition of water lessens the solvent
power of the glycol, causing the resin to precipitate and gel the vehicle.
Further gelling occurs as the solvent penetrates the substrate. This proc-
ess is used for paper bag printing. No significant emissions have been
observed from this process.
Water-base inks are based on aniline dyes, but are now usually pig-
mented suspensions in water. A dryer is often employed, but since the
solvent is water, no emission problems arise.
Gravure processes employ an image recessed relative to the surface of
the image carrier. Ink is transferred directly from the image carrier to
the paper, film, or other substrate. Since the ink is picked up in the
image area and the excess scraped off the nonimage area with a doctor blade,
10
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its viscosity is kept low by a relatively large amount of low-boiling sol-
vent. Control of solvent vapors around the ink fountain is necessary to
avoid explosions.
Gravure may be sheetfed or roll fed (rotogravure). Rotogravure is
used for coated or uncoated paper, film, foil, and combinations thereof.
The process employs either steam or hot air drying at 90° to 150° F- Sol-
vent vapor control is used at the press, the dryer, and the chill rolls.
Activated carbon can be used to absorb the vapors, since there are no com-
bustion products or solvent breakdown products in the exhaust. The concen-
tration of solvent in the exhaust from the activated carbon beds is not
known, and reliable data are not available.
U.S. plants have recently begun to apply heat-transfer printing to
textiles, using the gravure process. The desired pattern is applied to
dry-transfer paper, and heated to volatize it onto the fabric. Current pro-
duction is some 40 million yards of dry-transfer paper (ref. 9).
Screen printing employs a fine screen for the image area, through which
ink or paint can be forced. Nonimage areas are produced by coating the
screen to mask off the ink. The amount of organics exhausted into the air
depends on the type of ink used. When water colors (for posters), or water-
base emulsions (fabric printing) are used, there are no significant emis-
sions. This is also the case if oleoresinous poster inks or alkyd enamels
are used. Fast-drying lacquer inks cause significant emissions, however-
Evaporation takes place in the printer and the dryer. No information about
the percent solvent removed in each operation is available. It is predicted
that the solvent will continue to evaporate on the drying racks, although
the ink may dry enough to overprint. A study on solvent retention in poly
(methyl methacrylate) films—not inks—shows 6 percent residual toluene sol-
vent after 6 months air drying (ref. 3).
Flat and rotary screen printing processes are used to print textiles.
Resin-bonded pigments are frequently used (ref. 8).
Thermography is an extension of the printing process, in which the im-
age is raised on a printed page to give the effect of engraving. Either
resinous powders are deposited on the print or specially formulated inks
that swell on heating are used. Only a few manufacturers who specialize
in business or social stationery practice this process.
11
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There are five basic steps, if inks and powder are applied separately.
The form is printed as usual by letterpress, or lithography, each having
its own characteristic losses of solvents to the air. A raising powder is
applied to the printed sheets so that it adheres to the wet ink. Excess
powder is removed from the remainder of the sheet. The entire sheet is
heated so that the powder melts and fuses with the ink. The sheet is cooled,
causing the molten powder to harden. The powdered resins are a potential
air pollutant, in their recovery and recycle. Where inks contain the powder,
premixed, the process requires only two steps, printing and heating. There
is less danger of pollution.
SUPPORTING PROCESSES AND WATER POLLUTION
In addition to the printing processes themselves, there are certain
associated processes which are a part of the industry: binding, composi-
tion, photography, and platemaking. These appear to generate few problems
of air pollution, but are sources of water pollution.
Binding involves the application of hot glues to books, magazines, and
commercial forms. Unless solvents are used, the emissions are mostly water
vapor. Spiral binding involves the attachment of a plastic binder to spe-
cially punched text material. Dusts and waste paper are the principal poten-
tial pollutants; chemicals are not involved.
Composition is that step in which the "layout" or model of the copy is
converted to press-usable form, either by the hot type method or the cold
type method (see appendix A). The hot type method does not employ chemicals.
It is used mostly for letterpress printing. In linotype and monotype opera-
tions, water may be used for noncontact cooling although most of the machines
are air-cooled. Average usage would be about 11,000 liters/day per machine,
and a large newspaper would require 20 to 25 linotypes (ref. 10).
Cold type composition includes photo composing, where water is used in
the developing and fixing of the output from the typesetting machine.
Waste characteristics are similar to the photographic processing wastes to
be discussed next. Volumes are generally low, about 5,700 liters/day for
one machine, which is adequate for all but the largest printing operations.
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Photography is employed (essentially in all the basic printing proc-
esses) in the development of film for printmaking and in the development
of black and white prints in cold type processes. Organic vapors are emit-
ted from developing baths and dryers. Wash and rinse waters from automatic
film developers, and from tray developers, have been sampled and tested for
contamination (ref. 10). For the rinse waters, chemical oxygen demand (COD)
ranged from 100 to 310 milligrams per liter (mg/1), aluminum from 2.5 to
7 mg/1, and silver from 0.6 to 5.5 mg/1.
These wastes were toxic to unacclimated seed, and therefore no data on
biological oxygen demand were obtained. Other studies have shown that
these wastes are amenable to treatment in acclimated biological waste treat-
ment systems (ref. 11).
Photographic solution wastewaters showed COD's of up to 64,000,
aluminum up to 1,300 mg/1, and silver to 3,400 mg/1 before recovery.
In platemaking, potential for pollution varies with the printing proc-
ess involved. Flat-bed letterpress plate preparation does not use water,
nor are there solvent emissions to air in the simple assembly of type with
"half-tones," that is, engravings usually made in an engraver's shop.
Cylinder letterpress plate preparation requires water for prerinsing,
etching, and postetching rinses. The chemicals used depend upon the type
of plate. Magnesium plates are most commonly used. Zinc and aluminum are
alternatives. Prerinse solutions containing nitric acid, gum arabic, and
water prepare the plates for etching. About 0.5 liter is used per plate.
The wasted solutions have shown up to 31,000 mg/1 COD, 49 mg/1 aluminum,
0.26 mg/1 chromium, and 18 mg/1 zinc (ref. 10).
During the etching step, about 200 grams of magnesium are dissolved
from each plate, using a solution containing nitric acid, detergents, sur-
factants, and water-soluble solvent. Wastewaters from aluminum plate
etching have shown up to 27,000 mg/1 magnesium, 1,400 mg/1 aluminum, and
430 mg/1 zinc. Where aluminum or zinc plates are etched, wastes have shown
23,000 mg/1 aluminum and 56,000 mg/1 zinc, respectively.
Postetch rinses use about 6 to 10 liters of plain water per plate.
Grab samples have shown COD values to 3,100 mg/1, to 6 mg/1 aluminum, to
140 mg/1 magnesium, and to 2.9 mg/1 zinc.
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Flexography plates are etched with caustic. No sample data are
available; however, large platemakers are reported to use only about 95
liters of solution per week.
Offset plates for lithographic printing are rinsed free of developers.
Manual rinses require about 30 liters per plate. Automatic rinses use
more water, and usage is proportional to plate length (up to 176 liters
for a 140-cm-long plate). A typical large shop might process 35 plates per
day. The rinse waters have shown COD's up to 2,000 mg/1, and total sus-
t
pended solids of up to 100 mg/1.
Rotagravure plates (cylinders) are first washed with acetic acid, then
treated with nickel salt solutions, rinsed, and plated with a thin film of
copper. The plating solution is replenished but seldom discharged. After
plating, the cylinders are rinsed with about 30 liters of water. One plant's
waste shows up to 620 mg/1 copper and up to 1.2 mg/1 aluminum (ref. 10).
The plated cylinder is wet polished, and the effluent waters have shown to
90 mg/1 suspended copper. The polished surfaces are etched with concen-
trated ferric chloride, which is either used to depletion or replenished.
The etched surfaces are rinsed to remove dissolved metals. The rolls are
finally subjected to developing and cleansing washes requiring about 700
liters of water per cylinder. The chemicals used are usually sulfamic acid,
methanol, and diacetone alcohol. Postetched rinse wastes show up to
5,400 mg/1 iron, up to 600 mg/1 copper, and up to 290 mg/1 suspended solids.
SOLID WASTES AND ODORS
The amount of solid waste from printing operations varies widely, and
depends upon the size of the plant. Large plants spoil about 3 percent of
their paper, while smaller plants spoil much more (ref. 12). Most paper
scrap is baled for sale. Metal scrap is nearly all recycled. Silver is
usually recovered from photography wastewaters. Most of the problems of
solid wastes and their chemicals arise in the recycling and disposal indus-
tries, not in the printing operations themselves.
Since paper is recycled, treatment processes are applied to remove
the inks. Detergents are used, and salts are added to differentially pre-
cipitate the cellulose and ink particles suspended in water (ref. 13).
14
-------
Peroxides have been proposed for removal of printing inks (ref. 14). The
feasibility of feeding waste paper to farm animals as a source of cellulose
has been explored. The presence of polychlorinated biphenyls makes the
practice questionable (ref. 15).
Photographic developers and wash solutions usually contain odorous
volatile solvents. The odor of acetic acid is often present in photography
process areas. This acid has been shown to be harmful to workers' eyes,
and is usually removed from the work area with exhaust fans. It is doubt-
ful that the resulting concentrations in the ambient air would have a
detectable odor.
Some inks produce odors as the result of chemical reaction during the
printing or drying operations, and others, by interaction with the sub-
strate. Most of the odors from inks, however, are those of the solvents
employed. No crucial odor problems have been identified at this time.
TYPES OF CHEMICALS USED
A complete listing of the chemicals employed in printing processes
would be endless, even if it were possible.* Much of the formulations
utilized are bought by the printers from manufacturers who sell under
trade names and guarantee performance. The compositions of their formu-
lations are not disclosed. This itself is a problem in the search for
potential hazards needing controls and standards. The drying operations
employed in printing can decompose certain solvents contained in the inks,
so that emissions are not the same compounds as those fed to the system.
The extent to which such decompositions occur is known to be influenced
by the kind and quality of paper, textile, or other substrate employed.
At the present time, the restrictions imposed on hydrocarbon emis-
sions from stationary sources are expected to affect the printing industry
extensively because their chemicals yield these types of emissions. Sul-
fur oxides and carbon monoxide are not problems. Solid particulates do
not generally present problems, but plume opacity will be a problem. Nitro-
gen oxides may present problems where noncatalytic incineration is employed.
*A partial listing is given in appendix C.
15
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The modification of materials has been rapid and extensive in the last
several years so that many printers may have choices of inks and other
materials which can effectively control, or at least help control, their
pollution problems.
INKS
Letterpress inks are viscous pastes. Vehicles used are slow-drying
alkyds or vegetable oil (e.g., linseed oil) derivatives. These inks dry
by oxidation and polymerization, during which chemical changes occur that
can result in odorous products. Oxidation may be promoted by the addition
of reactive ingredients, and these may be volatile or may cause odors.
Polymerization may be catalyzed by certain metal salts of organic acids.
Although these inks do not dry for several hours, they set (with the assis-
tance of spray powders to protect the printed film) sufficiently to allow
satisfactory overprinting through successive units, such as in multicolor
work. They are not acceptable, however, for high-speed web operations in
letterpress and in offset. These require an ink that will dry in a second
or less. Heat-set inks were developed to fill this need. They contain
varnishes made by solubilizing solid resins in high-boiling hydrocarbon
solvents. A typical heat-set ink may contain 35 to 45 percent of petroleum
hydrocarbons with a boiling range of 450° to 550° F. The inks are dried by
rapidly removing the solvent as the paper web passes through a drier at
temperatures as high as 400° to 500° F. Some thermal degradation, principally
of ink and paper components, does occur.
Ink manufacturers have sought a more economical means of printing with
high-speed processes than putting solvent into an ink before printing and
promptly removing it immediately thereafter. New inks that represent
technological advancement beyond solvent reformulation include thermally
catalyzed single- and two-component (heat-reactive) systems and ultraviolet-
sensitive (photoreactive) systems. These have progressed to commercial
feasibility in the United States. Thermally-catalyzed inks contain a pre-
polymer, a cross-linking resin, and a catalyst. The catalyst activates at
350° F in the drier and converts the liquid into a solid polymeric film via
condensation polymerization reactions. Reaction byproducts are principally
16
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C-, -CM alcohols, moisture, and small amounts of formaldehyde; thus, conden-
sate buildup is prevented in the drier. Overall volatile content of such
inks is 20 percent or less of that of the conventional heat-set inks. The
smoking tendency is practically nil. Stack odor is said to be reduced
(refs. 17,18,19).
Because heat is required for drying, these inks cannot be used on
sheetfed presses. The inks have objectionable inplant odors. They are at
this time expensive (35-80 percent more than heat-set). They are reported
to permit buildup of static electricity in the folding operation. More in-
formation is needed concerning the extent of applicability and acceptance
of this product.
Photoreactive ink systems (UV-inks) consist minimally of one or more
monomers and a photosensitizer that selectively absorbs energy. No sol-
vents are contained in the mixture. There are no byproducts since the re-
action is addition polymerization. The paper is not heated above 50° C,
and a minimum of moisture is lost in the process. The inks do not react
until exposed to ultraviolet light; they therefore may be allowed to re-
main in the fountains and on the rollers for long periods of time. These
inks offer advantages to sheetfed lithography; eliminate "set-off," the
unintentional transfer of ink to adjacent sheets before the ink has dried
completely; eliminate use of powders that are applied to protect an ink
film that is "set" but not "dry"; and eliminate the storage of printed
sheets for ventilation, required in oxidative drying processes. Disadvan-
tages of this system include cost (75-100 percent more expensive than con-
ventional heat-set inks), the use of expensive UV lamp systems, hazards of
UV-radiation to operating personnel, and the formation of ozone by the
action of ultraviolet light on oxygen. Conventional commercial procedures
will not deink papers printed by this process. This process is, however,
at present in commercial use, and more information is required concerning
progress in its implementation.
Inks used in lithography are similar to those used in letterpress.
Flexography, however, uses inks of low viscosity, made of solvent-resin sys-
tems colored either with dyes, pigments, or combinations thereof. The
film-forming ingredients vary but usually are soluble in alcohol, alcohol-
hydrocarbons, or water. These inks are often employed in metal decorating.
17
-------
Some of them, when permitted to come in contact with metals, undergo a chem-
ical reaction and yield a marked odor which is offensive in products, but is
not a pollution problem.
Rotogravure inks are low-viscosity solutions of resins in suitable sol-
vents. Air drying presents potential pollution problems. Among the conven-
tional solvents used, toluene and xylene have appreciable odor. To some
extent the solvents have been replaced with alcohols having a much milder
and less objectionable odor.
Screen printing inks contain a variety of solvents, adhesives, water
colors, and emulsifiers. Fast-drying lacquer inks are a serious source of
pollution. Among new approaches to pollution control is the use of micro-
wave drying, which tends to evaporate polar solvents without degradation.
This technique is indicated for use in gravure and flexography and offers
a means of using extensively water-base gravure on plastic substrates.
Metal substrates present a problem because they reflect microwaves back to
the applicator and damage it. Microwaves are a potential health hazard
should leakage occur. Commercial trials in Europe with microwave units for
drying inks on cartons have been sufficiently successful that several large
European companies reportedly have installed such dryers (ref. 20). The
general acceptance of this system is a long time away.
Radio frequency drying is under experimental development. Electron
beam drying offers the potential for elimination of solvents and catalytic
agents in the inks, but has the disadvantages of degrading the paper under
the heavy dosage required, and of generating X-rays, thus necessitating
elaborate and expensive operator protection.
The following companies have introduced heat-reactive and/or photo-
reactive inks: Bowers Printing Ink Company; Kohl and Madden Printing Ink
Corporation; Richardson Ink Company; Roberts and Porter, Inc.; Sinclair
and Ballentine; and General Printing Ink Division of Sun Chemical Corpora-
tion. Three companies have advanced to the stage of press trials with
ultraviolet ink: Sinclair and Ballentine, Jensen Printing (a subsidiary of
Holden Industries, Minneapolis), and I. S. Berlin in Chicago.
Further information needs to be brought forth at this time concerning
solventless inks. The Lithium Corporation of America introduced in 1971 a
18
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new liquid, polybutadiene-alphamethylstyrene copolymer resin for solvent-
free manufacture of printing inks. Trademarked Lithene-Y, the resin series,
which was to be available in high and low molecular weights, eliminates the
need for solvents because of the low viscosity of the 100-percent reactive
materials. The Richardson Ink Company recently introduced its "Duralum
Mark V Ink," which should eliminate the need for overprint lacquer when
printing aluminum beverage cans. Further information concerning this prod-
uct would be desirable.
In recent years, there has been a tendency towards increased use of
pigments in textile printing. Pigments are molecular aggregates, insoluble
in the media to which they are subjected during application and use. They
may belong to any chemical class of colors, but they do not contain groups
capable of interaction with fibers. Their fixation is achieved, therefore,
with the use of a binder which encloses them and provides a bond between
them and the fiber- The binders are high-molecular-weight, film-forming
materials produced by polymerization of simple intermediates that are ini-
tially present in the printing paste. After evaporation of solvent, a thin
coherent coating is produced by heating. This film encloses the pigment
particles and adheres to the fiber. The rubbing, washing, and drycleaning
fastness properties of a pigment print are, therefore, those of the binder
film. The most important monomers in modern binders are derivatives of
acrylic acid, butadiene, and vinyl acetate. To some extent, urea, melamine,
and related products are significant as raw materials for the manufacture
of formaldehyde condensates suitable as binders. In pigment printing, white
spirit emulsions employed for thickening cause several problems: flammabil-
ity, odor, and air and water pollution. There is a need for reports of
development work underway to reduce or eliminate these problems. The recent
development of fully synthetic water-soluble thickeners has enabled the
first step to be taken toward avoidance of white spirit. These thickeners
are polyacids of very high molecular weight attained by special processes
and supplied in various formulations. Their common feature is their un-
usually high specific thickening action after neutralization.
Wastewaters from printing operations have been shown to contain
varying if not high amounts of metals, total suspended solids, and materials
19
-------
contributing to chemical oxygen demand. Because of this, the extent of
effluent reduction attainable through application of the best available
technology has been estimated (ref. 10). For example, rotagravure monthly
average limitations for effluents have been projected as follows: aluminum,
0.5; COD 5, 30; chromium, 0.5; hexavalent chromium, 0.05; copper, 0.5; pH,
6-9; silver, 0.05; total iron, 1; total suspended solids, 30. All units are
grams per cylinder except for pH, which is in conventional units for this
determination. More information is needed concerning the application of
treatment technology and the extent to which these recommended standards
can be met. Costs of complying with these standards also needs to be pro-
jected at this time.
SUMMARY AND RECOMMENDATIONS
This review of chemical usage in the printing industry shows the indus-
try to be a dynamic and varied enterprise now going through an era of sub-
stantial change, part of which has been motivated by the needs for pollution
control and for protection of worker health. The letterpress process now
has approximately 35 percent of the market which it supplies and is growing
at a rate of about 2-1/2 percent per year. Lithographic processes, however,
are enjoying a 12 percent per year annual growth. Flexography is predicted
to grow in newspaper and publishing areas. It will be adapted to letterpress
and offset processes in the near future. Gravure has about 8 percent of the
printing market and it is predicted to capture up to 11 percent in the 1980's,
Its growth is about 10 to 12 percent a year. It is concentrated in a few
highly specialized plants. The screen process now has 2 percent of the total
printing market; it is not expected to grow substantially except in the
printing of fabrics, textiles, and carpets. It is definitely, however, a
process to study in terms of pollution and health hazards. Composition,
photography, and platemaking aspects of the industry are undergoing rapid
changes, some of which direct toward more air pollution and less water
pollution.
Many of the solvents utilized in this industry are hydrocarbon in
nature, and amenably to control by incineration, absorption, and other conven-
tional processes. Industry is, however, beginning to be in the position of
20
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having a choice between the old solvent-base inks and materials and the new
nonsolvent-base inks employing different processes. Some of the new proc-
esses available for use with solventless inks involve new hazards which re-
quire some study and evaluation. In this connection, textile printing,
with its vast variety of pigments, dyes, colors, and inks, and its exten-
sive list of proprietary formulations, is almost a special category itself.
In view of the extensive innovations carried on in recent years, it is
recommended that a conference at this time concentrate on the clarification
of the findings of these innovations, on the extent of commercialization of
any processes or procedures that tend to alleviate pollution problems, and
on thoroughly delineating through discussion involving experts the advantages
and disadvantages of the approaches. The industry should be reviewed at
this time in terms of its future and current trends. The program partici-
pants must, if this recommendation is adopted, include personnel of com-
panies supplying materials—inks, papers, other substrates—and equipment
peculiar to the industry. Less factual information is available concerning
air pollution than concerning water pollution, primarily because more exten-
sive sampling and testing has been performed on wastewater samples. It is
recommended that part of the sessions of the conference focus upon new meas-
urements of the effluents and emissions from printing processes.
REFERENCES
1. R. R. Gadomski, et al., Evaluation of Emissions and Control Technologies
in the Graphic Arts Industries, Graphic Arts Technical Foundation,
NTIS No. PB195770, 1970.
2. D. R. Hays, Official Digest, Vol. 473, No. 36 (1963), pp. 605-624.
3. A. K. Doolittle, The Technology of Solvents and Plasticizers, John
Wiley and Sons, N.Y., 1954.
4. H. F. George, "Gravure: A Giant Bursting Its Bonds," Printing Magazine
National Lithographer, Vol. 91, No. 10 (October 1967), p. 54.
5. Printing Impressions, (U.S. Department of Commerce Quarterly Industry
Report), Vol. 17, No. 8 (January 1975), p. 16.
6. Harris Study, "Sheetfed Offset Commands Commercial Market," Graphic
Arts Monthly, Vol. 46, No. 12 (December 1974), p. 50.
21
-------
7- R. Bassinger, "Status of Ink: An Overview of What to Expect in
Tomorrow's Technology." Printing Magazine, Vol. 95, No. 5 (Way 1971),
p. 50.
8. W. Schwindt, et al., Resin Bonded Pigment Printing and Dying, Review of
Progress in Coloration, Vol. 2, 1971, pp. 33-41.
9. R. Brewer, "Heat Transfer in Perspective," Printing Trades Journal,
November 1974, p. 22-24.
10. A. N. Masse, "Development Document for Proposed Effluent Limitations
Guidelines and Standards for Performance for the Printing and Publishing
Industry," EPA, Office Air and Water Programs, Washington, D.C., Septem-
ber 1974.
11. "Photoprocessing and Environment," National Assoc. Photographic Manu-
facturers Seminar, Los Angeles, June 18-20, 1974.
12. R. C. Short, Solid Waste Management in the Printing and Publishing
Industry, Proceedings, National Industrial Solid Waste Management
Conference, Houston, 1970.
13. W. J. Krodel, et al., Process for De-Inking Printed Waste Paper, Great
Britain Patent No. 827, 503.
14. R. V. Stau, "More Waste Paper Recycling Possible and Desirable,"
Chemical Weekblad, Vol. 65, No. 36 (September 1972): N93-5.
15. "Digesting the News," Science News, Vol. 102, No. 25 (December 16, 1972),
p. 392.
16. R. W. Bassemir, "Avoiding Solvent Emissions," Sol vent!ess Inks, AICHE
Symposium, August 29 to September 1, 1971, Paper 48c.
17. Graphic Communications Weekly, Vol. 4, No. 42 (November 2, 1971),
pp. 8-9.
18. W. R. Surgeon, "Two New Ink Systems," Graphic Arts Monthly, Vol. 43,
No. 9 (September 1971), pp. 42-44.
19. B. V. Burachinsky, "Litho Inks and Air Quality," Modern Lithography,
Vol. 38, No. 11 (November 1970), pp. 56-57.
20. D. H. Woods, et al., "Microwave Drying of Inks," Amer. Ink Maker, Vol.
48 (December 12, 1970), pp. 29-40, 42, 44, 59-61.
22
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APPENDIX A
PRINTING PROCESSES. PRODUCTS, AND CHEMICAL USAGE
Process
1. Letterpren
(relief printing)
A. Sheet-Fad
Press ( Platen
Type* ( Cylinder
Composition:
Handset
Machine
Linotype
Ludlow
Line-casters
Status Products
35% of market; Gold stamping
Ave. annual growth Die cutting
1963-72: 2.5% (5) Forms
Stationery
Pamphlets, brochures
Books x
Magazines
Newspapers
Tags
Labels
4-color process
NCR forms*
Chemicals
Inks - Dry by
ebsorption, chemical
oxidation, and
evaporation.
Driers
Cobalt
Varnishes
Reducers
Retarders (nonskin)
Type wash*
Press and roller wash*
Spray powders
Flame dryers
B. Web-Fed
Print from:
Stereotyping
Electrotyplng
Photogelatln
plates
2.
Flexonraphv
(relief printing)
Print from rubber
or photopolymer
plates.
Bakellte plates
3. Lithography
(Planography)
A. Sheet-Fed
Newspapers
Books
Magazines
Predicted to grow
In newspaper and
Continuous forms
Snap-apart forms
Plastic film
Foil bags
Milk cartons
Cardboard cartons
Gummed tape
News Inks
Dry by ebsorption
Process Inks
Dryers
Varnishes
Reducers
Retardars
Type wash
Press and roller wash
Spray powders (to prevent
setoff)
Flame dryers
Water-base
catalyzed Inks
Ultraviolet inks
publishing Industry. (1) Bread and candy wrappers
Will be adapted to
letterpress and
offset processes
In future.
55% of market
Ave. annual growth
1963-72" 10.2% (5)
92% of lltho
commercial printing
In the next 5 years. (6)
Presently growing at
rate of 6-8% per
year. (7)
Newspapers and magazines
on Increase
Small newspapers
Greeting cards
Maps
Posters
Labels, tags
NCR papers
Forms
Stationery
Brochures, booklets
Magazines
Books
Pletemaklna
Sansitlzer coatings
Desensitlzers
Developers (lacquers)
Gum arable
(preservative)
Image removers
Subtractive developers
for subtractlve plates
Plate cleaner (to remove
toning)*
Carbon arc (can exceed
ozone limit* established
by OSHA)
Mercury lamps
Newspaper Industry - largest single Industry In terms of $ - predicted $10.8 billion In 1975.
* Identifies possible toxic materials.
23
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APPENDIX A (eon.)
Process
Status
Products
Chemicals
3. Lithography
(Planography)
A. Shot-Fed (con.)
B. Web-Fed
4. Gravure
(Intaglio)
A. Copperplate and
steelplate
B. Photogravure
C.
Rotogravure
Printing don* by
rotary presses.
Paper fad from
rolls (wab) Ink
In liquid form.
Pratantly growing at
10-12% paryaar. (7)
Will amount to 8% of
total lltho commercial
printing In next 5
years. (6) Farter
growth rate, but
It starting from a
smaller bate.
Newspapers
Magazines
Books
Foils
Plastics
Metal decorating
Continuous forms
Snap-apart forms
8% of printing market.
Predicted to capture 11%
In 1980's. Fastest
growth rate of 10-12%
per year. (5)
Highly concentrated In
few highly specialized
plants.
Slow and expensive,
limited use. Mostly
done by hand.
Most predominant of
gravure processes.
Fastest growth rate of
all printing processes
of 12-15% per year. (7)
Announcements
Invitations
Social stationery
Business stationery
Government currency
Government bonds
Postage stamps
Fine paintings
Photographs
Catalogs
Magazines
Wallpaper
Fabrics
17% specialty prlntlng(4)
27% packaging
50% publications
Plate materials
Aluminum - 96% of all;*
Zinc; Brass;
Copper; Chrome plate;
Steel
Pressroom
Gum arable
Fountain solutions to
maintain pH 1) glycerine
and 2) alcohol
Powder spray
dryers to prevent offset
Flame dryers to set Ink
Roller and blanket wash
Rubber rejuvenator
Inks
Reducers*, varnishes*,
driers*
Retarders (to prevent
"skin")*
Fluorescent Inks*
Metallic Inks
Regular Inks*
Plastic Ink
Foil Ink
Pressroom
Same as sheet-fed
Inks
Process Inks
Ultraviolet (UV) inks
Heat-reactive Inks
Plate making
Etches (25% nitric acid)
Fixers
Developers
Plates
Prepared photographically
and etched chemically.
Cyllndermaklng
Semlauto gravure
cylinder etching
machines
Electronic color
scanner*
' Identifies possible toxic materials.
24
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APPENDIX A (con.)
Process
Status
Products
Chemicals
4. Gravura
(Intaglio)
C. Rotogravure (con.)
For more Information:
Gravure Research Institute
Gravure Technical Association
Wood grain covering!
Vinyl sheeting
Decorative high-pressure
laminates
Foil
Electronic gravure
cylinder engraving
Pressroom
Electronic Ink transfer
process
Inks
6. Screen-Process
6. Thermonraohv
A process used to
raise the Image on a
printed page after
being printed by
letterpress or
lltho process.
Gives the effect
of engraving.
Process uses either a
resinous powder which It
deposited on Ink after
printing or specially
formulated Inks that
react to heat causing
Ink to expand or "swell"
thus raising the Image
from the paper.
2% of total printing
market. (6)
Not expected to grow
substantially.
Definitely a process
to study In terms of
pollution and health
hazards.
Process performed by
relatively few manu-
facturers who special-
ize In social and busl-
Iness stationery.
Posters
Billboards
Glass bottles and jars
Book covers and ribs
Toys
Furniture
Fabrics
Oilcloths
Glass plate
Felt banners
Printing circuits
Dials
Metal
Clay
Screenmaklng
Announcements
Invitations
Social and business
stationery
Pressroom (solvents,
sprays, etc.)
Lacquer thinners
Mineral spirits
Reducers
Inks
Oil paints, enamels,
poster paints, lacquers,
varnishes, vinyl (fusion),*
metallic, plastic inks,
adhesives
Wash up and cleaning
Inks
Resinous powders, e.g.,
embossograph Hi-Flo
neutral powder
Formulated inks
Flourescent powders
A. Bookbinding
B. Magazine binding
Hot glues
Hot glues
* Identifies possible toxic materials.
25
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APPENDIX A (con.)
Process
Status
Products
Chemicals
7. Binding (con.)
C. Forms padding
D. Spiral binding
8. Composition
A. Hot type
1. Hand compo-
sition
2. Monotype
3. Linotype
4. Ludlow
B. Cold type
Brands
1. Copy-
producing
typewriters
( Verityper
Justo writer
IBM
( Llthotype
2. Photocomposing
machines
Intertype
fotosetter
ATF photo
compositor
Computer compo-
sition
9. Photography
Used primarily for
letterpress printing.
Individual characters set
up in composing stick;
characters already
formed; used primarily
for large display
lines.
Individual characters
cast on machine.
Whole line of characters
cast on machine
Individual characters
strip rule, and spacing
material cast.
Used primarily for
lithographic printing
process;
also used in gravure,
silk screen and letter-
press.
Used In smaller plants
for copy preparation.
Used In large plants,
newspapers, publica-
tions, etc.
Padding cements
Lines of type made up
of Individual characters.
Lines of type made up
of individual character*.
Lines of type characters
cast together.
Lines of type characters
cast together.
No chemicals
Lead
Paper copy
None
Sensitized films on which
characters have been
photographed.
Developers
Fixers
Stop baths
Hardeners
Most extensive use in
litho process. Also
used in other printing
processes to reproduce
drawings. Illustrations,
photographs, complex
ruled forms, 4-color
process.
Large portion of
photography done In
trade shops that
specialize In photography
for printing Industry.
Negatives and positives
Films
Developers
Fixers
26
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APPENDIX A (eon.)
Pro CMS
Stitut
Products
Chemicals
10. Platemaklng
A. Lithographic
pittas
B. Photoengraving
1. Letterpress
2. Gravura
C. Electronic
aravura cylin-
der engraving
D. Steraotyping
To convert flat
printing surface
to curved print-
Ing surface.
E. Electrotyplng
F. Rubber plates
Q. Photo polymer
plates
Aluminum or bimetal
plates
Relief engravings of
photographs (color and black
and white) Illustrations.
Complex forms.
Intaglio engrevlngs of
everything produced by
gravure process.
Intaglio engraved cylinders.
Curved plates with
relief Images.
Covered under lltho
process.
Both sheet and web.
A photographic process
on sensitized thick
metal plates. Used In
sheet-fed letterpress
process.
Also covered under
gravura process
Used In rotogravure
Used primarily In news-
papers where duplicate
plates are needed In
high-speed web letter-
press operations.
Declining use.
Used primarily In pub- Same as stereotyping (above)
llcetlons Industry where but gives finer detail
duplicate plates are and more durable.
needed In web-letter-
press operations.
Declining use.
Very special lied-
not usually found
In printing plant.
High-Intensity light
Carbon-arc
Infrared light
Mercury
Nitric acid
Fixers
Essentially same es
above
Lead
Used extensively In
flexography, but also
In letterpress.
Used In web-letterpress
processes, primarily
publications Industry.
Used In screen print
process. Covered
under screen
printing.
Rubber pletes
Chrome \ Deposited by
Copper > electrochemical
Nickel J action
Lead bases
Wax
Baketlte plastic
Sansltlzers
Etch (caustic)
Rinse (water)
Rubber powders
27
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APPENDIX B
LIST OF ASSOCIATIONS TO BE CONSIDERED FOR
PRINTING CONFERENCE
Academy of Screen Printing Technology
Acme Printing Ink Company
Advertising Typographers Association of America
Alden Press Inc. (John Blair & Co.)
Ailing & Gary Company
Amalgamated Printers' Association
Ambassador College Chemistry Dept.
American Can Company Env. Services
American Color Print Society
American Dyestuff Reporter
American Education Publications (Xerox Family Educa-
tion Services)
American Photoplatemakers Association
American Printed Fabrics Council
Anchor Chemical Co., Inc.
ANPA Research Institute
Association of College and University Printers
Association of Flock Processors, Inc.
Baird-Ward Printing Co., Inc.
George Banta Co., Inc.
Basic Controls Systems, I nc.
Binding Industries of America
Bowers Printing Ink Company
Braden-Sutpkin Ink Company
Brown & Bigelow
Bruce Offset Company
Burd & Fletcher Company
C& I Girdler, Inc.
Cadillac Printing & Lithographing
Canada Printing Ink Co., Ltd.
Canadian Lithographers' Association
Canadian Printing Ink Manufacturers' Association
Capitol Printing Ink Co.
Case-Hoyt Corporation
Champion International
Chicago Department of Environmental Control
Chilton Printing Company
Cities Service Oil Company
J. L. Clark Manufacturing Company
Col well Press Inc.
Commercial Ink Industries
Consolidated Education Publications Inc.
Continental Can Company
Converters Ink Company
Courier Citizen Company
Consolidated Printing Ink Company
Creative Printers of America, Inc.
DeLuxe Check Printers, Inc.
A. B. Dick Company
R. R. Donnelly & Sons
Dow Chemical Company
E. I. duPont deNemours & Co., Inc.
Eastman Kodak Company
Egyptian Lacquer Manufacturing Co.
EPA National Field Investigation Center
Fawcett Printing Corporation
Flexographic Technical Association
Flint Ink Company
Foote & Davis
GATF Air Pollution Control Advisory Commission
General Foods Corporation
General Motors Photographic
Goudy Society
Granco Equipment Inc.
Graphic Arts Advertisers Council
Graphic Arts Association Executives
Graphic Arts Industries Association
Graphic Arts International Union
Graphic Arts Technical Foundation
Graphic Communications Computer Association
Gravure Research Institute
Gravure Technical Association
H-C Industries Inc.
W. F. Hall Printing Company
Hallmark Cards, Inc.
Harris Intertype Corporation
Harris-Seybold Company
Heeken Can Company
Herbick & Held Printing Company
Hercules, Inc.
Hirt Combustion Engineers
Hurletron Inc.
Illinois EPA, Naval Armory
In-Plant Printing Management Assn.
Inland Steel Container Company
Inmont Corporation
International Association of Printing House Craftsmen
International Association of Siderographers
International Business Forms Industries
International Paper Company
International Plate Makers, Die Stampers' and Engravers'
Union of North America
International Press Institute
International Printers Supply Salesmen's Guild
International Printing and Graphic Communications
Union
International Printing Pressmen's Union of North America
International Repro Graphic Blueprint Association
International Typographic Composition Association, Inc.
International Typographical Union
Kable Printing Company
Kimberly-Clark
Kingsport Press, Inc.
W. A. Krueger Company
Lassen & Jones
Los Angeles County Air Pollution Control District
McCall Printing Company
Machine Printers and Engravers Association
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M G D Graphic Systems
Magie Brothers Oil Company
Charles T. Main
Master Textile Printers Association
Meredith Printing Company
Mid-Atlantic Graphic Arts Review
Milier Printing Machine Company
Minnesota Mining & Manufacturing Co.
Mobil Chemical Company
Southern Murray
National Association of Grained Plate Manufacturers
National Association of Litho Clubs
National Association of Printers and Lithographers, Inc.
National Association of Printing Ink Manufacturers
National Composition Association
National Metal Decorators Association, Inc.
National Printing Equipment Association, Inc.
National Printing Ink Research Institute
National Publishing Company
New York News
Ohio Art Company
Parker Metal Decorating Company
Perry Printing Company, Inc.
Photopress Inc.
Platemakers Educational & Research Institute
Pollution Control Industries, Inc.
Post Card Manufacturers Association
Prairie Print Makers
Print Advertising Association
Print Council of America
Printing Estimators and Production Men's Club
Printing Industries of America
Printing Industry of Illinois Association
Printing Platemakers Association, Inc.
Rand McNally & Company
Readers Digest Association, Inc.
Regensteiner Publishing Enterprises, Inc.
Research and Engineering Council of the Graphic Arts
Industry, Inc.
Richardson Company
Riverside Press
Roberts & Porter, Inc.
Row Engineering
St. Regis Paper Company
Salesmen's Assn. of the Textile Dyeing and Printing
Industry
Screen Printing Association International
Shell Chemical Company
Sherwin-Williams Company
Silk and Rayon Printers & Dyers Association
Simplicity Patterns Co., Inc.
Standard Gravure
Standard Publishing
Steck-Warlick Company
Sun Chemical Company
Sunnyside Products Company
TEC Systems, Inc.
Textile Printers & Dyers Labor Relation Institute
Triangle Publications, Inc.
Von Hoffman Press
Vulcan-Cincinnati
The Webb Corporation
Western Publishing Co., Inc.
Westvaco Corporation
Wiley & Wilson, Inc.
Henry Wurst, Inc.
Young Printing Executives Club of New York
Zabel Brothers Company, Inc.
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APPENDIX C
TYPES OF CHEMICALS USED IN THE PRINTING INDUSTRY
INKS
SOLVENTS
Aromatic Compounds
Benzene
Toluene
Nylene
Ethylbenzine
Turpentine
Stoddard solvent
Varsol
Biphenyl
Orthophenylphonol
Binzoric acid
Phenol
Aliphatics
Pentane
Isooctane
Naphthenes
Maneral spirits
Naphthas
Heavy naphthas
Oxygen Containing Compounds
Methanol
Ethanol
Propanol
Isopropanol
Butanol
Isobutanol
Ethyleneglycol
Ethyleneglycol acetates
Ethyleneglycol butyretes
Acetone
Methyl Ethyl Ketone
Methyl phenyl carbinol
Acetophenne
Acetic Acid
Diethylene glycol
Urea
Glycerol
Chlorinated Compounds
Trichloroethylene
Trichloroocthane
Methylene chloride
Chlorinated paraffins
Chloroenzines
Pigment Bonding Agents
Melamine-formaldehyde
Poly acrylic acetate
Viscosity Stabilizers
Sodium nenamutaphosphate
Tetra-sodium pyrophosphate
Antifrosting Agents
Diethanolamide
Acid-Producing Agents
Acetic acid
Citric acid
Formic acid
Tartaric acid
Thickening Agents
Alginates
Cellulose ethers
Acrylamide - N-t-butyleery lamide copolymer
Dextrin
Phosphoric acid estus of onyethylated wan-alcohols
Fatty acid estus of ehtylene glycol
Ethylene oxide polymers with starch
Guar germs
Gum arable
Gum tragacanth
Polyacrylamide
Polyacrylic acids
Starches
Biosyuthetic-nanthan gums
Pigments*
•A comprehensive list of pigments is given in Textile Chemist and Colorist, Products/74, Vol. 5, No. 10A (October
1973), pp. 29-95.
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DISCUSSION
DR. ALBERT R. MATERAZZI (U.S. Government Printing Office, Washington, D.C.):
The statistics are in considerable need of updating; one in par-
ticular was the one on 3 percent paper spoilage.
The industry differentiates between spoilage and waste. Spoilage
is that which is done in error and waste is engineered into the sys-
tem—in trim waste, paper left on cores, outside wraps, running allow-
ances, etc. And, that figure runs closer to 20 or 25 percent,
unfortunately.
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22 September 1975
Session I:
PRINTING PROCESSES AND CHEMICALS USED
Bohdan V. Burachinsky, Ph.D.*
'Vice President, Corporate Research and Development, Inmont Corporation, Clifton, New Jersey
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SESSION INTRODUCTION
Bohdan V. Burachinsky, D.Sc.
Session Chairman
One of the objectives of this morning's session is to set the stage for
this conference by first describing the industry and defining the various
printing processes and then by listing the chemicals used and/or omitted
from each of the processes. Furthermore, several applicable EPA pollution
control regulations and standards for emission of effluents will be dis-
cussed.
Our panel of speakers is composed of representatives of a research or-
ganization, a trade association, a Federal Government agency, and a large
city department. I am sure this variety of background and viewpoints will
provide for quite an interesting session.
I represent an important supplier of chemicals to the printing industry,
but more importantly, I represent a technical arm of the National Associa-
tion of Printing Ink Manufacturers. On behalf of that association, I would
like to make a few comments. NAPIM is a technical institute which long ago
recognized the crucial importance of the environmental aspects of our indus-
try. Thus, NAPIM created a committee that concerns itself with pollution of
air and water, toxicity of products in effluents, safety and industrial hy-
giene in our plants, recycling of wastes, and dissemination of the data and
general information.
The fruits of the effort by this committee may be summed up. To date
we have issued a raw materials handbook, probably the first in the industry
to Indicate hazards, suggestions, and handling procedures for commercial
solvents. Later, plasticizers will also be described in a separate handbook.
Eventually, we will also publish a booklet on pigments.
NAPIM has also conducted a study of lead- and other heavy-metal-contain-
ing pigments. This was done in a joint effort with Dry Color Manufacturers
Association. We have tried to determine various hazards of and the important
impact of elimination of lead-containing pigments from printing inks. We
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have also worked on safety standards for use of equipment and handling of
potentially toxic or irritative substances in our plants.
NAPIM has worked closely with NIOSH on a simplified approach to gather-
ing data on printing ink ingredients. NIOSH had studied and still is study-
ing exposures to chemicals where men work. We have closely cooperated with
NIOSH and devised a model-formula approach whereby proprietary information
or proprietary formulation of member companies was protected. The informa-
tion was offered to NIOSH, and at the same time a tremendous amount of time
was saved in decoding the various formulas. So, when the industry, industry
associations, and the government agency had met and found a good cooperative
spirit, results were good, and objectives were accomplished.
It is clear, therefore, to me that formation and support of capable
technical organizations by the various trade organizations is now very
timely and quite an important step toward eliminating duplication of costs
and pooling scarce human resources, especially by the more fragmented and
smaller industries. There is the need for the various sister trade organi-
zations to cooperate and collaborate closely among themselves on the safety
and environmental aspects.
However, I think that government agencies and industry organizations
must work very closely, openly, and professionally in order to establish the
required controls and realistic standards, and to truly protect the public,
the worker and the consumer without unnecessarily harming, or even elimi-
nating any segments of our industries.
I would like to paraphrase Professor John McKetta of the University
of Texas. He writes that there are still some companies and cities today
that put toxic gases and liquids into our air and streams. On the other
extreme are those people who wish to have distilled water in the stream and
zero particulate in the atmosphere. These are impossible concentrations and
could not be achieved even if there were no people on this earth. McKetta
says further that the answer, obviously, is somewhere between the two ex-
tremes. We must have clean air to breathe and clean water to drink—not
distilled water, not absolutely pure air, but odorless, nontoxic, clean, and
healthy ones.
Actually, all of us, by driving a car, operating a press, smoking a
cigarette, or swallowing a medicine, are undertaking a risk. The question
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may be asked, is the risk a reasonable one? Mr. PUtle of the Consumer
Products Safety Commission has offered a very fine definition of reasonable
risks worth, In my opinion, adapting to environmental studies. Such risk 1s
one where the consumer or the user: 1) understands by way of adequate warn-
ing or by way of public knowledge that risk is associated with a product or
a process; 2) understands the probability of occurrence of an Injury; 3)
understands the potential severity of such an Injury; 4) has been told how
to cope with the risk; 5) cannot obtain the same benefits unless risking
ways at the same or less cost; 6) would not, if given a choice, pay addi-
tional cost to eliminate or reduce the danger; and finally, 7) voluntarily
accepts the risk to get the benefits of the products or the process.
We here, of course, would like to communicate, to protect those who do
not now, do not understand, have no choice or means, or are not here yet to
protect themselves from unreasonable risks.
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FEDERAL WATER POLLUTION CONTROL ACT - AN ASSOCIATION'S RESPONSE
Thomas J. Dufficy*
Abs tract
Virtually all of V. S. industry has been affected and will continue
to be affected by Federal* State3 and local environmental regulations.
This paper will review the impact of the Federal law and regulations3
discuss the areas of plant inspections and trade secrets. The activities
of the National Association of Photographic Manufacturers in environmental
matters will also be discussed in relation to how an industry can input
to the formulation of regulatory guidelines.
I am very pleased to be here this morning and share with you some
of the concerns of our association and some of our accomplishments re-
lating to the environment. I would also like to outline how we have
handled plant visits and trade secrets in relation to effluent limitations
guidelines. But first, let me tell you something about the National
Association of Photographic Manufacturers.
NAPM is a voluntary trade association composed of companies domestic
to the United States. We represent over 90 percent of the photographic
industry on a dollar and volume basis.
The U. S. photographic industry is the world leader—we supply 62.5
percent of the world's photographic needs—with Japan second and Germany
third. In 1973, in the amateur area alone approximately 6 billion "snap-
shots" were taken. You as a group do not have to be told of the tre-
mendous photographic uses in microfilm, professional and still-motion
pictures, aerial and medical X-ray, and the graphic arts.
The photographic industry has historically been interested in pol-
lution control. In the manufacture of film or cameras or in photo-
processing, an ordinary thing like a speck of dust can be a very un-
wanted pollutant. Several years ago, the NAPM formed a committee to
*Attorney at Law, National Association of Photographic Manufact-
uers, Harrison, New York.
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look into the environmental impact of photographic chemicals. Our initial
and major thrust was in the area of water pollution control.
All of you are aware of the legislation that is designed to clean
up our Nation's water. The Water Pollution Control Act of 1972 was en-
acted in an effort to get on with the job of cleaning up. The legisla-
tion prior to that amendment was geared to water quality standards for
navigable waters. In pre-1972 law, if the pollutants discharged into a
receiving water reduced the quality below permissable levels, legal
action could be commenced against the discharger. A causal relation had
to be established between the alleged polluter and the unacceptable water
quality. Over a span of 20 years, very few cases reached the courts.
The 1972 act replaced all of the previous legislation, including
the Water Quality Act of 1965, the Clean Water Restoration Act of 1966,
and the Water Quality Improvement Act of 1970, all of which had been amend-
ments of the Federal Water Pollution Control Act first passed in 1956.
The objective of the 1972 act is to restore and maintain the chem-
ical , physical, and biological integrity of the Nation's waters. Several
goals were established:
1. The National goal that the discharge of pollutants into the
navigable waters be eliminated by 1985.
2. The National goal that, wherever attainable, an interim goal
of water quality which provides for the protection and pro-
pagation of fish, shellfish, and wildlife and provides for
recreation in and on the water be achieved by July 1, 1983.
I do not intent to get into any detail concerning the various levels of
standards and guidelines under which permit conditions become tougher
and tougher, culminating in the "zero-discharge" condition.
As you are all aware, new sources under Section 306 (b) (1) (B)
will be required to apply the greatest degree of effluent reduction
achievable, through application of the "best available demonstrated con-
trol technologies, processes, operating methods or other alternatives,
including, where practicable, a standard permitting no discharge of
pollutants."
-------
Existing sources Section 301 (b) of the act provides:
-Not later than July 1, 1977, effluent limitations for point sources,
other than publicly owned treatment works shall require the application
of the best practicable control technology currently available.
-Not later than July 1, 1983, effluent limitations for categories
and classes of point sources shall require application of the best avail-
able technology economically achievable.
In light of the foregoing regulations, what did the photographic
industry do? We knew that the EPA, the States, and the municipalities
would eventually be looking at our industry. Quite a large amount of
information was around, but not in any cogent form. We at NAPM felt we
were in a good position to commission a study, and one was started over
3 years ago. Hydroscience, Inc., a very respected firm in the waste-
water area, conducted the study of some 45 chemicals commonly used in
the photoprocessing industry. It is now complete and published in
two volumes.
The effects of the 45 chemicals on conventional biological waste-
water treatment systems and on representative aquatic organisms were
studied through a multiphase program. Also included in the study were:
1) determination of the responses of the chemicals to analyses common
to wastewater management, 2) investigation of the impact of a combined
photoprocessing effluent, and 3) the development of a simplified dilu-
tion model to predict approximate downstream concentration of various
constituents discharged to receiving water.
The study yielded four major conclusions. The first is that on
the basis of information developed during the study, it was determined
that photoprocessing wastes do not present a hazard to biological systems
encountered in conventional wastewater treatment schemes or to aquatic
organisms indigenous to natural receiving water systems. The assumption
inherent in the above statement is that a photoprocessing waste is not
directly discharged to a natural receiving water without adequate treat-
ment before discharge.
The results indicate that photoprocessing wastes are amenable to
biological treatment, with a removal efficiency approximately equivalent
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to that encountered with domestic wastewaters. The concentrations ex-
pected to occur in municipal or regional sewerage systems and in a re-
ceiving water upon treatment will not adversely affect biological systems.
The second conclusion is that the 45 photoprocessing chemicals
investigated in this study have no significant impact on the activity
or efficiency of the biomass of a conventional biological wastewater
treatment system, at the concentrations realistically attainable in
municipal or regional sewerage systems. The chemical concentration ex-
pected to occur in the discharge from a photoprocessing laboratory may
be estimated by applying a one-hundredfold dilution to the working
solution concentrations.
Bioassay experiments were conducted to determine the impact of the
photoprocessing chemicals on aquatic organisms representing different
levels in the food chain. The experimental results led to the third
conclusion that, at the concentrations estimated to occur in the receiv-
ing water at the point of discharge from a municipal biological treat-
ment plant, none of the photoprocessing chemicals examined would ad-
versely affect the types of organisms represented by the test species.
Fourth, there is no typical photoprocessing waste. Each photo-
processor represents a unique combination of processes and modes of
operation. The list of chemicals chosen for study was certainly not
all-inclusive, but it is judged that the selected chemicals are repre-
sentative of many commercial processes and that the results of the study
could be applied to other chemicals of a similar nature. The Kodak E-4
color reversal process waste, specifically used to evaluate the impact
of a composite photoprocessing effluent, for instance, is not typical,
but is considered to represent a broad cross section of chemicals used
in photoprocessing.
After the Hydroscience study was completed, we ran several seminars
in New York, Chicago, and Los Angeles to disseminate the information and
also to provide regulatory people in the industry with some basic infor-
mation on what the photoprocessing effluent looks like and how to treat it.
Just as our study was winding up, two developments of interest were
taking place. First, EPA was getting ready to award a contract for the
development of effluent limitations guidelines and standards of performance
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in the miscellaneous chemical area. Miscellaneous chemicals were divided
into eight industries, the photographic processing industry being one
of the eight and being composed of the following SIC codes: 7221—photo-
graphic studios; 7333—commercial photography, arts and graphic; 7395—
photofinishing laboratories; 7819—developing and printing of commercial
motion picture film. The contract was awarded to Roy F. Weston; a draft
development document has been circulated and the NAPM has submitted com-
ments.
The second development of interest was the awarding of a contract
for effluent limitation guidelines in the machinery and mechanical pro-
ducts manufacturing area. Photographic manufacturing was included in
this basket study, which included some 175 separate industry categories.
The list included steel foundries, plumbing fixtures, ammunition, elec-
tric lamps, and ended, perhaps significantly, with SIC code 3995—burial
caskets.
This contract was awarded to Hamilton Standard, which has submitted
its four-volume draft development document for comment. One thing you
will find is that EPA is under some unreasonable time pressures and that
it passes the unreasonableness on to the industry. Comments were to be
made by August 29th—we did not make the deadline. We are meeting in 2
days to finalize our comments.
This brings me to a very important part of the whole procedure—the
comments on EPA's proposed regulations. I think all parties will agree—
and I include the various regulatory bodies, industry, and other inter-
ested persons—that it is much better for all concerned that issues be
settled at the administrative level. Most trade associations and
companies try to make their best case with the agency. We all know it
is much harder to change proposed rules than to get good rules proposed
in the first place. We at NAPM have been spending our time in developing
data upon which good rules can be established. If a case does get into
the court system, the most that can be expected initially is a remand.
The courts for the most part are unwilling and unable to write new regu-
lations.
Courts that review the regulations of government agencies do not
take testimony; the record is all the evidence that they can use to
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decide the case. It is of course imperative that the record be complete
on both sides of the issue. To that end, we have urged our members to
cooperate fully with EPA. He have had some minor problems involving non-
disclosure arguments, but in general things seemed to have worked out.
We have urged our member companies to develop data and information
that can be used to challenge a point. We want specific items, not
generalizations. We always ask for split samples; we have challenged
analytical results, flow rates, and descriptions of processes.
We assume, and I believe correctly, that EPA and its contractors
are professionals who are seeking to do the best job humanly possible.
We are trying to help them.
There are, of course, many considerations that a company must make
prior to the disclosure of certain facts and figures. In addition,
there seems to be a continuous movement toward full disclosure. Perhaps
this is due to the influence of the Federal courts, which have a long
history of requiring that all of a litigant's case be included on record
prior to a trial, through the use of discovery proceedings.
In the case of effluent guidelines, you can look at the so-called
Supplement B, which contains the working papers and data that formed the
basis of the contractor's draft development document. We shall soon
see if the regulations reflect any industry input.
There are such things as proprietary formulas, production data,
new products, manufacturing processes, and information of that nature
that ordinarily will come into the hands of EPA or its agents in the
course of running various EPA programs. And all of us are aware that
industrial competitors, both foreign and domestic, would very much like
to have any information they can get.
EPA proposed regulations for the treatment of trade secrets and
confidential data in May 1975; these were scheduled to go into effect
sometime in July. The EPA regulations include a requirement that it
is the responsibility of a business which makes a confidentiality claim
to substantiate that claim. EPA in its part must allow a reasonable
time for the business to do so, and it should honor a demonstration of
confidentiality in releasing the information gained. Furthermore,
judicial intervention should be a consideration in an injunctive relief
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type of situation.
It has been our experience that the EPA program sounds good but has
many areas of possible breakdown and that it overlooks some areas. One
thing that might be done is to establish a requirement that any contrac-
tors performing work under an EPA contract execute a secrecy agreement.
This would restrict the disclosure of any technical information not in
the possession of the contractor prior to the date of disclosure to all
but EPA. The agreement would have certain provisos to lift the restric-
tion if the data is available from other sources, etc.
In addition to providing input to the creation of government regu-
lations, NAPM has been involved in the development of national stan-
dards. Any competent chemist can tell you that analytical methods can
yield erroneous results in the presence of certain "contaminants"; I
believe these results are called "interferences." However, the standard
analytical methods employed by chemists have most of the probable inter-
ferences eliminated, or else ways have been found to obviate their
effects. The term "most probable" would not include photographic
chemicals because they are not significant in most industrial or do-
mestic wastes.
NAPM is also the secretariat of several American National Standards
Institute (ANSI) committees dealing with photographic standards. A
committee under ANSI-PH4-5 examined the standard methods for various
parameters in the light of the interferences that could be expected from
photographic chemicals. The committee also examined analytical methods
for classes of chemicals such as phenols to establish whether the speci-
fic compounds used in photography would respond to the standard methods;
some do not.
ANSI Committee PH4-5 developed a standard that furnishes or refers
to acceptable analytical methods for analyzing photographic processing
wastes. Included in the standard is an appendix with detailed analytical
methods for the following situations: 1) where no method exists in the
standard reference sources; 2) where it is necessary to provide for pre-
treatment, etc., to eliminate interferences likely to be present in
photographic wastes; 3) where it is necessary to provide methods that
are not affected by interfering photographic chemicals, as are the
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published standard methods. The standard also includes some other
methods, such as "ferrocyanide in photographic waste effluents and the
determination of the chlorine requirement of photographic processing
effluents."
One of our ANSI committees is working on a guide to effluent man-
agement for photographic processing facilities. It is not yet close to
publication; we have decided to wait and see what the effluent guidelines
for miscellaneous chemicals say, and we will then tailor the guide
accordingly.
The format of the guide should be helpful. We are going to give
some brief information on the Water Pollution Control Act of 1972--how
it will effect the photoprocessor, how the States and localities come
into the picture, and some of the key dates. The guide will provide
checkoff lists for effluent characterization, where the discharge goes,
and some basic ideas on how to start an effluent management system.
The guide will be intended as a preliminary approach to defining a
particular effluent problem. Where answers are general in nature, they
will be supplied; where the information is specific, appropriate space
will be provided for calculations and insertions of data. A biblio-
graphy and directory will be included for further information.
This wraps up my presentation. I hope that hearing about the NAPM's
response on behalf of its members to the Water Pollution Control Act
of 1972 will be of help to you in meeting similar challenges.
DISCUSSION
MR. SALTZMAN (Bureau of Solid Waste Management, New Jersey Department
of Environmental Protection, Trenton, New Jersey): Consideration,
as I understand, is being given to taking the wastes and treating
them prior to taking them to municipal disposal facilities. Is
consideration being given to taking these wastes and disposing them
in, say, class 1 chemical dump facilities or disposal facilities?
MR. DUFFICY: Consideration is being given to that. And that, of course,
is going to depend on the locale and what its situation is from an
economical standpoint.
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I did not mention it in my talk, but we have recently commissioned
a study looking into leaching characteristics. Part of the study is
going to be a lysimeter test, just to see what happens to silver and
ferricyanide, what happens to an inland fill, things of that nature.
This is something that is being considered.
Most of the photoprocessors do have all kinds of pretreatment
going now, silver recovery being one, bleach regeneration being another.
And they are continually trying to make their particular operation as
economical as possible. They're doing it in plants right now, in
most places.
CHAIRMAN BURACHINSKY: Are there any other questions?
MR. WILLIAM S. BEGGS (New Jersey Department of Environmental Protection,
Trenton, New Jersey): I wanted to ask you about the 45 chemicals
that you have. Do you have a brochure on that?
MR. DUFFICY: Yes.
MR. BEGGS: I would like to get a copy of it.
MR. DUFFICY: This is the brochure. I would like to hold onto it for just
a little while. This comes in two volumes--Volume 1 and Volume 2.
We have provided it to regulatory people—EPA; the State; the New
Jersey Department; the various governmental agencies; Departments
of the Army, Navy, Air Force, etc.--free. We thought it would
be worth our while to get it to them. We charged anyone else $25.
If anyone would like any of this information, get in touch with us.
Are there any other questions?
CHAIRMAN BURACHINSKY: I would like to modify my comment that every trade
organization, besides having a good technical arm, should not forget
to have the services of a competent and experienced attorney.
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HYDROCARBON EMISSION REGULATIONS
James A. McCarthy*
Abstract
Future hydrocarbon emission regulations will have impact on the plans
and profits of the printing and related industries. This paper presents
background information on hydrocarbons^ their effects, and current thinking
about their control. The author presents his views on future trends in
hydrocarbon regulations.
It is a pleasure to meet with you today to discuss hydrocarbon emission
regulations. This is a subject in which I believe many of you will be
interested because the levels and extent of future hydrocarbon regulations
could have an impact on both the plans and profits of the printing and related
industries. During my talk, I will review some background concerning hydro-
carbon emissions, their effects, and past regulatory efforts. Then I will
discuss current thinking about hydrocarbon emission control. Finally, I will
describe what I see in the future for hydrocarbon control.
First, I think it would be valuable to describe briefly our organization
and my part in the overall picture. I am in the Control Technology Office
of the Emission Standards and Engineering Division of EPA. EPA's offices at
Research Triangle Park, North Carolina, have a prime responsibility for EPA
activities in controlling air pollution from stationary sources. We are
partially responsible for approving State air pollution regulations and for
technically assisting State agencies. We are also responsible for developing
air pollution standards for new sources, an area that is assuming greater
significance in terms of the nationwide goal to clear the air.
Let me begin by answering a few commonly asked questions. One of the most
frequent is: why control hydrocarbons? The answer is, very simply, to re-
duce oxidant concentrations in the air we breathe. Oxidants, including ozone,
are the main irritants in photochemical smog. Oxidants are formed in the
presence of sunlight by the reaction of organic compounds from fuel combus-
tion, solvent evaporation, and industrial processes with nitrogen oxides from
*Chemical Engineer, Environmental Protection Agency, Durham, North
Carolina.
45
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fuel combustion processes. The reaction products--oxidants—are not only
dangerous to man and animals, but also adversely affect vegetation and
materials such as rubber, cotton, nylon, and polyesters.
Another question is: what are hydrocarbons? Strictly speaking, a
hydrocarbon is a compound containing only carbon and hydrogen atoms. In
actuality, however, we are concerned with any gaseous organic compound
emitted into the atmosphere in sufficient quantity to pose a potential oxi-
dant problem. Many people refer to this group of compounds as hydrocarbons
for simplicity.
Lastly, how does printing contribute to the overall problem? Of the
more than 25 million tons of hydrocarbons estimated to be emitted nationwide
each year, stationary sources of all types contribute about one half. Of
that quantity, printing represents a small percentage. The printing industry
is, however, localized and, in certain metropolitan areas, is a significant
source. A larger emission source, with which some of you may be involved, is
paper coating.
Hydrocarbon emissions are typically reduced in two ways. First, control
devices can be added to recover the hydrocarbons from the exhaust stream or
to convert them, by incineration for example, to a less noxious state; or
second, processes or materials can be altered in such a way as to reduce or
limit the use of hydrocarbons. Each way has advantages and disadvantages.
Add-on devices usually represent nonproductive capital expenditures, but can
be implemented fairly rapidly. Process or material changes, while more
efficient and less costly, can affect final product characteristics. The
decision to use any specific system must be made in light of all available
technical and economic information.
Air pollution control agencies and the Congress have developed mecha-
nisms by which controls can be instituted and emissions consequently reduced.
The Environmental Protection Agency's air pollution effort is based on the
Clean Air Act of 1963. The Clean Air Amendments of 1970 were a major
revision to the Clean Air Act, and there were minor changes in 1974.
Under the Clean Air Act, the system works like this. EPA establishes
ambient air quality standards for proven adverse air pollutants. A national
ambient air quality standard is the maximum level of a pollutant which will
be permitted in the ambient air, i.e., the air we breathe. These standards
apply to specifically designated pollutants known as "criteria pollutants."
46
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In April 1971, the Environmental Protection Agency promulgated national
ambient air quality standards for six pollutants, including photochemical
oxidants and hydrocarbons. States then prepared implementation plans de-
scribing the controls required within their jurisdictions. Variations are
expected owing to the difference in sources, emissions, existing air quality,
and meteorology between States. Required time frames are aJso outlined, with
certain deadlines being required by the act. EPA then passes on the adequacy
of State plans. We cannot make State plans less stringent, but we must
tighten plans if necessary to insure that ambient air concentration goals are
met.
The act also requires that EPA develop emission standards for new
sources, but it gives EPA the discretion to select and move as it sees fit.
The key was that Congress believed that new sources should use the best
available control technology, taking costs into account, and that the latest
technology should be installed when new plants are built, even when it is not
necessary to meet the ambient air quality criteria. This was and is believed
to be the most effective and least expensive way to prevent major air pollu-
tion problems from recurring in the future.
New source performance standards have been set for 13 industries and
proposed for 10 others. Studies are underway by EPA on another 30. Only one
new source performance standard involving hydrocarbons has been promulgated
or proposed to date, that for large petroleum liquid storage vessels. How-
ever, in the current group of 30 industries being studied are several involv-
ing hydrocarbons. I will discuss these a little later.
Two points should be emphasized with regard to new source performance
standards. First, best available control is meant to emphasize new technol-
ogy, not rely on the old. Second, a new source, as defined, not only refers
to newly constructed facilities, but also includes existing facilities when
they are modified if such modification results in an increase in the emission
of an air pollutant.
It is also important to stress that States have a great deal of author-
ity over which EPA has little direct control. We serve in many instances as
a source of technical information for the States. We can, and often do, make
engineering recommendations, but the burden is on the States to control
existing sources.
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Hydrocarbon control strategies are in a state of evolution. In past years
photochemical smog was believed to be primarily an urban problem, and con-
trol was oriented toward that end. For example, Los Angeles County limited
emissions of the more photochemically reactive materials in order to attack
its local oxidant problem. The slower reacting materials are called "exempt"
solvents. Furthermore, automobiles were considered to be the principal
emitters of hydrocarbons so that controls relied heavily on the Federal
Motor Vehicle Control Program. However, as more and more data are being
gathered, it is becoming apparent that strategies emphasizing control of
only the most reactive local emissions, or those concerned mainly with auto-
motive emissions control are not entirely satisfactory. Let me give you some
specifics.
First, it has been found that emissions from stationary sources cannot
be neglected. They are larger than was initially realized and represent an
ever increasing fraction of the total pollution problem as more and more
automobiles with hydrocarbon controls replace older automobiles with less
control.
Second, high concentrations of oxidants have been found in basically
rural areas and at considerable distances downwind of urban areas. This
seems to indicate that oxidants are moved or formed over wide areas of the
country. In time, almost any organic will react. Thus "exempt" solvents
contribute to oxidant problems in distant locations.
Third, world situations are changing. Energy supplies and costs are
crucial factors that must be considered.
It is becoming clear that: 1) oxidants are a stationary source problem,
in addition to being a mobile source problem; 2) oxidants are a national, not
just a local problem; and 3) EPA must focus much more of its attention toward
resolving these issues along with considering the costs and availability of
fuel.
EPA is mounting a major new effort aimed at developing and promulgating
performance standards for significant emitters of hydrocarbons. Standards
have been promulgated for petroleum storage and gasoline marketing. Also
underway are studies of the drycleam'ng and degreasing industries. Most
importantly for you, we are also in the process of initiating a major study
of the industrial surface-coatings industry, including paper and paperboard
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coating. Engineering studies will narrow the scope to a manageable number
of significant emitters, and then detailed engineering, economic, and envi-
ronmental impact studies will be performed in order for new source perform-
ance standards to be developed. By late 1976 or in 1977 these new source
performance standards may be proposed.
EPA will supply our regional offices and State and local officials with
a continuing dialogue in an effort to keep them abreast of new, demonstrated
technology and to make recommendations for their future actions. Both print-
ing and paper and paperboard coating will come under closer scrutiny by State
officials.
I also strongly suspect that, in the near future, some States will begin
to move toward emphasizing new coatings technology and away from add-on
controls and the use of "exempt" solvents. I expect "exempt" solvents to be
allowed as an interim control option, but only if no other reasonable option
is available. It seems clear that in the long run "exempt" solvents as the
sole control method will be phased down significantly.
In summary, hydrocarbon control regulations over the past few years have
been turbulent and confusing. I wish I could tell you that this situation
is resolved. I cannot. The future will also be.turbulent, but I firmly
believe that we are in the process of developing more rational approaches
to solving the many problems, and you can soon begin to plan your future
thinking in terms of pollution control with more confidence. EPA will work
with you, through our regional offices and our engineering and enforcement
activities. We are always available to help you solve your problems in as
equitable a manner as possible.
We collectively face a very great challenge, but it is a challenge that
we can meet if we work together-
DISCUSSION
MR. ED J. HEISER (Dow Chemical, U.S.A., Midland, Michigan): You mentioned
a study to include paper and paperboard coatings. Are you talking about
hydrocarbon emissions from these test applications?
MR. MCCARTHY: Yes.
MR. HEISER: Because coatings cover this application, aqueous system, too?
49
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You are not considering that?
MR. MCCARTHY: We are considering aqueous systems. In some aqueous systems
you have some solvents or a monomer emission of an aqueous polymeric
application. And that is a hydrocarbon emission. Paper and paperboard
coating is not my specific area, but I understand a lot of it involves
adhesives. A lot of hydrocarbon emissions are from the application of
adhesives. But I understand that even the water-base systems have a
monomer emission problem.
DR. WILLIAM D. SCHAEFFER (Graphic Arts Technical Foundation, Pittsburgh,
Pennsylvania): Is it in order for you to say anything about EPA's
prospective on Congressional actions within the year or next year in
the extension of the action?
MR. MCCARTHY: I really have not even seen the latest markup of the act.
I do not think it is going to have a significant effect on us. I
think it is going to make EPA more flexible in meeting deadlines.
We have more flexibility to work and make the deadlines more reasonable.
That is my understanding of what is happening.
MR. BILL MAGIE (Magie Brothers Oil Company, Franklin Park, Illinois): How
have you determined that some of the exempt solvents eventually do
become photochemically reactive?
MR. MCCARTHY: Well, the way that they rank solvents as exempt in the first
place is by testing them in test chambers—smog chambers--where they
simulate the action of sunlight, NOV, and hydrocarbons. Some compounds
. /\
just react immediately. I think the criteria was something like less
than 6 hours was considered to be a reactive solvent, meaning that in a
1-day type situation it would turn into oxidants. If you keep com-
pounds—really, anything but methane and probably the fluorinated com-
pounds and a few others--in there long enough, they react. You can
measure that they do. Over a week or 2 weeks, they all react. So it
is experimental empirical evidence that says that all these compounds
react to form oxidents.
MR. WILLIAM S. BEGGS (New Jersey Department of Environmental Protection,
Trenton, New Jersey): Most chemical reactions are chain reactions. You
are speaking about the immediate reaction with sunlight to produce these
50
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smog-producing chemicals. It seems to me that there is also another
aspect of it; that is, the destruction of the product. In other words,
in a sense it is an intermediate—
MR. MCCARTHY: I'm sorry, I'm not following you.
MR. BEGGS: We know that most chemical reactions are chain reactions.
MR. MCCARTHY: Right.
MR. BEGGS: There is the effect of sunlight, and then reaction with NOX to
produce an oxidant, you see. Now then because of the varied activity
of these things, they degrade further, presumably to carbon dioxide,
so that you have the building up of these oxidants and their destruction
at the same time. The concentration of any one oxidant would therefore
be determined by the rate constants of its formation and its destruction.
Have you made any studies along these lines?
MR. MCCARTHY; There are a lot of problems involved when simulating happens
in the atmosphere. There has been criticism with what they do in smog
chambers as being much too intense. For reasons of measurement tech-
niques, they usually use concentrations in a small chamber that are not
typical of what is found in an urban atmosphere. I think they have done
some recently with some sophisticated instruments where they do use very
low concentrations. They do know what the end products are. Carbon
dioxide is formed; ozone is formed. Ozone will react with almost any-
thing.
Materials Belong To:
OPPT'tiL-iry
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51
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THE ORGANIC EMISSION PROGRAM OF CHICAGO
George T. Czerniak,* William Thorp,
and Philip Byron
Abstract
The information presented in this paper is directed to those interested
in the program undertaken by the City of Chicago to implement its Organic
Emission Ordinance. After the adoption of the ordinance in May of 1974 f the
Department of Environmental Control developed a program of data collection.
The purpose of the program was to determine whether or not a company was in
compliance and to update the Emission Inventory. Discussed in -tine paper are
the procedures of data collection, data analysis* and control programs for
noncompliant sources.
INTRODUCTION
BACKGROUND
The term air pollutant, when considered strictly, includes any sub-
stance not normally found in the air in significant concentrations. However,
the connotation of the term has come to include only those substances which
have detrimental effects on life. Organic gases are considered to be air
pollutants under this definition.
Organic gas emissions occur primarily as the result of the incomplete
oxidation and cracking of fuels during combustion. There is also a signif-
icant contribution by the evaporative losses of liquid organic materials.
The major interest in organic gas emissions stems from their ability
to participate in atmospheric photo-oxidation reactions. Organic gases, in
the presence of oxides of nitrogen, react under radiation from the sun to
form various substituted organics. Many of these intermediates are associated
with the irritating effects of photochemical smog.
As far back as the 1940's, Los Angeles County enacted the first regu-
lations designed to deal with the problem of organic emissions. These
*Environmental Control Engineer, City of Chicago Department of En-
vironmental Control, Chicago, Illinois.
52
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regulations evolved into their present "Rule 66." This rule took into ac-
count the varying reactivities of different classes of organic compounds
and limited the emissions of formulations containing over certain percent-
ages of these classes.
On May 29, 1974, the Chicago City Council adopted an amendment to
Chapter 17 Article I1C of the Environmental Control Ordinance of the Muni-
cipal Code of Chicago entitled "Control of Emissions of Organic Substances."
This amendment regulates the storage and handling of organic material as
well as emissions from stationary sources. Although similar in intent to
the Los Angeles County and State of Illinois regulations, the specific
language of the Chicago ordinance required some different interpretations.
These will be discussed later.
GOALS OF ORGANIC EMISSIONS SURVEY
The adoption of the new ordinance necessitated that the Chicago Depart-
ment of Environmental Control institute a plan to bring all companies in the
city into compliance. This plan was called the Organic Emissions Survey.
Other objectives of this survey were:
1. To update the previous annual emission inventory figures to more
accurately reflect solvent emissions by company and arrive at an
organic emission figure for the city.
2. To organize and maintain the collected data to be useful in any
future studies of atmospheric photo-oxidation reactions and their
related effects.
SCOPE OF ORGANIC EMISSIONS PROGRAM
Organic emission survey forms were first sent to companies emitting at
least 2,000 gal/yr according to the 1973 and 1974 emission inventories. The
2,000 gal/yr cutoff point was chosen for two reasons: 1) When averaged over
and 8-hr work day and 250 d/yr, this figure would not produce in excess of
8 Ib/hr solvent emissions (even if there is only one emission source in the
plant); 2) The contributions by many low-usage companies to the total emis-
sions are minimal and the man-hours necessary to gather and analyze the
additional data would not be justified by the amount of information gained.
Assuming that all large emitters were accounted for on either the 1973
53
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or 1974 emission inventory, it can be said that this survey will provide an
accurate picture of solvent emissions from industrial stationary sources in
Chicago.
ATTITUDE OF PROGRAM
Once the goals of the Organic Emissions Program were established, it
was necessary to develop the proper administrative attitude which would en-
able us to swiftly realize those goals. It was felt that a cooperative
attitude, would be more likely to give the results that we required in the
shortest period of time. In keeping with this, the department functioned
as an advisor to the companies in the following capacities: assisting in
the completion of the appropriate forms; advising the companies on the al-
ternative means of achieving compliance; guiding companies through the
steps necessary to allow time to achieve compliance.
»T
INTERPRETATION OF ORDINANCE
The first major task necessary to the development of the Organic Emis-
sions Survey Program was to gain an understanding of the adopted ordinance.
This was made difficult in some portions because the intents were not clear
or seemed to be at odds with the specific language of the ordinance.
For these particular portions, an interpretation had to be made which
would be compatible with the overall intent of the amendment and yet follow
the specific language closely enough as to be enforceable. These portions
are listed in exhibit 1.* The first column of exhibit 1 is the section of
the ordinance as it was adopted. The second column gives a clarification of
the stated section. The third column gives examples and applications if
necessary.
METHODS OF SELECTING COMPANIES TO BE SURVEYED
The companies that were surveyed were selected based on the solvent
emissions from the 1973 emission inventory. A "Hydrocarbon Data Form" (copy
included as exhibit 3) and an accompanying cover letter (copy included as
exhibit 2) were mailed to the selected companies. In order to distribute
*A11 exhibits are located in the appendix.
54
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the work load associated with processing the data forms, the forms were first
mailed to the major solvent emitters. This enabled rapid collection of data
relating to the majority of solvent emitted.
During August 1974, 12 companies were required to complete the Hydro-
carbon Data Form. In addition to the collection of emission data, the pur-
pose of these forms was to obtain feedback concerning the form itself. As
a result of this feedback, the "Hydrocarbon Data Form" was modified slightly.
During October 1974, companies whose solvent emissions were 6,000 gal/yr
or greater were required to complete the Hydrocarbon Data Form. Therefore,
an additional 107 companies were required to complete the form. Included in
this category were 31 companies engaged in some form of printing.
During March 1975, a modified version of the Hydrocarbon Data Form was
sent to 134 firms whose solvent emissions were greater than or equal to 2,000
gal/yr and less than 6,000 gal/yr.
During the summer of 1975, the 1974 annual emission inventory was com-
pleted. The 1974 emission inventory listed 70 additional companies whose
solvent emissions were 2,000 gal/yr or greater and who had not been included
in that category in the 1973 emission inventory. These companies were mailed
forms in August of 1975. In addition to the above mentioned requests for
data, other requests were made at various times. These added companies were
not listed on the current emission inventory and were brought to our atten-
tion by the Annual Survey Section.
FORMS USED TO COLLECT DATA
The Hydrocarbon Data Form is a questionnaire designed to determine the
compliance of an industrial facility with Chapter 17, Article II-C. The form
dealt with five sections of Article II-C that past experience indicated were
applicable to industrial facilities in Chicago. The general topics covered
in each of the five sections are:
Section I Storage of organics;
Section II Loading of organics into a railroad tank car, tank
truck, or trailer;
Section III The use of an oil/water separator;
Section IV The use of liquid organic material in a process;
Section V The use of a vapor blowdown or safety relief valve
set.
55
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After obtaining feedback concerning the form from 12 companies that
were required to complete the form during August 1975, the form was modified
slightly. During October 1974, additional companies were required to com-
plete the form.
Later, after analyzing the data submitted on the forms and the com-
panies' reactions, the Hydrocarbon Data Form was modified and renamed the
"Organic Emission Data Form." Basically, the modifications consisted of:
1) deleting Section II, III, and V, since there was a negligible number of
companies involved with processes covered in these sections, 2) changing
the format of the section dealing with the use of liquid organic material
in a process, in order to simplify the completion of the section; and 3)
adding a number of questions concerning plant operation, and status before
other environmental control agencies. The purpose of the modifications was
to make the form easier to complete and to obtain additional information.
As a result, the Organic Emission Data Form consists of three sections deal-
ing with the following general topics:
Section I Storage of organics;
Section II Use of liquid organic material in a process;
Section III Several "yes" or "no" questions concerning plant
operation, and status before other pollution
control agencies.
A copy of the Organic Emission Data Form is included as exhibit 3.
FOLLOWUP ON ORIGINAL MAILING
When a company was required to complete the data form, it was advised
in the cover letter (see exhibit 2) that it was allowed 30 days to complete
and return the form. However, if a company requested an extension of the
30-day deadline, it was normally granted; this was necessitated when a com-
pany had to gather data (in-plant and supplier). In general, companies re-
quested the extension by a written communication. Extensions were granted
for approximately 30 days, to give the company ample time but not to let
the matter slip out of mind. The companies usually acted in good faith to
expedite the completion of the form. The procedure for additional exten-
sions was the same as for the first.
Approximately 40 days after the data requests were mailed, the file
was reviewed to determine which companies had not replied or requested an
56
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extension, and a followup letter (exhibit 4) was sent to these companies.
This letter was a courteous reminder that the form was due, and served to
advise the company that a time extension and/or assistance was available.
If a company did not respond in some manner to the first followup
letter, a second followup letter was sent by certified mail. A copy of the
second followup letter Is included as exhibit 5. This letter advised that
if the forms were not submitted within 15 days, enforcement action would be
taken. In four cases, the companies did not show a good faith effort to
complete the form; these companies received a citation. We are awaiting
the results of the court hearing regarding these citations.
DATA ANALYSIS:
ORGANIC EMISSION COMPLIANCE
The analysis of Section II of the Organic Emission Data form was
facilitated by the use of two computer programs. Those programs were writ-
ten for use on the Wang 700A computer-calculator in conjunction with the
IBM 701 output writer. These programs enabled a rapid determination of
compliance and a breakdown of data into usable categories.
The "compliance check program" determined the following items:
1. Whether or not the coating as furnished from the supplier was
photochemically reactive;
2. Whether or not a material added to the coating at the plant was
photochemical ly reacti ve;
3. Whether or not the mixture of the coating and the materials
added at the plant was photochemically reactive;
4. The average and maximum pounds per hour of solvent emitted due
to the use of the mixture; and
5. Whether or not the mixture qualified to be exempted from the
ordinance under the high-solids or water-base classifications.
Knowing which items in a mixture were photochemically reactive was
helpful when discussing a possible violation with a company. If a company
considered reformulation, it was advised which components of .the mixture
needed to be reformulated. The average and maximum pounds per hour figure
was useful in determining the emissions from sources using the specific
solvent.
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Exhibit 6 is a copy of the format sheet used with the compliance check
program. The data listed in vertical columns on the left side of the sheet
are entered into the computer. This information is furnished by the company
on the Organic Emission Data Form. The data listed in the horizontal rows
on the right hand side of the sheet are the output from the computer, as
explained above.
Exhibit 7 is a flow diagram illustrating the general logic of the com-
pliance check program but not the detailed calculations involved in the
decisionmaking. In order to clarify the definition of a photochemically
reactive material, it is necessary to present the detailed calculations in-
volved in the determination of whether or not a material is photochemically
reactive. The calculation must be clarified because the definition of a
photochemically reactive material specifies certain percentages by volume of
designated chemical compounds. The percentage is based on the total organics,
including liquid and solids, in the compound. However, the percentage avail-
abe from a company is based on the liquid organics in the compound. There-
fore, it is necessary to perform a calculation which converts the percentages
given on page 9, rows 6c, 6d, and 6e of the Organic Emissions Data Form to
the basis of total organics in order to evaluate whether or not a material
is defined as photochemically reactive.
Following is the calculation method used to change the basis of the
volume percentage of Class 1 material from total liquid organic to total
organic:
Volume % of total organics = (volume % organic solvent) + (volume %
solids/100) x (volume % solids organic).
Volume % of Glass 1 material in the formulation = (volume % of Class
1 compounds ) x (volume % organic solvent/100).
Volume % of Class 1 material based on total organics = (volume % of
class 1 material in the formulation)/(volume % of total organics).
The volume percentage based on total organics of the two other classes of
materials is determined in the same manner as used for Class 1 material.
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DATA ANALYSIS: SUMMARY FORMS
The "Summary Program" determines the following items (all figures are
in gal/yr; the bracketed phrase refers to the label given to the figure
on the format sheet):
1. The total amount of formulations used (Formulation Used);
2. Total solvent contained in 1 (Potential Solvent);
3. Total solvent from 2 which is captured by a control device
(Solvent Controlled);
4. Solvent emitted to the atmosphere (Solvent Emitted);
5. Total solvent emitted that is defined as photochemically reactive
(PCR Solv. By Def.);
6. The total of the various classes of solvent used to define a
photochemically reactive solvent contained in coatings that are
defined as photochemically reactive (1,2,3 in PCR Material);
7. The total of the various classes of solvent used to define
nonphotochemically reactive (1,2,3 in NPCR Material);
8. The total of each of the three classes of materials used in the
definition of a photochemically reactive material--(Class 1),
(Class 2), (Class 3);
9. The total of each of the three classes of materials used in the
definition of a photochemically reactive material which is con-
tained in material defined as photochemically reactive or non-
photochemically reactive; for example, Class 1 material contained
in photochemically reactive material and nonphotochemically
reactive material is referred to as PCR 1 and NPCR 1, respectively,
on the format sheet: (PCR 1), (NPCR 1), (PCR 2), (NPCR 2), (PCR 3).
(NPCR 3).
10. Total photochemically reactive solvent associated with a particu-
lar coating (B);
11. Total of each of the three classes of materials used in the de-
finition of photochemically reactive material contained in 10:
(Gal/Yr Class 1), (Gal/Yr Class 2), (Gal/Yr Class 3).
12. Total of the three classes of materials given in 11 (C).
Exhibit 8 is a copy of the format sheet used with the Summary Program.
For the data listed in the vertical columns labeled 1»2,3, etc., items 1
through 20 are furnished by the company and entered into the computer. The
remainder of the information on the sheet is the output from the computer, as
explained above. Each vertical column refers to a single coating. The in-
formation listed in the two rows at the bottom of the sheet are totals for
59
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all of the coatings used by a company.
Exhibit 9 is a flow diagram illustrating the general logic of the Sum-
mary Program.
In order to better understand the format sheet used with the Summary
Program, it is necessary to know the distinction between a) material that
is photochemically reactive by definition and b) material that falls into
one of the three classes of chemical compounds which are used in the defini-
tion of a photochemically reactive material. The definition of photochemi-
cally reactive material states that when an organic material consists of
more than a specified percentage (by volume) of any of the three listed
classes of chemical compounds, or more than 20 percent (by volume), or an
aggregate of the three listed classes of chemical compounds, it is defined
as photochemically reactive.
The entire formulation is defined as photochemically reactive when it
meets the requirements of the definition. This is the case even though
there are some exempt compounds in the formulation.
A compound included in one of the three classes of chemical compounds
used in the definition of a photochemically reactive material may or may not
cause the formulation of which it is part to be defined as photochemically
reactive. Since these three classes of compounds have been determined to
be highly photochemically reactive, the ordinance has been designed so as to
control the use of formulations that contain a significant amount of these
three classes of compounds. However, a formulation may contain less than
the specified amounts of the three classes of chemical compounds and there-
fore not be defined as photochemically reactive. When a formulation is not
defined as photochemically reactive, the emissions of it to the atmosphere
are not regulated by the ordinance, unless there happens to be an odor
nuisance.
The purpose of making this distinction is to show that even though a
formulation may not be defined as photochemically reactive, it may contain
a significant amount of material that in actuality is very photochemically
reactive. Significant quantities of the three classes of the chemical corn-
ponds used in the definition of photochemically reactive material are emit-
ted from processes which are in compliance with the ordinance. This compli-
ance is achieved by either the formulation being nonphotochemically reactive
-------
by definition, or the emissions of the formulation being less than 8 Ib/hr
from each emission source, or the use of a control device. The point to be
considered here is that the emissions of reactive material in compliance
with the ordinance will most likely not be reduced, because in general the
reactive material is less expensive and more readily available than nonre-
active material. Also to be considered is the fact that when a noncomplaint
formulation is brought into compliance through reformulation, the emission
of the three classes of chemical compounds used in the definition of photo-
chemical^ reactive material will be reduced, but the reduction will not
necessarily be 100 percent.
DATA ANALYSIS:
COMPLIANCE OF OTHER SECTIONS OF THE FORM
Analysis of Sections I and III of the Organic Emission Data Form was
made by inspection. The company's specific situation was reviewed in light
of the applicable regulations. This approach was used because each situa-
tion varied and it was therefore not practicable to use a computer method.
CORRECTIVE PROGRAMS
When it was determined that a company could possibly be in violation of
the Organic Emission Ordinance, the company was requested to attend an in-
formal meeting in the department's office to discuss the matter. At the
meeting, the information submitted on the data form was verified and the
process using the photochemically reactive material was discussed. It was
necessary to verify the data because a company may have changed its material
since the form had been completed or the company may not have interpreted
the data form correctly.
The process using the photochemically reactive material was discussed
in order to determine the nature of the process, the type of equipment used,
and the rate of material usage. The process itself may affect total emis-
sions due to solvent retention.
Important considerations regarding the equipment are the number of
pieces of equipment and associated vents to the atmosphere. In some cases,
61
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a company used a photochemically reactive material in a number of machines,
each with its own vent to the atmosphere so as to allow each machine to be
defined as a source. In these cases, the companies may have been emitting
a substantial amount of photochemically reactive material; however, they
were not in violation since no one source exceeded the ordinance limitation
of 8 Ib/hr. Another important consideration is the sequence in which the
equipment is used. Application areas, conveyors, and drying or baking de-
vices may be used in various sequence. The location of the emission will
be affected by the "flash off" rate of the material and the flash off forced
by a piece of equipment, as well as by the equipment sequence. For example,
during a conveyor spray coating operation, solvent will "flash off" in the
spray booth, on the conveyor to the drying oven, and in the oven. If the
coating has a high flash off rate, as lacquer does, a majority of the sol-
vent in the lacquer will flash off immediately in the booth. However, if
the coating has a low "flash off" rate, such as an enamel, a substantial por-
tion of the solvent will remain in the coating until it is forced to flash
off in the drying oven.
Material usage was discussed to determine the rate of usage associated
with each piece of equipment. In most cases, when a company used several
pieces of the same type of equipment, the usage rate of various pieces varied.
For example, one piece may be for touch-up or special work.
After the discussion relating to the data form and the process, the De-
partment determined whether or not there were a potential violation or wheth-
er additional information were required. If the company was determined to
be in compliance, they were advised accordingly. If a potential violation
were determined or additional information were required, a plant visit was
scheduled.
The purpose of the plant visit was to acquire additional information to
verify a possible violation or to make a determination of whether or not the
company were in violation.
In the case that a violation was verified at the meeting in the depart-
ment's office, it was felt that this determination should be further substan-
tiated by an inspection of the process. This procedure was followed in
order to be certain that a company was in violation of the ordinance prior
to requiring the company to take action to remedy the violation.
62
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In some cases, the information obtained at the meeting at the depart-
ment's office was not sufficient to determine the company's status. In these
cases, information obtained during the plant inspection was sufficient to
make the necessary determination regarding compliance.
After it was determined that a company was not in compliance with the
ordinance, the company was advised of the procedure which provides exemp-
tion from the operation of Chapter 17 of the ordinance in order to allow the
company time to cqme into compliance. The effect of this procedure is to
allow the company exemption from enforcement action during the time that they
are ordering and installing control equipment and/or developing replacement
materials.
The procedure consists of the company requesting, in writing, that the
Commissioner of the Department of Environmental Control grant a period of
grace in which to come into compliance with the applicable section of the
ordinance. The information needed to evaluate the request consists of: 1)
present status of subject process; 2) proposed methods of remedying the vio-
lation; and 3) the time schedule for completing the program.
The present status was usally determined as a result of the previous
data. The proposed method was evaluated so the department could determine
whether or not the method would have a likelihood of success in the specific
case at hand. If the department did not believe that the proposed method
had a likelihood of success, the company was advised accordingly. The time
schedule was evaluated as to the reasonableness of the time necessary for
the particular proposed method. If the compliance program required more
than 90 days, the company's case was referred to the Appeal Board of the De-
partment of Environmental Control.
CONCLUDING REMARKS
This paper has presented the Organic Emission Survey Program of the City
of Chicago's Department of Environmental Control as a workable and efficient
method of bringing about compliance with new legislation. Following the com-
pletion of the program, a yearly updating will take place through our estab-
lished Annual Inspection Program. This will allow for the addition of new
companies, the deletion of some old ones, and the annual variations in usage.
63
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As of the writing of this paper, 323 firms have been requested to com-
plete the Organic Emission Data Form. These firms use organic-base sol-
vents in a variety of processes, for example: printing,-spray painting,
finishing, coating, material treating, dry cleaning, degreasing, and storage.
Of the 197 data forms that have been returned and evaluated, 88 percent
(174 companies) were found to be in compliance initially. The 23 companies
found to'be in violation of the hydrocarbon ordinance were-placed on control
programs: 10 of these companies have completed their programs and 'are now in
compliance. The methods used to achieve compliance included; thermal and/or
catalytic incineration; absorption; ultraviolet curing; and reformulation
by exempt solvents, water-base material, or high-solids materials. Due to
the compliance programs of the above-mentioned 10 companies, 1,611 tons of
photochemically reactive material by definition have been abated. The meth-
ods being implemented to achieve compliance by the remaining 13 companies
are similar to those noted above. When these companies complete their pro-
grams we will be able to determine their .reductions of,pollutants emitted.
The data collected enabled us to update our Emission Inventory. Based
on the data evaluated to date, we have determined that the potential.-solvent
emissions are 15.7 percent greater than those given in the previous Emission
Inventory. •
. Accoring to Chapter 17 of the Municipal Code of Chicago, major emitters
are required to file and abide by an episode action plan. These plans call
for emission reduction when specifics-pollutant levels are reached in the
City and take into account whether or not a company is in compliance with
the applicable ordinances. Exhibit 10 presents the criteria of the "Episode
Alert Program" of the City of Chicago.
The development and implementation of the Organic Emission Survey Pro-
gram has been a unique experience for us. In this age of specialization, it
is rare that one has the opportunity to maintain such intimate contact with
every phase of a program. Being able to deal on a personal basis with'most
of the surveyed companies has given us insight into many problems which
might otherwise, if gone unresolved, have served only to increase the appre-
hension with which industry deals with regulatory agencies.
This relationship allowed us to efficiently collect our data while re-;
quiring only the minimum input by the-company.
64
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It is hoped that this paper has communicated what we have learned
and incorporated in our program.
ACKNOWLEDGMENT
The authors would like to acknowledge the guidance, interest, and sup-
1 : J r-
port given to their work by Edward J. Petkus, Director of Engineering, and
Don B. Gallay, Assistant Director of Engineering.
APPENDIX
NOTE. - The 10 exhibits called out in text are shown on the following
pages.
65
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Exhibit 1
ANALYSIS OF HYDROCARBON AMENDMENT SECTION 17-2
AND PERTINENT DEFINITIONS
en
AMENDMENTS AS WRITTEN
Photochemically Reactive Material: Any
organic material with an aggregate of
more than 20% of its total volume com-
posed of compounds classified below or
the composition of which exceeds any of
the following individual percentage, com-
position limitations:
(1) A combination of hydrocarbons,
alchohols, aldehydes, esters,
ethers or ketones having an
olefinic or cyclo-olefinic type of
unsaturation: 5%. This defini-
tion does not apply to perchlor-
oethylene or trichloroethylene.
(2) A combination of aromatic com-
pounds with eight or more car-
bon atoms to the molecule ex-
cept ethylbenzene: 8%.
(3) A combination of ethylbenzene,
ketones having branched hydro-
carbon structures or toluene: 20%
Whenever any photochemically reactive
material or any constituent of any or-
ganic material may be classified from its
chemical structure (1), (2), (3), it
INTERPRETATION
Photochemically Reactive
Material: Any organic
material whose composition
exceeds 20% by volume of
the totaled categories be-
low, or exceeds any of
the individual percen-
centages.
1. Olefins or cyclo-
olefins - 5%
2. C8 and above - 8%
3. Toluene, ethyl ben-
zene and branched
ketones - 20%
EXAMPLE
The percent of photochemically
reactive compound in a formu-
lation is determined in the
following manner:
Volume of photochemically re-
active compound in solvent di-
vided by the volume of organic
solids plus the volume of sol-
vent. (See calculations in text.)
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Cr>
AMENDMENTS AS WRITTEN
shall be considered as a member of the
most reactive group, that is. that group
having the least allowable percent of the
total organic materials.
Organic Substance: Any chemical com-
pound of carbon including diluents
and thinners which are liquids at stan-
dard conditions and which have such
uses as dissolvers, viscosity reducers
or cleaning agents, but excluding
methane, carbon monoxide, carbonic
acid, metallic carbonic acid, metallic
carbide, metallic carbonates and am-
monium carbonate.
Volatile Organic Material: Any or-
ganic substance which has a vapor
pressure of 2.5 pounds per square
inch absolute (psia) or greater
at 70°F.
17-2B.7. No person shall cause or
allow the discharge or more than 8
pounds per hour from the use of
organic substances into the atmos-
Exhibit 1 (con.)
INTERPRETATIONS
EXAMPLE
Organic Substance: Any
compound of carbon (solid
liquid or gaseous), along
with the inclusions and ex-
clusions stated.
Volatile Organic Material As
It Differs From Volatile Con-
tent; Volatile organic ma-
terial is defined as an organic
substance with a vapor pres-
sure of 2.5 psia at 1 ATM and
70°F; however, in sections 17-
2B.7(2)b and 17-2B.7(2)c, the
phrase volatile content is used
to mean something different.
Volatile content is construed to
mean liquid phase in those par-
ticular sections.
Discharge From Emission
Sources: Cannot discharge
more than 8 Ibs/hr of or-
ganic substances into the
A company could emit 8 Ibs/hr
or less of any organic substance
and be in compliance.
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Ot
00
AMENDMENTS AS WRITTEN
phere from any emission source ex-
cept as provided in the following sub-
sections .
(1) Alternative Standard: Emissions
of photochemically reactive material
in excess of those permitted in para-
graph 17-2B.7 above are allowable
if such emissions are controlled by
one of the following methods.
(a) flame, thermal or catalytic incin-
eration so as either to reduce such
emissions to 10 ppm equivalent methane
(molecular weight 16) or less, or to
convert 85% of the hydrocarbons to
carbon dioxide and Water; or
(b) a vapor recovery system which
which absorbs and/or condenses at
least 85% of the total uncontrolled
organic substance that would be other-
wise emitted to the atmosphere; or
(c) any other pollution control equip-
ment approved by the Commissioner
capable of reducing by 85% or more the
uncontrolled organic substance that
Exhibit 1 (con.)
INTERPRETATION
atmosphere from any emis-
sion source.
EXCEPT
1. More than 8 Ibs/hr e-
mission of photochemically
reactive material is permis-
sible provided that the e-
missions are controlled by
one of the following:
(a) Incineration - must be
controlled to 10 ppm cal-
culated as methane or to
85% efficiency.
EXAMPLE
(b) Vapor recovery sys-
tem - must be at least 85%
efficient.
(c) Any other approved de-
vice - must be 85% efficiency.
(a) A company has the op-
tion to reduce emissions by
incineration 85% or to 10 ppm
calculated as methane. This
would mean that for concen-
trations of 66 ppm (Calcu-
lated as methane) or less, con-
trol device of less than 85%
efficiency would be adequate.
Because this could bring the
ppm calculated as methane
below 10.
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would be otherwise emitted to the
atmosphere.
(2) Exceptions: The provisions of this
paragraph 17-2B.7 shall not apply to the
following:
(a) The spraying or use of insecti-
cides, herbicides, or other pesticides.
(b) To the use of any substance in
any article, process, or machine
equipment, or device if:
(i) the volatile content of such
substance consists only of water
and organic substances; and
(ii) the organic substance com-
prises not more than 30% of said
volatile content.
(c) To the use of any substance in any
article process, or machine, equipment
or device if the volatile content of such
substance does not exceed 30% by vol-
ume of said substance.
(d) The transport and application of
paving asphalt and paving marking paint.
(3) Further Exceptions: If no odor
nuisance exists, this paragraph 17-
2B.7 shall apply only to photochemi-
cally reactive material.
Exhibit 1 (con.)
(2) Exceptions: 8 Ib/hr
limitation does not apply
to:
a. Spraying or use of
insecticides, herbicides or
pesticides.
b. The use of substances
whose liquid phase is com-
prised only of water and
organics. The organic por-
tion does not exceed 30% by
volume of the liquid phase.
c. The use of substances
whose liquid phase does not
exceed 30% by volume, of
the substance.
d. Transport and appli-
cation of paving asphalt and
and paving marking paint.
(3) Further Exceptions; If
no odor nuisance exists,
the 8 Ib/hr limitation ap-
plies only to photochemically
reactive material except
#1 and #2.
2b. A company using a formu-
lation, classified as photochemi-
cally reactive, composed of a
solid phase, and a liquid phase
consisting of only water and
organics, could emit greater
than 8 Ib. and be in compli-
ance provided that the organics
comprise 30% or less of the liquid
phase.
2c. A company can discharge in
excess of 8 Ib/hr of a material
classified as photochemically
reactive provided that the mater-
ial's liquid phase comprises not
more than 30% of the total volume.
3. If there is no odor nui-
sance the company can emit
an unlimited amount of ma-
terial that is classified non-
photochemically reactive, but
to 8 Ib/hr of reactive material
unless exemption #1 or #2 is met.
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Exhibit 2
ITY OF CHICAGO
DEPARTMENT OF ENVIRONMENTAL CONTROL
RICHARD J. DALEY H. W. POSTON
MAYOI COMMIHIONd
XYZ Company
123 1st St.
Chicago, 111. 60600
Attn: Mr. J. Jones, President
Gentlemen:
On May 29, 1974, the City Council for the City of Chicago adopted a
new hydrocarbon amendment to Chapter 17 of the Municipal Code which be-
came effective on June 8, 1974,
You are required to complete the enclosed data so that this depart-
ment can determine whether or not your emission sources are in compliance.
Your response should be forwarded to the attention of Messrs George
Czerniak or William T. Thorp within thirty (30) days from the date of this
letter.
Your cooperation in this matter is appreciated.
Sincerely yours,
Edward J. Petkus
Director of Engineering
Enclosure
320 North Clark Street Chicago, Illinois 606)0 Phone Area Code 312 744-4070
Mnnd on 100% lUcycM fop*
70
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Exhibit 3 - Attachment
Article IIC
CONTROL OF EMISSIONS
OF ORGANIC SUBSTANCES
Defiattfaas
17-2C.1. For the purpose of thi» Article, whenever any of the following word*
terms or definitions an used herein, they shall have the meaning ascribed to them in
this Section.
Air Contaminant: Any smoke, soot, fly ash, dust, cinders, dirt, noxious or obnox-
ious acids, fumes, oxides, gases, vapors, odors, toxic or radioactive substances, waste,
particulate. solid, liquid or gaseous matter, or any other materials in such place, man-
ner or concentration as to cause injury, detriment, nuisance, or annoyance to the pub-
Ik, or to endanger the health, safety or welfare of the public, or as to cause or have •
tendency to cause injury or damage to business or property.
Architectural Coating: Any coating used for residential, commercial or industrial
building* and their appurtenances, that is on site applied.
Ooaaenradoa Vent Valve: A weight-loaded valve designed and used to reduce evap-
oration losses of volatile organic substances by limiting the amount of air admitted to,
or vapors released from the vapor space of a closed storage vessel.
Control Apparatus: Any device which prevents, eliminates, or controls the emis-
sion of any air contaminant
Equipment: Any device capable of causing the emission of an air contaminant
into the open air, and any stack, chimney, conduit, flue, duct, vent or similar device
connected or attached or serving the equipment. This shall include equipment in
which the preponderance of the air contaminants emitted is caused by a manufactur-
ing process.
Floating Roof: A storage vessel cover consisting of a double deck, pontoon single
deck, internal floating cover or covered floating roof, which rests upon and is sup-
ported by the liquid content being contained, and is equipped with a closure seal or
seals to close the space between the roof edge and tank wall.
Manufacturing Process: Any action, operation or treatment embracing chemical,
industrial manufacturing, or processing factors, methods or forms including, but not
limited to, furnaces, kettles, ovens, converters, cupolas, kilns, crucibles, stills, dryers.
roasters, crushers, grinders, mixers, reactors, regenerators, separators. Alters, reboilers.
columns, classifiers, screens, quenchers, cookers, digesters, towers, washers, scrubbers.
mills, condensers or absorbers.
Maximum Allowable Emission Rate: The maximum amount of an air contami-
nant which may be emitted into the outdoor air during any prescribed interval of time.
Odor Nuisance: Any noxious odor in sufficient quantities and of such character-
istics and duration as to be injurious to human, plant, or animal life, to health, or to
property, or to unreasonably interfere with the enjoyment of life or property.
Oil-Effluent Water Separator: Any tank, box sump, or other container or group of
such containers in which any organic material floating on, or entrained, or contained
in water entering such containers is physically separated and removed from such
water prior to the exit from the container of such water.
Organic Substance: Any chemical compound of carbon including diluents and
thinner* which are liquids at standard conditions and which have such uses as dis-
solvers, viscosity reducers or cleaning agents, but excluding methane, carbon monoxide,
carbon dioxide, carbonic acid, metallic carbonic acid, metallic carbide, metallic carbon-
ates and ammonium carbonate.
Organic Vapor: Gaseous phase of an organic substance or a mixture of organic
substances present in the atmosphere.
71
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Exhibit 3 - Attachment (con.)
Partioulate Matter: Any solid or liquid material, other than water, which exists in
finely divided form.
lasjaMs; Any crude petroleum, conderaato. and any finished or inter-
mediate product* manufactured in a petroleum refinery but does not mean Number 2
through Number 6 fuel oil* a* specified in A8TM-D-396-69. gas turbine fuel oils Num-
ben 2-OT through 4-GT as specified in ASTM-D-2880-71. or dieeel fuel oils Numben
2-D and 4-D as specified in A8TM-D-976-68.
Uy Reactive Material: Any organic material with an aggregate of
more than 20 percent of it* total volume composed of the chemical compound! clasai-
fied below or the composition of which exceeds any of the following individual per-
centage, composition limitations:
(1) A combination of hydrocarbons, alcohol*, aldehydes, eaten, ethers or ketonaa
having an olefinic or cyclooleflnic type of unsaturation: 5 percent This defi-
nition does not apply to perchloroethylene or trichloroethylene.
(2) A combination of aromatic compounds with eight or more carbon atoms to
the molecule except ethylbenaene: 8 percent
(8) A combination of ethylbencene, ketones having branched hydrocarbon struc-
tures or toluene: 20 percent
Whenever any photochemically reactive material or any constituent of any organic
material may be classified from its chemical structure (1), (2), (3). it shall be consid-
ered as a member of the most reactive group, that is, that group having, the least allow-
able percent of the total organic materials.
Tank: A tank in which fluids are stored at a pressure greater than at-
mospheric pressure.
Stack or Chimney: A flue, conduit or opening designed and constructed for the
purpose of emitting air contaminants into the outdoor air.
Standard Conditions: Shall be 70°F. and one atmosphere pressure (14.7 psia or
760 mm Hg).
True Vapor Pressure: The equilibrium partial pressure exerted by a petroleum liq-
uid as determined in accordance with methods described in American Petroleum Insti-
tute Bulletin 2617, Evaporation Loss From Floating Roof Tanks, 1962.
Volatile Organic Material: Any organic substance which has a vapor pressure of
2£ pounds per square inch absolute (psia) or greater at 70*F.
Emissions from I/ftrg» Tanks
17-2G2A. No person shall cause or allow the storage of any volatile organic ma-
terial in any stationary tank, reservoir or other container of more than 40,000 gallons
capacity unless such tank, reservoir or other container:
(1) is a pressure tank capable of withstanding the vapor pressure of such mate-
rials, so as to prevent vapor or gas loss to the atmosphere at all times; or
(2) is designed and equipped with one of the following vapor loss control devices:
(a) a floating roof which rests on the surface of the volatile organic material
and is equipped with a closure seal or seals to close the space between the
roof edge and the tank wall. Such floating roof shall not be permitted if
the volatile organic material has a vapor pressure of 12.6 pounds per
square inch absolute or greater at 70°F. No parson shall cause or allow
the emission of air contaminants into the atmosphere from any gauging or
sampling devices attached to such tanks, except during, sampling-
(b) a vapor recovery system consisting of:
(i) a vapor gathering system capable of collecting 86% or more of the un-
controlled volatile organic material that would be otherwise emitted
to the atmosphere; and
(ii) « vapor disposal system capable of processing such volatile organic
material so as to prevent their emission to the atmosphere. No person
shall cause or allow the emission of air contaminants into the atmos-
phere from any gauging or sampling devices attached to such tank.
reservoir or other container except during sampling.
(c) other equipment or means of equal efficiency approved by the Commis-
sioner.
72
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Exhibit 3 - Attachment (con.)
(3) is an existing con* roof tank used exclusively for OM storage of Illinois crude
oil. if all the following eonditioM are mat:
(a) the vapor pressure of such crude oil is las* than 5 pound* per square inch
absolute (psia); and.
(b) the location of §uch tank is outride a major metropolitan area; and.
(c) Mich tank is equipped with positive pressure tank vent valves and vacuum
breakers.
Petroleum Liquid Storage
17-2CJB. Tlie owner or operator of any new storage vessel for petroleum liquid*
which has a storage capacity of greater than 40.000 gallons shall store petroleum liq-
uids as follows:
(1) If the true vapor pressure of the petroleum liquid, as stored, is equal to or
greater than 78 mm Hg (1.5 psia) but not greater than 670 mm Hg (11.1
psia). the storage vessel shall be equipped with a floating roof, a vapor recov-
ery system, or their equivalents.
(2) If the true vapor pressure of the petroleum liquid as stored is greater than 670
mm Hg (11.1 psia), the storage vessel shall be equipped with a vapor recovery
system or its equivalent
Loading Facilities
17-3C.3. (1) No person shall cause or allow the discharge of more than 8 pounds
per hour of volatile organic material into the atmosphere during the loading of any vol-
atile organic material from the aggregate loading pipes of any loading facility having a
throughput of greater than 40.000 gallons per day into any railroad tank car, tank track
or trailer unless such loading facility is equipped with submerged loading pipes or a de-
vice that is equally effective in controlling emissions and is approved by the Commis-
sioner according to the provisions of this Ordinance.
(2) No person shall cause or allow the loading of any volatile organic material
into any stationary tank having a storage capacity of greater than 260 gallons, unless
such tank is equipped with a permanent submerged loading pipe or an equivalent de-
vice approved by the Commissioner according to the provisions of Article I of this
Chapter, or unless such tank is a pressure tank or is fitted with a recovery system as
described in Section 17-2C.2A(2)(b).
(a) Exception: This Subparagraph 17-2C.3(2) shall not apply to: (1) the loading
of such volatile organic substances into any tank having a capacity of less than 2.000
gallons which was installed underground or below street-grade level prior to the date of
the adoption of this rule, and (2) in-plant tanks used exclusively for blending, mixing
or weighing.
Water Separator
17-2C.4. No person shall use any single- or multiple-compartment effluent water
separator which receives effluent water containing 200 gallons a day or more of organic
substance from any equipment processing, refining, treating, sorting, or handling or-
ganic substance unless such effluent water separator is equipped with air pollution con-
trol equipment capable of reducing by 86 percent or more the uncontrolled organic sub-
stance emitted to the atmosphere.
Exception: If no odor nuisance exists, this Paragraph 17-2C.4 shall apply only to
volatile organic material.
Pump or Compressor Volatile*
17-SC.5. No person shall cause or allow the discharge of more than two cubic
inches of liquid volatile organic materials into the atmosphere from any pump or com-
pressor in any 15 minute period at standard conditions.
Architectural CoaUag*
17-2G6. No person shall cause or allow the sale or use in the City of Chicago of
any architectural coating containing more than 20 percent by volume of photochemi-
cally reactive material in containers having a capacity of more than one gallon.
No person shall thin or dilute any architectural coating for use in the City of Chi-
cago with a solvent containing a photochemically reactive material in quantity greater
than one quart of solvent per gallon of architectural coating.
73
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Exhibit 3 - Attachment (con.)
17-XC.7. No person shall cause or allow the discharge of more than 8 pounds per
hour from the use of organic substances into the atmosphere from any emission aoarce
except as provkUd in the following subsections:
(1) Alternative Standard: Emissions of photochemically reactive material in ex-
oaai of thoaa permitted in Paragraph 17-2C.7 above are allowable if auch emissions are
controlled by one of the following method*:
(a) flame, thermal or catalytic incineration *o a* either to reduce *uch emissions to
10 ppu equivalent methane (molecular weight 16) or lea*, or to convert 85 per-
cent of the hydrocarbon* to carbon dioxide and water; or
(b) a vapor recovery system which absorb* and/or condense* at leut 86 percent of
the total uncontrolled organic substance that would he otherwise emitted to
the atmosphere; or
(c) any other pollution control equipment approved by the Commiarioner capable
of reducing by 86 percent or more the uncontrolled organic substance that
would be otherwise emitted to the atmosphere.
(2) Exceptions: The provisions of this Paragraph 17-2C.7 ahall not apply to the
following:
(a) The *pmying or use of insecticide*, herbicides, or other pesticides.
(b) To the use of any substance in any article, process, or machine, equipment, or
device if:
(i) the volatile content of such substance consists only of water and organic
substances; and
(ii) the organic substances comprise not more than 30 percent of said volatile
content
(c) To the use of any substance in any article, process, or machine, equipment or
device if the volatile content of such substance does not exceed 30 percent by
volume of said substance.
(d) The transport and application of paving asphalt and paving marking paint.
(3) Further Exceptions: If no odor nuisance exists, this Paragraph 17-2C.7 shall
apply only to photochemically reactive material.
Odors
17-3C.8. No peraon shall cause, suffer, allow or permit to be emitted into the out-
door air volatile organic material which will result in odors detectable by sense oi
smell in any area of public use or occupancy off the premises, and which constitute an
odor nuisance, as defined in 17-2C.1, notwithstanding compliance with the require-
ments of other Sections of this Chapter.
Exception: Inedible rendering plants a* defined in 17-2D.1 and covered in 17-2D.2.
Measurement
17-2C.9. The total organic substance concentrations in an effluent stream shall be
measured by a Flame lonixation Detector, or by other methods approved by the Com-
missioner.
Petroleum Refinery and Petrochemical Manufacturing Process Emissions
17-2C.10. No peraon shall cause or allow the discharge of organic substance in
the atmosphere from:
(a) Any catalyst regenerator of a petroleum cracking system; or
(b) Any petroleum fluid coker; or
.'c) Any other waste gas stream from any petroleum or petrochemical manufactur-
ing process; in excess of 100 ppm equivalent methane (molecular weight 16.0).
Vapor Slowdown
17-2C.11. No person shall cause or allow the emission of organic substance into
the atmosphere from any vapor blowdown system or any safety relief valve, except
such safety relief valves not capable of causing an excessive release, unless such emia-
sion is controlled —
(a) To 10 ppm equivalent methane (molecular weight 16.0) or leas; or
(b) By combustion in a smokeless flare; or
(c) By other air pollution control equipment approved by the Commissioner.
74
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Exhibit 3 - Attachment (con.)
Safety Relief Valves
17-aC.ia. Sets of Unregulated Safety Relief Valves Capable of Causing Excessive
Releases. Section 17-2C.11 shall not apply to any set of unregulated sufety relief valve*
capable of causing excessive releases, provided that the owner or ope rator thereof, by
the effective date of the ordinance, provides the Commissioner with UH> following:
(a) A historical record of each such set (or. if such records are tins vailable, of sim-
ilar sets which, by virtue of operation under similar circumsta nce», may reas-
onably be presumed to have the same or greater frequency of excessive re-
leases) for a three-year period immediately preceding the effective date of the
ordinance, indicating:
(1) Dates on which excessive releases occurred from each suck >»*t; and
(2) Duration in minutes of each such excessive release; and
(3) Quantities (in pounds) of mercaptans and/or hydrogen suJflde emitted
into the atmosphere during, each such excessive release;
(b) Proof, using such three-year historical records, that no exceaai\re release is
likely to occur from any such set either alone or in combination w ith such ex-
cessive release* from other sets owned or operated by the same pet-son and lo-
cated within a tea mile radius from the center point of any such sett, more fre-
quently than 3 times in any 12 month period; and
(c) Accurate maintenance records pursuant to the requirement of Paragraph 17-
2C.12(a) of this Section; and
(d) Proof, at three-year intervals, using such three-year historical record*, that
such set conforms to the requirements of Paragraph 17-2C.12(c) of this
Section.
Cfoan-up Operations
17-2C.18. Emissions of organic material released during clean-up operati one and
disposal shall be included with other emissions of organic substance from the related
•mission source or air pollution control equipment in determining total emission s.
Disposal of Mora Than Five Gallons
17-2C.14. No person shall during any one day discard a total of more than 5 gal-
lons of any volatile organic substance by any means which will permit evapornti on of
such substance into the atmosphere.
Effootfr* Date
17-SC.lft. Every owner or operator of a new emission source, the plans for which
are 50% or less completed by the effective date of this Chapter, shall comply with the
standards and limitations on the effective date of this Chapter.
Every owner or operator of an existing emission source shall comply with the
standards and limitations within BO days of the effective date of this Chapter.
Submersed Loading Pipe; Any loading pipe the discharge ope'ning
of which is entirely submerged when the liquid level is six inches
above the bottom of the tank. When applied to a tank which is
loaded from the side, any loading pipe the discharge of which is
entirely submerged when the liquid level is 18 inches or two times
the loading pipe diameter, whichever is greater, above the bottom
of the tank. This definition shall also apply to any loading pipe
which is continuously submerged during loading operations.
75
-------
/EXHIBIT 3 - PAGE 1 of FORM
ORGANIC EMISSION DATA FORM
( formerly "Hydrocarbon Data Form")
Please complete this form to the best of your ability. The information required
to complete this form should be readily available from either your suppliers or your
I
knowledge of plant equipment and operations. You are not required to perform any
/
calculations or testing in order to complete this form.
This form consists of three sections concerning your plant operations. Also
included on pages 13, 14 and 15 is a copy of Chapter 17, Article II C of Municipal Code
of Chicago and a v/orking definition of a submerged loading pipe.
'/
If you requi re any assistance in the completion of this form, call either
7
George Czemiak, William Thorp or Philip Byron at (312) 744-3118.
*•
!
/
*' GENERAL DATA
COMPANY NAME: ADDRESS: (ZIP CODE)
I _
1
TELEPHONE: DATE:
NAME OF PERSON RESPONSIBLE TITLE: SIGNATURE:
FOR SECT',OK:
mr ,
M i
III
( Form '2, Jan 10, 1975)
76
-------
I (Exhibit 3 Page 2 of Form)
Instructions for completing Section I.
Complete this section if you use one or more stationary tanks with a capacity of
greater than 250 gallons, otherwise mark non-applicable.
Complete one column on Table I for each tank.
The information requested in part A should be available from your supplier.
The information requested in parts B and C should be available upon inspection
or from plant records.
For each tank enter the following information (parts A, B, and C) in the provided
spaces on the following pages:
Al Organic Stored - Enter either the trade name or chemical name of each organic stored.
A2 Petroleum Liquid - Check if organic stored is a petroleum liquid. (Includes gasoline).
A3 Vapor Pressure - Enter the vapor pressure of each organic in units of PSIA at 70 F.
If the organic is a petroleum liquid, enter the true vapor pressure of the liquid as
determined in accordance with methods described in American Petroleum Institute
Bulletin 2517.
Bl Capacity of Container - Enter the container capacity in units of gallons.
B2 Above - Below Grade - State whether the storage container is above or below grade.
B3 Outdoors - Check column if storage container is outdoors.
B4 Pressure Rating - If storage tank is a pressure tank, enter pressure rating.
B5 Submerged Loading Pipes (note the working definition of submerged loading pipes
before completing this part, see page 15). - Check if storage tank is equipped with
permanent submerged loading pipes.
B6 Installed Since 6/74 - Check if storage container was installed since 6/74.
B7 Mix, Blend, or Weight - Is this an in plant tank used exclusively for mixing,
blending or weighing (state yes or no).
C1 Control Device - Describe any vapor loss control device.
C2 Use - Describe the use of the stored organic (fuel, thinner, etc.).
C3 Sketch - Roughly sketch and label each storage system, including tank, loading
pipes, control device. Sketch on Page No. 4.
77
-------
SECTION I - TABLE I
(Exhibit 3 Page 3 of Form)
Al Organic Stored
A2 Petroleum Liquid
A3 Vapor Pressure
B1 Capacity of Container
B2 Above - Below Grade
B3 Outdoors '
B4 Pressure Rating
B5 Submerged Loading Pipes
B6 Installed Since 6/74
B7 Mix, Blend or Weigh
Cl Control Device
C2 Use
[ED. NOTE: Page 4 of this form Is blank.]
-------
C-3 (Exhibit 3 Page 4 of Form)
79
-------
(Exhibit 3 Page 5 of Form)
SECTION II
Instructions for completing Section II.
Complete this section if you use one or more liquid compounds in a
process.
Section II A relates to the compound used in the process, bection II B relates
to material used to thin the compounds given in Section II A.
Complete one column on Table II A for each liquid compound used in a
process. This information is to be based on the compound as delivered from the
manufacturer. If you thin the compound, then complete Section II B. Section II A
contains an explanation of the information requested in Table II A.
If you use a large number of compounds (20 or SO) please give us a call
for assistance. t
If you are required to complete Section II B, complete one row of Table II B
for each thinner used. This information is to be based on the thinner as delivered from
the manufacturer. The information for each thinner need be listed only once on Table II B.
Section II B contains an explanation of the information requested in Table II B.
If you require additional space on either Table II A or Table II B make a copy of
the table and enter the additional information on the copy. On the original table
indicate the number of added table copies.
The information requested in Table II A, 2a thru 3c (inclusive) and 8a thru lOb
(inclusive) should be available from your plant records, all other information requested in
Table II A should be available from your supplier.
All of the information requested in Table II B, except 3, should be available
from your supplier.
80
-------
(Exhibit 3 Page 6 of Form)
SECTION II A
Explanation of the information requested in Table II A.
la. Formulation Iked - Enter trade name and/or identification number of liquid
compound used.
Ib. Photo Reactive - To the best of your knowledge is the formulation photochemical Iy
reactive as defined in Chapter 17-2C. 1 of the Municipal Code of Chicago. (See
page 13 of this form). State yes or no.
2a. Avg Gal/Day - Enter the average number of gallons per day used in the process.
2b. Days/Year - Enter the number of days per year that the process using this
formulation is in operation.
2c. Hours/Day - Enter the number of working hours per day for the process using
this formulation (this number is not to include down time).
3a. Max Gal/Day - Enter the maximum number of gallons of formulation used per day
in the process.
3b. Days/Year - Enter the number of days per year that the maximum amount of
formulation is used.
3c. Hours/Day - Enter the number of working hours per day for the process when using
the maximum amount of the formulation (this number is not to include down time).
4. Weight/Gal - Enter the weight per gallon of the formulation (Ibs.).
5a. Volume % Solids - Enter the volume percent of the formulation which is comprised
of solid material.
5b. Weight % Solids - Enter the weight % of the formulation which is comprised of
solid material.
5c. Volume % Solids Organic - Enter the volume percent of the solid portion of the
formulation which is comprised of organic material.
81
-------
(Exhibit 3 Page 7 of Form)
6a. Volume % Organic Solvent - Enter the volume percent of the formulation which
is comprised of organic solvent.
6b. Weight % Organic Solvent - Enter the weight percent of the formulation which
is comprised of organic solvent. .-,
6c. Volume % Class (1) Compounds - Enter the volume percent of the organic solvent
portion which is comprised of material classified in (1) of the definition of
"PhotochemicalIy Reactive Material" given on page 13 of this form.
6d. Volume % Class (2) Compounds - Enter the volume percent of the organic solvent
portion which is comprised of material classified in (2) of the definition of
"Photochemically Reactive Material" given on page 13 of this form.
6e. Volume % Class (3) Compounds - Enter the volume percent of the organic solvent
portion which is comprised of material classified in (3) of the definition of
"Photochemically Reactive Material" given on page 13 of this form.
7a. Name of Other - If applicable, enter the name of other material (besides solids
and organic solvent) which is used to make up the formulation.
7b. Weight % of Other - Enter the weight percent of the formulation which is
comprised of other material.
7c. Volume % of Other - Enter the volume percent of the formulation which is
comprised of other material.
8a. Process - Describe the process in which the formulation is used; ie printing,
painting, cleanup, etc.
8b. Control Device - Describe any control device used in conjunction with the process.
If stack test results are available, these should be submitted.
82
-------
(Exhibit 3 Page 8 of Form)
9a. Thinner '] - If the formulation, as delivered from the manufacturer, is thinned at
your plant, enter the name of the thinner in column 9a. If two thinners ore used,
enter the neme of the second thinner in column lOa. If more than two thinners are
used prepare an addendum to this form in which the names of the additional thinners
for this formulation are labeled lla, 12a, etc. as required. (Also include in the
addendum lib, 12b, giving the respective thinner rate).
9b. Thinner Rate 'l - Enter the number of gallons of thinner *1 used per gallon of
the formulation.
lOa. Thinner *2 - Enter the name of the second thinner (if used).
lOb. Thinner Rate *2 - Enter the number of gallons of thinner *2 used per gallon of
the formulation.
83
-------
seai ON ii A
TABLED A
(Exhibit 3 Page 9 of Form)
la Formulation Used
Ib Photo Reactive
2a Avg. Gal/Day
2b DaysAear
2c Hours/bay
3a Max. Gal/Day
3b Days/Year
3c Hours/bay
4 Weight/Gal
5a Volume % Solids
5b Weight % Solids
5c Volume % Solids Organic
6a Volume % Organic Solvent
6b Weight % Organic Solvent
6c Volume % Class (1) Compounds
6d Volume % Class (2) Compounds
6e Volume % Class (3) Compounds
7a Name of Other
7b Weight % of Other
7c Volume % of Other
8a Process
8b Control Device
9a Thinner 'l
9b Thinner Rate '1
lOa Thinner ?2
lOb Thinner Rate '2
84
-------
(Exhibit 3 Page 10 of Form)
SECTION II B
Explanation of the information requested in Table II B.
la Name of Thinner - Enter the trade name and/or identification number of the
liquid compound used.
Ib Photo Reactive - To the best of your knowledge is the compound photochemically
reactive as defined in Chapter 17-2C.1 of the Municipal Code of Chicago.
(See page 13 of this form). State yes or no .
2. Weight/Gal - Enter the weight per gallon of the formulation (Ibs.).
3. Gal/Day - Enter the average number of gal Ions per day used.
4a. Volume % Class (1) Compound - Enter the volume percent of the thinner which
is comprised of material classified in (1) o': the definition of "Photochemically
Reactive Material" given on page 13 of this form.
4b. Volume % Class (2) Compound - Enter thus volume percent of the thinner which is
comprised of material classified in (2) of the definition of "Photochemically
Reactive Material" given on page 13 of this form.
4c. Volume % Class (3) Compound - Enter the volume percent of the thinner which is
comprised of material classified in (3) of the definition of "Photochemically
Reactive Material" given on page 13 of this form.
85
-------
(la)
00
Nome of Thinner (
Photo
Ib) Reactive
seai ON ii
Weight
(2) Gal
B
Gal
(3) Day (<
TABLE II B
Volume %
Class (1)
la) Compound (
• •
— (Exhibit 3 Page
Volume %
Clou (2)
4b) Compound
1 1 of Form)
Volume %
Oass (3)
(4c) Compound
.-.
t* '
-------
(Exhibit 3 Page 12 of Form)
SECTION III
Answer the following questions yes or no.
A. Do you load more than 40,000 gallons per day of organic material into
railroad tank cars, tank trucks or trailers?
B. Do you use a single or multiple compartment effluent water separator? _
C. Is there a vapor blowdown system or a safety release valve associated
with your plant?
D. Do you presently have or are you requesting a compliance program or a
variance with the State of Illinois for hydrocarbon emissions?
(If your answer is yes, include a status report and a copy of relevant material,
such as the order of the Pollution Control Board, petitions, compliance plan,
etc.)
NOTE: Due to the format specifications of this
paper, pages 13 thru 15 of the "Organic
Emission Data Form" have been replaced
with the following 5 pages.
87
-------
Exhibit 4
ITY OF CHICAGO ;•
DEPARTMENT OF ENVIRONMENTAL CONTROL
RICHARD J . DALEY H. W. POSTON
MAVOI
XYZ Company
123 1st St.
Chicago, 111. 60600
Attn: Mr. J. Jones, President
Gentlemen:
In October, 1974, your firm was sent information and guidance
pertaining to the new hydrocarbon amendment of the City ordinance.
At that time you were requested to fill out the attached data
sheets. It has come to our attention that additional time may be re-
quired in the preparation of these data sheets.
If your company requires any assistance or a time extension,
please feel free to call Messrs George Czerniak, William Thorp or Philip
Byron at 744-3118 or 3119.
Sincerely,
Edward J. Petkus
Director of Engineering
320 North Clark Street Chicago, Illinoii 60610 Phone Area Code 312 744-4070
PrinM o» IOCS l«r
-------
Exhibit 5
ITY OF CHICAGO
DEPARTMENT OF ENVIRONMENTAL CONTROL
•ICMAUD J. DALEY M. W. POSTON
COMMUSIOMl
XYZ Company
123 1st St.
Chicago, 111. 60600
Attn: Mr. J. Jones, President
Dear Sir:
Your firm was notified on October 17, 1974, and November 25, 1974,
of the necessity to complete certain hydrocarbon data sheets so that
a determination could be made as to your emission sources compli-
ance.
To date, your firm has not complied with these requests, therefore,
if the referenced forms are not on file with this department by January
17, 1975, enforcement action will be taken.
Very truly yours.
Edward J. Petkus
Director of Engineering
cc: Enforcement Division
Corporation Counsel
320 North Clark Street Chicago, Illinois 60610 Phone Area Code 312 744-4070
89
-------
Exhibit 6
HYDROCARBON COMPLIANCE SUMMARY
10
o
COMPANY NAME: XYZ CO.
COAT-
ING
RE AC.
THINNER THINNER FORMU- OTHER
1 2 LATION EXEMP- AVG. MAX.
REACTIVE REACTIVE REACTIVE TION LB/HR LB/HR
FORMULATION #
AVG. GAL/DAY
HRS . /DAY
MAX. GAL/DAY
HRS . /DAY
WT./GAL
VOL. % SOLIDS
VOL. % SOLIDS ORGANIC
WT. % ORGANIC SOLVENT
VOL. % CLASS 1
VOL. % CLASS 2
VOL. % CLASS 3
NAME OF OTHER
VOL. % OTHER
THINNER RATE #1
THINNER RATE #2
CONTROL EFFICIENCY
THIN. #1 WT./GAL
THIN. #1 GAL. /DAY
THIN. #1 VOL. % CLASS 1
THIN. #1 VOL. % CLASS 2
THIN. #1 VOL. % CLASS 3
THIN. #2 WT./GAL
THIN. #2 GAL. /DAY
THIN. #2 VOL. % CLASS 1
THIN. #2 VOL. % CLASS 2
THIN. #2 VOL. % CLASS 3
1
6.00
8.00
9.00
8.00
8.00
.14
.66
.76
.00
.01
.49
.00
.00
1.00
.00
.00
6.86
6.00
.00
.00
.19
.00
.00
.00
.00
.00
2
3.00 8
8.00 10
6.00 16
8.00 10
7.40 20
.11
.80
.80
.09
.00
.00
.00
.00
1.00
.00
.00
6.86
3.00
.00
.00
.19
.00
.00
.00
.00
.00
3
.00
.00 YES
.00
.00
.00
.80
. 00 YES
.15
.00
.00
.00
.00 NO
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
FORMULATION // 1
NO N/A YES NONE 9.68 14.52
FORMULATION # 2
NO N/A NO NONE 4.78 9.56
FORMULATION // 3
N/A N/A NO HI SOL 2.40 4.80
-------
Exhibit 7
HYDROCARBON COMPLIANCE SUMMARY
FLOW DIAGRAM
ENTER AND STORE
DATA
PRINT
DATA
T
INITIALIZE
COUNTER
N -O
•N- IS A COUNTER WHICH IS USED
TO DIRECT THE FLOW Of THE PROGRAM.
EACH TIME "N- IS INCREMENTED AND
THEN SEARCHED, ANOTHER BRANCH OF
THE PROGRAM IS FOLLOWED..
91
-------
Exhibit 7 (con.)
HYDROCARBON COMPLIANCE SUMMARY
FLOW DIAGRAM
C N O J CN1 J
CHECK
IF
COATING IS
P.C. REACTIVE
CHECK if
THINNED 'I
ISP.C. REACTIVE
c *•» )
COATING
CUT WITH
THINNER
•31
CHECK IF
THINNER '2
IS P.C. REACTIVE
CHECK IF
FORMULATION
P.C.
92
-------
Exhibit 7 (con.)
HYDROCARBON COMPLIANCE SUMMARY
FLOW DIAGRAM
C N=
CALCULATE
AVERAGE
I
PRINT
AVERAGE
IB/Ha
CALCULATE
MAXIMUM
1
PRINT
MAXIMUM
L8/HH
CHECK
YES ^ ANOTHER
FORMULATION
93
-------
Exhibit 7 (con.)
HYDROCARBON COMPLIANCE SUMMARY
FLOW DIAGRAM
94
-------
10
en
Exhibit 8
HYDROCARBON DATA SUMMARY
COMPANY:
DATE:
FORMULATION NO.
1. PHOTO-CHEM REACTIVE BY DBF. 1.
2. AVG. GAL/DAT 2.
3. DAYS/YEAR 3.
4. VOL. Z SOLVENT 4.
5. VOL. Z CLASS 1
6. VOL. Z CLASS 2
7. VOL. Z CLASS 3
8. THINNER RATE 1
9. THINNER RATE 2
10. THINNER RATE 3
11. CONTROL EFFICIENCY
12. 11 VOL. Z CLASS 1
13. 11 VOL. Z CLASS 2
14. 11 VOL. Z CLASS 3
15. « VOL. Z CLASS 1
16. 12 VOL. Z CLASS 2
17. « VOL. Z CLASS 3
18. 13 VOL. Z CLASS 1
19. 13 VOL. Z CLASS 2
20. 13 VOL. Z CLASS 3
21. B
22. GAL/YR CLASS 1
23. GAL/YR CLASS 2
24. GAL/YR CLASS 3
25. C
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
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.
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.
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.
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.
FORMULATION
USED
PCR
1
POTENTIAL
SOLVENT
NPCR
1
SOLVENT
CONTROLLED
PCR
2
SOLVENT
EMITTED
NPCR
2
PCR SOLV.
BY DBF.
PCR
3
1,2,3 IN
PCR
MATERIAL
NPCR
3
1,2,3 IN
PCR
MATERIAL
CLASS
1
CLASS
2
CLASS
3
-------
Exhibit 9
HYDROCARBON DATA SUMMARY
ENTER AND STORE
DATA
I
PRINT
DATA
CALCULATE
FORMULATION
TOTALS
I
PRINT
FORMULATION
TOTALS
CONTINUE
(ANOTHER
FORMULATION)?
96
-------
Exhibit 9 (con.)
HYDROCARBON DATA SUMMARY
CALCULATE
COMPANY
TOTALS
PRINT
COMPANY
TOTALS
I
END
PROGRAM
Chicago Department of Environmental Control
97
-------
Exhibit 10
REQUIREMENTS FOR WATCH
1. ASA received for any area within state
OR
2. National Weather Service forecast for next 24 hours does not indicate
substantial improvement.
AND
two hour average of following pollutants at any monitoring station
have reached or exceeded these levels;
SO, -30 ppm for 2 hr. average
COH 5.0 COH's for 2 hr. average
Product of SO2 x COH 1.0 for 2 hr. average
CO 30 ppm for 2 hr. average
O3 .07 ppm for 2 hr. average
NO- -40 ppm for 2 hr. average
{*
REQUIREMENTS FOR YELLOW ALERT
1. Watch in effect for four hours where yellow alert is to be declared
AND
2. Official National Weather Service forecast for next 12 hours does not
indicate substantial improvement
AND
98
-------
Exhibit 10 (con.)
Yellow alert levels at any monitoring station for the following pollu-
tants reach or exceed these levels.
SO2 .30 ppm for 4 hr. average
COH 3.0 COH's for 24 hr. average
Product of COH x SO2 1.0 for 4 hr. average
Product of COH x SO2 .20 for 24 hr. average
CO 15 ppm for 8 hr. average
O .10 ppm for 1 hr average
NO2 .60 ppm for 1 hr. average
NO-, .15 ppm for 24 hr. average
REQUIREMENTS FOR RED ALERT
Yellow alert in effect for 4 hours where red alert is to be declared
AND
Official National Weather Service forecast for next 12 hours does not
indicate substantial improvement AND EITHER OF THE FOLLOWING
CONDITIONS IS MET:
EITHER
99
-------
Exhibit 10 (con.)
3a. Red alert levels at any monitoring station for the following pollutants
reach or exceed these levels;
SO- .35 ppm for 4 hr. average
COH 5.0 COH's for 24 hr. average
Product of SO x COH 2.0 for 4 hr. average
Product of SO2 x COH .80 for 24 hr. average
CO 30 ppm for 8 hr. average
Oo .40 ppm for 1 hr. average
NO2 1.20 ppm for 1 hr. average
NO2 .30 ppm for 24 hr. average
OR
3b. Yellow alert levels at any monitoring station for the following pol-
lutant reach or exceed these levels;
SO, .30 ppm for 24 hr. average
COH 3.0 COH's for 24 hr. average
Product of COH x SO2 .20 for 24 hr. average
CO 15 ppm for 24 hr. average
O~ .10 ppm for 24 hr. average
NO .15 ppm for 24 hr. average
£t
REQUIREMENTS FOR EMERGENCY
1. Red alert has been in effect for 12 hours where emergency is to be
declared.
100
-------
Exhibit 10 (con.)
Official National Weather Service forecast for next 12 hours does not
indicate substantial improvement AND ANY OF THE FOLLOWING CON-
DITIONS IS MET:
EITHER
Emergency levels at any monitoring station for the following pollutants
reach or exceed these levels;
SO2 .40 ppm for 4 hr. average
COH 7.0 COH's for 24 hr. average
Product of SO2 x COH 2.40 for 4 hr. average
Product of SO2 x COH 1.20 for 24 hr. average
CO 40 ppm f°r 8 hr. average
O-3 .60 ppm for 1 hr. average
1.6 ppm for 1 hr. average
.40 ppm for 24 hr. average
OR
Red alert levels at any monitoring station for the following pollutants
reach or exceed these levels;
SO2 .35 ppm for 24 hr. average
COH 5.0 COH's for 24 hr. average
Product of SO2 x COH .80 for 24 hr. average
CO 30 ppm for 24 hr. average
Oj .40 ppm for 24 hr. average
NO .30 ppm for 24 hr. average
101
-------
Exhibit 10 (con.)
OR
3c. Yellow alert levels at any monitoring station for the following pollutants
reach or exceed these levels;
so2
COH
Products of COH x SO-
CO
°3
NO.,
.30 ppm for 36 hr. average
3.0 COH's for 36 hr. average
.20 for 36 hr. average
15 ppm for 36 hr. average
.10 ppm for 36 hr. average
.15 ppm for 36 hr. average
102
-------
DISCUSSION
THE FLOOR; To what extent is Chicago a model for other cities?
MR. CZERNIAK: As of this point, we are not really dealing with other cities,
and they have not contacted us about our program. Possibly with this
paper there will be some interest. And we would be glad to help out
anyone who would be interested.
DR. HERMAN F. KRAYBILL (National Cancer Institute, Bethesda, Maryland):
You were speaking lately about the air emissions and earlier, I guess,
about the water emissions. I take it that these reached Lake Michigan,
Lake Huron; is that correct? Would they reach Lake Michigan?
MR. CZERNIAK: In this paper, I was not speaking about water emissions.
But the effluent, as it is from these processes that we are consider-
ing today, would not reach Lake Michigan.
DR. KRAYBILL: Other bodies of water?
MR. CZERNIAK: Other bodies of water, such—
DR. KRAYBILL: Are those other sources for drinking water?
MR. CZERNIAK: They are used by some other cities farther downstream.
DR. KRAYBILL: Have you made any correlation into this and the levels in the
drinking water?
MR. CZERNIAK: No, we have not, not under this project. Possibly that will
be a further part of the study.
MR. CHARLES R. WARNER (National Cancer Institute, Bethesda, Maryland): Could
I ask about some of the exempt solvents? What are the identities?
MR. CZERNIAK: There is quite a list, and many of them have tradenames. In
other words, they do not give the chemical name of the chemical. The
list is just interminable; if you give me your name, I could certainly
get you a list of those.
DR. KRAYBILL; Another question, again, on the area. Who does the monitor-
ing, the plant?
MR. CZERNIAK: When a test is required, we will be doing the testing.
THE FLOOR: Have you traced how far away from that particular plant the con-
centration of this effluent carries?
103
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MR. CZERNIAK: No, not under this program. But from our technical services
people, I understand that there is a project proposed by the Navy in
which we would trace certain pollutants farther downstream.
THE FLOOR: How did you arrive at your guidelines for high solids or aqueous?
MR. CZERNIAK: These guidelines, I believe, are in Los Angeles Rule 66, and
they are also in the Illinois EPA regulations. And to some extent,
they were based on that. They differ only in the actual percentages
allowed.
MR. DONALD M. GARDNER (Monsanto Corporation, Indian Orchard, Massachusetts):
What percentages of companies got into compliance by switching to ultra-
violet curing inks?
MR. CZERNIAK: The companies that are currently using ultraviolet inks are
classified, probably, in the last 25 percent. They use the combina-
tion of methods. I will not give their names. They are some of the
largest emitters. And they have just developed the technology in the
coatings to be able to do this.
Just last week I was at one company that began production. It has
been pretty successful, and they plan to use additional units in the
future.
104
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22 September 1975
Session II:
ENVIRONMENTAL IMPACT OF CHEMICALS USED
William D. Schaeffer, Ph.D.*
Chairman
"Director, Research Department, Graphic Arts Technical Foundation, Pittsburgh, Pennsylvania
105
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SESSION INTRODUCTION
William D. Schaeffer, Ph.D.
Session Chairman
I am delighted to be here and want to express my appreciation to Dr.
Fisher, who organized the conference on behalf of the Environmental Protec-
tion Agency, and to Mr. Ayer and his associates of Research Triangle Insti-
tute for doing so much in the development of the background work that goes
•into organizing a conference of this type.
I am sure that many of you out there in the audience are not totally
aware, even after this morning's sessions and excellent presentations, of
the entire nature of the graphic arts industry. I thought that, for the
first moment or so, I might describe a few of the elements in the industry,
namely my own organization and its related activities.
The Graphic Arts Technical Foundation is a corporate membership founda-
tion devoted to technology and education in the graphic arts industry. It
currently has about 1,000 corporate members, 80 percent in North America and
approximately 20 percent distributed among the rest of the world.
We've become aware of the environment. As a matter of fact, some of
our first studies went back to 1967 and have gradually grown since. But the
problems of the environment by no means start or stop with one association,
as you will hear in the following two sessions. Because of the fragmentation
of the industry, about which I will have more to say later and which you will
hear a number of speakers address themselves to, it was felt that a broader,
more inclusive effort had to be made within the industry in order to deal
with the types of problems that we will be learning about. The best way we
could handle this problem was to try to bring all the groups in the industry
together: the business associations, the technical associations, and the
corporations themselves.
To that end, there was a move made back in 1971 to form what is called
the Environmental Conservation Board of the Graphic Communications Indus-
tries, Incorporated, a long moniker. That group is really acting as a com-
munications body today. Many of the actions taken on behalf of the industry
are emanating from the voluntary involvement of the business associations
106
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and some of the largest corporations in the industry. We're attempting to
speak on behalf of approximately 6,000 companies in the industry, repre-
sented by the approximately 20 associations in the ECB, as we call the
Environmental Conservation Board. So much for background.
Let's get to the next two sessions and their general context, the en-
vironmental impact of chemicals used. I think the purpose of these two ses-
sions is at least twofold. Certainly, the first purpose is awareness. The
conference can make some of us more aware and can extend to others of us new
awareness of the problems we in the industry and our associates in the govern-
ment face in working with the diverse problems in this area. Our responsi-
bility in this conference is to indicate the current status of knowledge and
of the developments that are emanated from the many groups and organizations
in the industry and in the government which have been directly involved in
studies.
Perhaps it would be useful to our associates in the government to rein-
force simply a few of the comments that were made this morning on the nature
of the graphic arts or printing industry in the United States.
Under the industrial census, as you were told, the printing industry is
classified number one in terms of number of establishments—approximately
40,000-- and employs more than 1 million persons. It was indicated this
morning that approximately 50 percent of these companies employ something
less than 100 people. The statistics in this area are, I think, even more
dramatic than that particular point. More than 90 percent of the 18,000 com-
mercial printing establishments have fewer than 50 employees, with almost 80
percent having fewer than 20 employees. Those statistics in themselves give
you some idea of the nature of the problems that we face in dealing with an
industry that is widespread geographically, but which is admittedly concen-
trated in certain urban areas.
The industry has in the past been severely segmented by differences in
the printing processes, which were generally outlined to you this morning.
Fortunately, the differences among companies, or the differences due to the
utilization of different printing processes, are gradually disappearing, in-
sofar as many, many plants have or are developing multiprocess capabilities.
Residual, however, from ages past is a fragmentation among the product groups:
107
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for example, fragmentation in terms of products such as newspapers; maga-
zines; periodicals; commercial, legal, and package printing; metal decorat-
ing; etc. We can readily count more than 20 different product groups in the
industry.
And fortunately or unfortunately, but a fact of life is that we have
more than 200 business associations serving the various groups within the
industry. Now communication, I think you can see, becomes something of a
major problem under these circumstances.
Let's go back to the title of these next two sessions, because I would
like to consider for a moment the implications of the words and phrases ex-
tracted from the title: namely, Environmental Impact of Chemicals Used.
In addressing ourselves to environmental impact within this conference,
we certainly have to recognize the several levels of the environment that
are involved. I think we should have to include the manufacturer of the
basic chemicals, the formulator of chemicals and products, the industrial
users—that would be the printer and/or packager and the user of the printed
page and/or package—and finally, the waste collectors, the salvagers, the
recyclers, and the disposers. In short, environmental impact within the
framework of this conference could include much of society because communi-
cation is the name of the game, and the printed page is still fundamental
to the communication process.
The breadth of the conference troubles me because of the scope and the
magnitude of the problems that we are asked to consider in this brief period
of time. The fact that the legislation and the regulations controlling the
several environmental areas are different; the fact that EPA, the conference
organizer, bears only partial responsibility for the environments in which we
work and live; the fact that legislation and regulations were developed in
many cases with limited scientific and medical knowledge; the fact that we
in the laboratory and in the industry use many materials without adequate
knowledge; all these facts we have to subordinate within the framework of
the conference. The most important aspect of environmental impact is the
scope and magnitude of the problems.
There are a few individuals, a few companies, a few agencies that may be
able to recognize and deal with the problems in all their complexities.
108
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Frankly, most of us in the industry cannot. Resources are finite, and they
must be marshaled for use in the priority-project areas. Resources of the
industry are very limited. I do not like to see them dissipated in shifting
priorities and projects, and goodness knows we have had plenty of that.
Thus, in the course of the conference, I certainly would like to see—
and I hope some more of you will make your feelings felt—that we are able
to make some assessment of where our priorities are and, possibly, where
they should be.
The scope of the environmental impact problem has been recognized, cer-
tainly, in the planning of this conference. In the next two sessions we are
going to have speakers from printing companies, supplier companies, includ-
ing the printing ink, paper, industry association speakers, government agen-
cy contributors and medical research personnel. More important than the
sponsors of the speakers, however, are the scientific and medical disciplines
in which the speakers are schooled.
Environmental impact is not a problem for chemists alone, not a problem
for a physicist alone, not a problem for medical doctors alone, not a prob-
lem for industrial hygienists alone. It is another example of the multi-
disciplinary problem that many of us in the printing industry, which repre-
sents multidisciplinary approaches, have recognized. I don't think there is
any question that we need this approach to assess and deal with the problems
of environmental impact. Communications have to be made between people in
these various disciplines if any progress is to be made at all.
We have an unusual opportunity in the next few days to talk with one
another and to learn what we are doing, how we are making out in our ap-
proaches, and how we look at the nature of the general environmental impact
problems that we face.
The second part of the session, entitled the Chemicals Used, seems sim-
ple enough to the chemists among us, despite the large numbers of chemicals
involved. I would suggest to you, however, that specific chemical identifi-
cation is frequently difficult. Commercial chemical supplies, first of all,
do contain numerous components, which frequently are not identified chemical-
ly. Second, chemical products synthesized by the printing supply industry
may or, more frequently, may not be identified as to chemical structures.
Often, it has not been thought necessary, or even economic to do so.
109
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And last, the influence of the printing process itself on the chemical
structure has to be considered. Whether we are dealing with films, plates,
development, or drying of heat set inks, comparatively little has been pub-
lished to indicate the specific composition of the chemicals entering the
environment.
Another factor of significant importance in this area is that the large
majority of printing supplies is based on proprietary compositions. A few
words were said in this direction this morning. In many cases the formula-
tions and compositions represent major investments of companies, not only in
assuring the performance of the product in the field, but also in safeguard-
ing their own in-plant environment as well as that of their customer. Not
surprisingly, information on specific chemical identification is often not
provided readily. In addition, chemical identification in supplies and
products can present real technical problems which are complicated by the
traditional structure of the industry based on proprietary supplies.
In summary, then, the next two sessions are going to be dealing with
environmental problems in the printing industry at several levels. Perhaps—
I certainly hope—a sense of priorities will emerge.
This conference will go a long way toward establishing communication
channels, both within the industry and between the industry and the govern-
ment agencies. I think many of our speakers are going to be dealing directly
with this communication problem.
110
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TOXICOLOGICAL EVALUATION OF CHEMICALS USED IN THE
PRINTING AND PRINTING INKS INDUSTRIES
Kingsley Kay, Ph.D.*
During the recent boom years, the graphic arts industry has been among
the most active in growth and technical development. There has been a trend
from letterpress to lithography, with the introduction of photo-sensitive
polymers for plates. Radiation-sensitive polymers have been developed for
use in sol vent!ess inks in order to meet ecological and energy requirements.
However, it must be noted that flexography and gravure, high-speed processes,
still require the use of liquid inks containing high-volatility solvents,
many of which have been demonstrated to be neurotoxic. Apart from the fore-
going there has been growing interest in the extent of occurrence of poten-
tial carcinogens in occupational situations. This has directed attention
toward carcinogenicity evaluation of the materials commonly used in the
printing industry, including ink pigments, solvents and the new polymers.
Site visits have been made to 25 companies in the printing and printing
ink formulation industries of New York and New Jersey, with the purpose of
identifying potentially toxic chemicals in the work environments and assess-
ing the toxicological possibilities for damage to the health of exposed
workers. In this effort there have been extensive consultations with manage-
ment, engineering specialists and chemists, as well as with pertinent na-
tional trade associations, concerned unions, the Division of Organic Coat-
ings and Plastics Chemistry of the American Chemical Society, the National
Cancer Institute, and the International Agency for Research on Cancer.
This report will consider, among several aspects, the carcinogenic
potential of chemicals in printing. It is therefore important to establish
that several chromophores or metabolic products thereof have been found
cancer-associated.
1. Monoazo compounds, first exemplified by carcinogenic dimethyl ami no-
azobenzene (butter yellow).
*Associate Professor, Environmental Sciences Laboratory, The Mount
Sinai School of Medicine, New York, N.Y. 10029.
Supported by National Institute of Environmental Health Sciences
Grant ES 00928 and American Cancer Society Grant R-53.
Ill
-------
2. Disazobenzidines, shown to reduce (hepatic azoreductase) to ben-
zidines and to be present in urine of monkeys fed the chromophore.
3. Triarylmethanes-ami no derivatives.
4. Xanthenes-amino derivatives.
5. 4,4'-diaminostilbenes, numerous triazenes and triazines.
One enzyme, azoreductase, which breaks azo groups, has been identified
in microsomal liver tissue, but there is conflicting evidence as to whether
the azoreductase level quantitatively correlates with cardnogenicity.
Nevertheless, in the case of disazobenzidines, the benzidine and 3,3'-di-
jchlorobenzidine fragments have been shown independently to be carcinogenic.
Furthermore, it has been reported from Japan that female kimono painters
using disazobenzidines have experienced high bladder cancer Incidence.
There are important problems in estimating carcinogenesis. To begin
with, exposure to a carcinogen must cover a substantial proportion of the
life span to eventualize in carcinogen!city, except in the case of newborn
animals, which can develop cancer soon after exposure to a carcinogen. As
an example, vinyl chloride was tested for 6 months on rats in 1961 and was
found carcinogenically inactive. However, when the experiment was repeated
in 1970, cancers attributable to the vinyl chloride were demonstrated at
around 12 months. Another related aspect of carcinogenicity testing on ani-
mal models is the effect of noncarcinogenic toxicity on life span. For
instance, the insecticide dieldrin is neurotoxic and hepatotoxic. Early
experiments to determine its carcinogenicity produced misleading results
because, at the level of dosage used, the dosed rats died from the neuro-
toxic and hepatotoxic action long before carcinogenicity could develop.
Another aspect of carcinogenicity testing on animals is the signifi-
cance of injection-site tumors when metastages to other organs does not
occur. Many experts consider injection-site tumors without metastases to
be of low significance. The neoplastic significance, if any, of so called
benign tumors has also aroused controversy, since, in some instances, with-
drawal of the provoking agent has been found to result in regression of the
growth. On the other hand, if dosage is continued, benign tumors may be-
come neoplastic
Various species and strains have a propensity for developing tumors
without the administration of carcinogenic chemicals, possibly due to un-
112
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known water, air, and food carcinogens. As a result, the number and variety
of tumors occurring in dosed animals can prove difficult to differentiate
reliably from the number and variety of the spontaneous type, even with the
use of sophisticated statistical methods. Furthermore, the target organs
may differ from species to species for the same chemical carcinogens and so
may the characteristic organ cancers of the spontaneous type. Finally, it
is known that housing conditions, age, sex, nutrition, and viruses influence
the occurrence of spontaneous tumors.
There are several problems in identifying occupationally occurring chem-
icals as ^etiological agents in human cancer. In the first place, it requires
upwards of 20 years of exposure to easily metabolized chemicals for cancer
to develop in man, or a similar elapsed time during which organ deposits,
such as lung asbestos, provide tissue insult when further exposure may have
ceased. Thus, the occupational origin of some cancers in persons who have
changed occupations or retired may not be recognized. The occupational ex-
posure may also involve a complex of chemicals as well as those associated
with cigarette smoking.
A most fundamental problem in identifying etiological agents of human
carcinogenesis is the difficulty of assembling large enough worker cohorts i
either retrospectively or prospectively to permit valid statistical compari-
son of cancer incidence between the occupational cohort and the general pop-,
ulation. This is especially true for cancers of organs such as the lung,
which occur in relatively high incidence among the general population. If
the cancers are of rarely occurring type, their occurrence in a worker group
even in small incidence will be striking. This was dramatically demonstrated
by the recent identification of vinyl chloride as etiological agent in the
causation of hemangiosarcomas of the liver in polyvinyl chloride production
workers. It was estimated that in all history only around 120 cases had been
reported, whereas among a few hundred workers in one PVC plant, 4 cases of
this hepatoma were recognized in a short period of time. For several reasons
just set forth, evidence of carcinogen!city in laboratory models has sometimes
been accepted under the Federal Occupational Safety and Health Act and the
Food and Drugs Act in the absence of incontrovertible proof that a chemical
carcinogen affects man.
113
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INK PIGMENTS AND DYES
Many pigments and dyes were found in the formulation laboratories of the
various printing ink concerns visited because they were "custom" businesses.
However, only a limited number of color compounds were used in substantial
quantities. In this situation, the president of a major New York printing
ink concern cooperated by analyzing the extent of use of color components in
the manufacture of his printing inks. A list of the 37 used in largest quan-
tity was provided. These are shown in tables la-lc along with the data re-
quired for carcinogenic evaluation of the chemicals. The 11st was reviewed
by the National Association of Printing Ink Manufacturers and was considered
to be representative.
As shown in table 2, there were 4 components cancer-positive in man or
animals, 15 probable by virtue of chemical class, and 5 were negative. The
evidence was conflicting for four, and on nine no information could be found.
Obviously pigments and dyes used in printing have not been comprehensively
evaluated for carcinogem'city.
Recent findings on laboratory animals introduce the possibility of non-
malignant kidney damage in persons exposed not only to lead pigments (refs.
44-47) but also to benzidine-based colorants (refs. 48-51) and 2-aminoanthra-
quinone (ref. 52).
In the printing ink establishments visited, the main occupational cate-
gories and potential colorant exposures were as shown in table 3. A control-
ling factor in colorant exposure 1s the necessity for a high degree of
cleanliness to preserve the integrity of formulations during processing.
Additionally, many colorants are worked up as pastes, though some are dry in
the early stages of formulation and are dusty to handle.
The significance of the foregoing in relation to cancer risk must be
deemed speculative pending the measurement of cancer incidence among the
workers in printing ink formulation and printing.*
*A recent personal communication from Dr. W. Fokkens, Rotterdamsch
Radio-Therapeutisch Instituut, notes that higher than expected incidence
of bladder cancer has been found in graphics industry workers.
114
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Table la. A summary of findings on the carcinogenictty of
37 major printing ink constituents
Name
of
component
Titanium
dioxide
Lead
chroma te
Molybdate
orange
Phthalo-
cyanine blue
Calcium
carbonate
Diary lide
Alkali blue
Clay
Barium
sulfate
Lithol red
ron blue
Carbon
Generic
name1
Cl pigment
white 6
No name
Cl pigment
red 104
Cl pigment
blue 15
No name
Cl pigment
yellow 1 2
Cl acid
blue 110
No name
Cl pigment
white 21 -22
Cl pigment
red 49
Cl pigment
blue 27
No name
Cl
number1
77891
77600
77605
74160
No number
21090
42750
No number
77120
15630
77510
No number
Chemical
class
Inorganic
PbCrO4
PbCr04-
PbMoO,
Copper
complex
CaCo,
Disazo
benzidine*
Triphenyl
methane deriv.
Silicates
BaS04
Monoazo
Nasalt
Ferric
ferrocyanide
Elemental
Usage as
XTiO,
100
40
20
20
20
15
15
15
15
10
10
10
Species
-
Man and
rats
See above
Mice
-
Route of
entry to
the body
-
Inhalation
subcutan.
See above
Subcutaneous
-
Exposure
or dose
level
-
Occupatnl.
10%aqun.
See above
0.5 mg/wk
-
Duration
-
Years
37 weeks
See above
8 months
-
Target
organs
-
Lungs
inj. site
See above
Nil
-
Some disazobenzidines reduce
(hepatic azoreductase) to carcinogenic
3,3'-dichlorobenzidine.
A variety of members of this chemical class
have been found to be carcinogenic.
-
-
Rats
-
Mice
-
-
Ingest ion
-
Skin surf.
subcutan.
-
-
0-1% of
diet
-
Various
-
-
2 years
-
To 20 mo.
-
-
Nil
-
Skin injec.
site
Lrtrefs.
No refs.
1.2,3
1.2,3
4
No refs.
5-10.
11 (p. 241)
11 (p. 22),
12-17
No refs.
No refs.
18
No refs.
19-22
cn
'Assigned by British Society of Dyers and Colourists, and the American Association of Textile Dyers and Colorists. Published as The Color Index.
33,3'-dichlorobenzidine 3 acetoacetanilide.
-------
Table 1 b. A summary of the findings on the cartinogenicity of
37 major printing ink constituents
Name
of
component
Magnesium
carbonate
Red lake C
Lithol
rubine
BON red
Red2B
Rhodamine3
Methyl
violet
Victoria
blue
Phthalocy-
anine green
Aluminum
hydrate
Phloxine
red
Naphthol
red
Generic
name1
Cl pigment
white 18
Cl pigment
red 53
Cl pigment
red 57
Cl pigment
red 52
Cl pigment
red 48
Cl basic
red 1
Cl basic
violet 1
Cl basic
blue 7
Cl pigment
green 7
Cl pigment
white 24
Clacid
red 87
Cl pigment
red 22
Cl
number1
77713
15585
15850
15860
15865
45160
42535
42595
74260
77002
45380
12315
Chemical
class
Inorganic
Monoazo
Nasalt
Monoazo
Nasalt
Monoazo
Nasalt
Monoazo
Nasalt
Xanthene
derivative
Triaryl
methane
Triaryl
methane
Chlorinated
Cu complex
AI,Oj and
AI,(SO4),(OH),
Xanthene
derivative
Monoazo
Usage as
%TiOa
10
7
7
7
5
5
5
5
5
5
3
2
Species
-
Rats
Route of
entry to
the body
-
Ingest ion
Exposure
or dose
level
-
0-1% diet
Ba salt
Duration
-
2 years
Target
organs
-
Nil
Related members of this chemical class
found carcinogenic.
Related members of this chemical class
found carcinogenic.
Related members of this chemical class
found carcinogenic.
Conflicting experimental evidence.
Conflicting experimental evidence.
A variety of members of this chemical class
have been found to be carcinogenic.
-
-
-
-
Various experimental protocols.
-
Nil
Conflicting experimental evidence.
Related members of this chemical class
found carcinogenic.
Lit refs.
No refs.
23
1 1 (p. 200)
1 1 (p. 200)
1 1 (p. 200)
1 1 (p. 23),24
1 1 (p. 22),
12-17,25
11
-------
Table 1c. A summary of the findings on the cartinogenictty of
37 major printing ink constituents
Name
of
component
Magenta3
Hansa
yellow
Bronze
powder
Aluminum
powder
Silica
aerogel
Cadmium
red
Fire red
Para red
Toluidine
red
Diarylide
orange
)initroanil-
ine orange
Cadmium
yellow
Talc
Generic
name1
Cl basic
violet 1 0
Cl pigment
yellow 1
Cl pigment
metal 2
No name
No name
Cl pigment
red 1 08
Cl pigment
red 4
Cl pigment
redl
Cl pigment
red 3
Cl pigment
orange 13
Cl pigment
orange 5
Cl pigment
yellow 37
-
Cl
number1
45170
11680
77400
No number
No number
77196
12085
12070
12120
21110
12075
77199
-
Chemical
class
Xanthene
derivative
Monoazo
Copper-zinc-
iron alloy
Elemental
SiO,
amorphous
Cadmium
selenide
Monoazo
Monoazo
Monoazo
Disazo
benzidine3
Monoazo
Cadmium
sulfide
Silicate
Usage as
XTiO,
2
2
2
2
2
<1
<1
<1
<1
<1
<1
<1
<1
Species
Route of
entry to
the body
Exposure
or dose
level
Duration
Target
organs
Conflicting experimental evidence.
Related members of this chemical class
found carcinogenic.
-
-
-
-
Various experimental protocols.
-
—
-
—
-
Nil
—
Other cadmium salts have been found
carcinogenic to animals.
Related members of this chemical class
found carcinogenic.
Related members of this chemical clas»
found carcinogenic.
Related members of this chemical class
found carcinogenic.
Some disazobenzidines reduce
(hepatic azoreductase)
to carcinogenic
3,3'-dichlorobenzidine.
Related members of this chemical class
found carcinogenic.
Rats
Man
Subcutan.
intramusc.
Inhalation
25 mg single
50 mg single
Various
Up to 1 5
months
Years
Injection
site
Lungs
Lit. Refs.
11 (p. 23),
16,17,24,
32-36
1 1 (p. 200)
No refs.
28,30,
37-39
No refs.
3,40,41
1 1 (p. 200)
1 1 (p. 200)
1 1 (p. 200)
5-1 0 and
11 (p. 241)
1 1 (p. 200)
40-41
4243
I
' Auij *c! by n itish Society of Dyers and Colourists, and the American Association of Textile Dyers end Colorists. Published in The Color lnri<;x.
"The -'"-.stitution number covsrs rhodamine B in Thp Color Index, where magenta is either Cl basic VIOM 14 142510) or the
-i'id i,.li of r
B '45170 2) listed as rr.sgenu. lake B. Cl bnsic violet 14 is a trifhenvlmethane triammo
'S.S'-rtlchlorober.zidine ~* 3-methyl-1-phenyl-5-pytazolone.
-------
00
iiura «. bonovmra HSMsnwni 01 we nrcinagenicny 01 j/ priming inn
color-related components including usage as percentage of TiO, used
Positive
Lead chroma te
Lead chromate-
lead molybdate
Carbon
Cadmium
sulfide
Total 4
'/« Probable' % Conflicting X Negative3
TiO, TiO, evidence TiO,
40 2di$azo 15 3 xanthenes 10 Phthalocyanine
benzidines <1 ' blue
20 2 triaryl 20 1 triaryl 5 2 monoazos
methanet methane
10 9 monoazos 25 Aluminum
hydrate
<1 Cadmium <1 Aluminum
selenide powder
Talc <1
*
70+ Total 15 60+ Total 4 15 Totals
% No
TiO, Information4
20 Titanium
dioxide
17 Calcium
carbonate
5 Clay
2 Barium sulfate
Ferric
ferrocyanide
Magnesium
carbonate
Chlorinated
copper complex
Bronze powder
Silica aerogel
44 Total 9
%
TiO,
20
15
15
10
10
5
2
2
79
1 In man and/or laboratory animals.
1A variety of members of these chemical classes have been found carcinogenic.
3 Negative to the extent tested (see tables la to 1c for details).
« No information on these or related members of their chemical classes.
-------
Table 3. Typical occupations in printing
ink formulation
Occupation
Bander and labeler
Combination man
Container washer
Driver
Shipper and receiver
Maintenance
Messenger
Mi 11 hand
Porter
Rollermaker
Sewing machine operator
Utility man
Varnishman
Weigher and mixer
Working foreman
Laboratory staff
Estimated pigment exposure
Slight
Slight
Medium
Slight
Slight
Medium
Slight
Medium
Medium
Slight
Slight
Medi urn
Slight
Substantial
Medi urn
Substantial
SOLVENTS
High-volatility solvents are used in formulation of liquid inks for
flexography and gravure, where fast drying is required. In the printing
establishments visited, the chlorinated hydrocarbon solvents—methyl chloro-
form and methylene chloride—were employed for hand cleaning of typeface.
It was an operation with substantial albeit intermittent exposure for the
typeface cleaner and adjacent workers.
An extensive range of volatile solvents was seen on the site visits.
Details on others were provided by the National Association of Printing Ink
Manufacturers. Table 4 lists the solvents, concentrations used, and the
threshold limit values recommended by the American Conference of Governmen-
tal Industrial Hygienists. Table 5 summarizes toxicological data on selected
solvents, including some used in printing and ink formulation.
It is now known that methylene chloride is metabolized in man to carbon
monoxide (refs. 111-117). Stewart et al. (ref. Ill) found abnormal levels of
119
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Table 4. Solvents used in gravure, flexography, and screen printing inks
Acetate ester of C2-C4
Aromatic hydrocarbon2
Bis-(2-ethoxy, ethoxy)ethanol
Diethylaminoethanol
Ethanol (denatured)
Ethyleneglycolmonoethylether
n-Heptane (•> 10% aromatic)
n-Hexane
Isopropanol
Isopropyl acetate
Lactol spirits3
Methanol
Methyl ethyl ketone
Mineral spirits4
n-Propanol
Textile spirits5
Toluene
Percentage
in organic
pigment ink
12
6
2-4
3-5
0-45
3
3-14
as above
2-14
10-20
4-51
12
0
58
0-14
43
5-62
Percentage
in inorganic
pigment ink
10
6
2-4
3-4
5-29
0
3-7
as above
0-12
6-15
12-30
5
11
53
5-18
30
3-7
TLV1
400
1000
400
100
400
250
200
200
200
100
'ppm in 1974.
2 Aromatic hydrocarbon solvent-C8 and higher aromatic hydrocarbons, 97%; saturated hydrocarbons,
3%; b.p. range 370°-410° F.
3 Lactol spirits - C6-C8 paraffins. 48%; C6 to C8 cycloparaffins, 35%; other than C8-C9, 10%; b.p.
range 250°-300° F.
4Mineral spirits - saturated aliphatic hydrocarbon|, 82.6%; aromatic (toluol or ethyl benzene), 15%;
C8 and higher hydrocarbons, 2.4%; b.p. circa 313 ° F.
5Textile spirits - CS-C6 paraffins, 70%; CS-C6 cycloparaffins. 24%; aromatics, 6%; b.p. circa 150° F.
120
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Table 5. Target organs in the systemic toxicity1
of selected industrial solvents1
Solvent
Benzene
Carbon tetra-
chloride
Chloroform
Dimethyl-
nitrosamine
Diethylene
glycol
Ethylene
dibromide
n-Hexane
Methyl-
chloroform
Methylene
chloride
Methyl n-butyl
ketone
Toluene
Trichlor-
ethylene
Turpentine
Carcinogenic
Leu kern ongenic
—man 63-69
Neg. -rats 59a
Liver 66-70
Liver 77
Liver, kidney.
etc., 82-89
Bladder 92
No Info.
Stomach 97,$7a
No info.
No info.
No info.
No info.
No info.
Liver (tentative)
128,129
No info.
Neurotoxic
Narcotic3 60, 61
PN4, hypotensive
71-74
Anesthetic, hypo-
tensive 78-80
No info.
Narcotic, CNS
depressant 93-95
CNS depressant
98 (p. 1285)
PN 100
CNS depressant.
hypotensive, 101,102
CNS depressant
98 (p. 1259)
110
PN (motor)
118-125
Narcotic 98
(p. 1226), 126
PN; cranial
130-133
CNS effects 78
Nephrotoxic
No info.6
TD5
TD 78-80
Glomerular 90
TD 92,96
Tubular swelling
99
No info.
No info.
No info.
Tubular congestion
98 (p. 1737)
TD, anuria
126.127
TD; acute renal
failure, 79,134
Hematuria,
albuminuria 136
Hepatotoxic
and other
Bone marrow 63,64
Cardiac senst. 65
Nonmalignant 75,76
Cardiac senst. 65
Nonmalignant 81
Cardiac senst. 65
Nonmalignant 91
Nonmalignant
92,96
Fatty infiltra-
tion 99
No info.
Mild 101,103-105
Cardiac senst.
106-109
No info.; con-
verts to CO,
111-117
Congestion
98 (p. 1 737)
Jaundice
127
Slightly 135
Cardiac senst. 65
No info.
1 In man and/or laboratory animals.
9 Numbers in the table refer to the bibliography. References are selected when a substantial literature exists.
'In large doses.
4 Peripheral neuropathy.
'Tubular damage.
'The reader is cautioned that the front page abstract of German reference 62 has "benzin" erroneously translated as
"benzene." The correct translation is "benzine." There is no published evidence at hand identifying benzene as
nephrotoxic.
121
-------
carboxyhemoglobin in blood (6 to 8 percent) after human exposure at levels
below the then-prevailing TLV (500 ppm). Signs of central nervous system
depression were also demonstrated, using the visual evoked response test,
which provided a measure of the cerebral electric response to a pulse of
light (refs. 137-138).
It has been known for several years that cytochrome P450 is inhibited
by carbon monoxide in vitro and in the housefly. The literature was reviewed
in 1969 (ref. 139). This effect was demonstrated in vivo with rats (ref.
140) in an experiment which showed that hexobarbital and zoxazolamine metabo-
lism were reduced in rats exposed to carbon monoxide (at substantial dosages).
Since methylene chloride has been found to produce carbon monoxide as a
metabolic product, reduction in drug metabolic activity of exposed workers
might be interesting to test for. This is especially noteworthy in that a
reduction in drug metabolism may change the reponse to a number of drugs,
such as warfarin and perhaps more importantly, alcohol, and undoubtedly the
carcinogenic polycyclic hydrocarbons, whose metabolism in the body responds
to the variations in the activity of the mixed-function oxidizing enzymes.
There is now evidence (ref. 141) that 1,1,1-trichlorethane stimulates
the drug-metabolizing power of the liver, which can lead to increased drug
metabolism. This effect may be reflected in levels of body burdens of DDT
and other adipose-stored chlorinated hydrocarbons. Most volatile solvents
are soluble in fat and fat-solubilizing. It may therefore be supposed that
they are stored in body fat. That there are body burdens of solvents in ex-
posed persons has been established by breath analysis (ref. 142).
Table 5 shows that many solvents produce prenarcotic effects as well as
abnormalities of nerve and muscle in over-exposed persons. EEG and memory
tests have been found useful as indicators of disturbances in the central
nervous system following exposure to a number of chlorinated hydrocarbons,
for instance the tests in 1960 by Chalupa et al. (ref. 143). Persons ex-
posed to 350 and 450 ppm of 1,1,1-trichlorethane (TLV 350 ppm) have been
tested for psychophysiological function by means of: 1) a perception test
with tachistoscopic presentation, 2) the Weschsler Memory Scale, 3) a com-
plex reaction time test, and 4) a manual dexterity test. There was little
evidence of psychophysiological change (ref. 144). Furthermore, the extent
of statistical work involved does not encourage this approach. It should
122
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be noted, however, that 110 ppm of trichlorethylene (TLV 100 ppm) caused a
very significant decrease in performance ability by all tests (ref. 145).
Other test batteries have been developed for trichlorethylene (ref. 146)
and methylene chloride (ref. 147).
In 1970, neuromuscular function of workers exposed to chlorinated hydro-
carbon insecticides was examined (ref. 148). EMG signs of impaired nerve and
muscle function were found in 4 percent of the exposed. So far no reports
of use of EMG on workers exposed to chlorinated hydrocarbon solvents have
been found. It is pertinent to note that the absorption of the volatile
solvents would be at a much higher level than for the chlorinated hydrocar-
bon insecticides and presumably would affect the EMG of a higher percentage
of subjects.
No environmental data on the level of exposure of proof pullers and
type cleaners to the cleaning solvents have been found in the literature.
Such measurements should be carried out as a basis for interpreting the
findings from clinical examinations.
Methyl chloroform has been shown to sensitize hearts of experimental
animals to stress-induced chemicals of the adrenalin class (table 5), but
similar effects on workers have not been reported.
Chloroform, carbon tetrachloride, and tentatively trichlorethylene have
been incriminated as cancer-producing in laboratory animals (see table 5).
Methyl chloroform is currently under test (ref. 149). A substantial number
of chlorinated hydrocarbon pesticides has been shown to be carcinogenic in
laboratory tests over recent years (ref. 150). Apart from chlorinated
hydrocarbon solvents, exposure to benzene has been shown to be associated
with leukemia in workers (see table 5). This may be of great health signi-
ficance since it has long been known that toluene and other hydrocarbon sol-
vents can contain benzene as a process impurity. Not withstanding, benzene
has not yet been shown to be carcinogenic in animal models (59a).
CANCER AMONG PRINTERS
It was found that ink was heavily dispersed into the workroom atmos-
phere during newspaper printing, to such an extent that a clean piece of
paper placed on printing equipment was very soon blackened by atmospheric
123
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fallout. Clearly, printing ink was entering the lungs of exposed personnel.
Nevertheless, occurrence of lung neoplasias or pulmonary defects in news-
paper printers, in excess of the incidence in the average population, has
not yet been established. As indicated by footnote at the end of the Ink
Pigments and Dyes section, excessive bladder cancer has been noted in the
graphics industry in the Netherlands.
In 1955, Ask-Upmark (ref. 151) found the bronchogenic cancer incidence
of a group of typographers to be 18 times higher than normal (without
adjustment for smoking habits). Dunn and Weir (ref. 152) followed the can-
cer experience of several occupations progressively and concluded in 1965
that printers did not show higher than normal incidence. A small excess of
lung cancer deaths in British newpaper workers was noted by Moss et al.
(ref. 153) for the period 1952-1966.
Several years ago, 22 printing inks of unidentified composition were
tested in England by subcutaneous injection in mice (ref. 154). Seventeen
were negative and five caused injection site neoplasms, of which two showed
metastases to the lung. Indeed, as long ago as 1929, Steinbruck (refs. 155-
156) painted mouse skin with a printing ink and produced skin epitheliomas
with lung metastases, and lymphomas.
Much investigation of the carcinogenicity of carbon has been carried out
(refs. 19-22) and it would appear that apart from source differences, bio-
logical activity is dependent on particle size and adsorptivity (ref. 22).
Carbon blacks of average particle diameter 17 my tenaciously held benzo[a]-
pyrene and were biologically inactive. However the presence of the eluent
tricaprylin evoked carcinogenicity at sites of subcutaneous injection. It
would have to be determined whether the high-boiling oils used with carbon
black in inks would also act as eluents for cancer-producing chemicals ad-
sorbed on the carbon.
LEAD
Apart from consideration of lead chromate as a pigment, it may be men-
tioned that in 1943, Black (ref. 157) advanced lead as a possible inciting
factor in bronchogenic carcinoma. In 1963, Dingwall-Fordyce and Lane (ref.
158) reported no association between lead exposure and incidence of malig-
124
-------
nant neoplasms in a small cohort of battery workers. More recently, lead
phosphate, acetate, and tetraethyl lead have been found to produce cancers
in laboratory animals (ref. 159).
The problem of a lead hazard in the printing industry was widely inves-
tigated many years ago (refs. 160-173). Measures to control exposure to
lead vapor and dust were introduced throughout the industry, with the result
that classical lead poisoning cases are rare today. However, with more re-
fined techniques available for estimating functional abnormalities of nerve
and muscle, reexamination of this aspect would be desirable.
It is now believed that lead acts as a competitive inhibitor of the
mechanism for release of acetylcholine at synaptic and neuroeffector junc-
tions. Normally calcium fulfills this role. Peripheral neuropathy has been
encountered in overexposed lead workers (and pica-eating children). For in-
stance, Catton et al. (ref. 174) found a minimal defect of peripheral nerve
function in a group of lead battery workers without clinical evidence of a
neurological lesion. Abnormal chronaxie was described among Japanese print-
ers in 1936 (ref. 175). Behavioral aspects of lead exposure were dealt with
last year (refs. 176,177).
«
Thus, examination for functional abnormalities of nerve and muscle in
printers might be considered if, for instance, blood levels proved to be in
the region 40 yg lead per 100 ml blood and over. In view of the demonstrat-
ed effects of lead on the CNS and on peripheral nerve and muscle function
(ref. 178), it is suggested that an assessment of the accident frequency of
typographers would be rational. In 1963 it was reported (ref. 158) that
cerebrovascular deaths were of higher-than-normal incidence in a small popu-
lation of battery workers. However, other investigators (ref. 179) failed
to find a relationship between lead exposure and hypertension.
AMMONIA EXPOSURE
The use of large tanks of anhydrous ammonia adjunct to photo-offset
machines was found to be associated with gassings from time to time due to
faulty lines from tanks. There is also a continuous ammonia exposure during
normal operation of the machines. The amount of ammonia released varies
from machine to machine and no doubt depends on servicing. There should be
125
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environmental assessment of the levels of ammonia present in the air adjacent
to the machines.
Two papers from Scandinavia describe cerebral effects of acute ammonia
intoxication (refs. 180,181). Intraperitoneally injected ammonia has been
found to be rapidly taken up by red cells, with a subsequent flight of K+,
but no change in Na+ (ref. 182).
Some consideration should be given to pulmonary response of exposed
workers since it is known that ammonia, at least in high air concentrations,
induces a pneumonitic response.
POLYMERS
Evaluation of the potential toxicity of polymers used in the printing
trade has been initiated on the basis of observations made during the site
visits to 25 establishments. Many well-known polymers are used in printing
inks to bind pigment to the printed surface. Conventional plasticizers and
oxidation accelerators are also ink ingredients. The recent development of
solventless inks has resulted in the introduction of an extensive range of
new polymers having radiation-sensitive prSperties for use in photolitho-
graphy inks and plate coatings. A toxicity evaluation of polymers used in
printing will be presented at a later date.
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DISCUSSION
MR. THEOPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
On this carbon, is it possible that it could be contaminated with PNA,
polyneuclear aromatics? As a food additive, we even check solvents for
PNA's, because this is where the greatest amount of impurities could be
found.
DR. KAY : Yes. I should have mentioned that. That is what I was talking
about; carcinogens in carbon black are believed to be polycyclic aro-
matic hydrocarbons.
GENERAL CHAIRMAN FISHER : In this regard, I would just like to interject what
happened at the first conference in this series, which was on the rubber
Industry, where we discussed the question of whether or not carbon black
was a carcinogen. We had three speakers on the subject, and a rather
heated discussion which went well into the evening.
There definitely are different points of view. My overall impres-
sion is that there appears to be no question but that carbon black does
have adsorbed on it materials which in other contexts are known carcino-
gens—polynuclear aromatics. There also appears to be fairly strong
evidence, at least under injection or inhalation-type conditions, that
these materials are not removed from the carbon black and do not seem
to have the effects that they would have if administered alone, without
the carbon black.
Now as to whether or not in the presence of an organic solvent during
administration, these may come off is a question which I don't think any-
body really is able to answer at this point.
DR. KAY: It has been said by Steiner that the reason it has not been possi-
ble to produce lung cancers in laboratory animals with carbon alone is
because the lung does not contain any waxes like the skin. And Steiner
claims that you can produce cancers with carbon black on skin because
you have the wax in the skin, and the wax acts as an eluent. I think
as long as some carbon blacks have been shown to be carcinogenic in ani-
mals, we have to take that point of view about all of them.
CHAIRMAN SCHAEFFER: May the Chairman ask a question of that point? Are we
sure that we are talking about some carbon blacks or are we talking
about ground charcoal? Ground charcoal, I think, definitely has been
140
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cited. I am not sure about some carbon ...
DR. KAY ; I am including ground charcoal.
CHAIRMAN SCHAEFFER: Okay.
DR. KAY: I guess carbon black is ...
CHAIRMAN SCHAEFFER: Is not ground charcoal.
DR. KAY: ... not the best description.
CHAIRMAN SCHAEFFER: No.
DR. KAY : I think this does apply to ground charcoal. In fact I know that
it has been studied.
CHAIRMAN SCHAEFFER: I think there is one more question here, please.
MR. GEORGE A. REMUS (R. R. Donnelley Company, Chicago, Illinois): Has poly-
vinyl chloride been shown to be carcinogenic?
DR. KAY: Not to my knowledge.
141
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POTENTIAL HAZARDS OF ORGANIC SOLVENTS
IN THE GRAPHIC ARTS INDUSTRY
Jacqueline M. Fetsko*
Abstract
Physical, chemical, and other data relevant to fire and health hazards
were compiled for 123 organic solvents. The selection of solvents was baaed
on use by the printing ink industry as ingredients in inks* intermediates,
or washup solvents.
Analysis of the data indicates that the typical organic solvent is apt
to be flammable, to cause irritation of some form, and, if absorbed into the
body, to depress the central nervous system or be injurious to a vital organ,
or both.
The potential hazards may be minimized by adequate ventilation to avoid
flammable- or toxic-vapor concentrations and by strict hygienic measures to
prevent skin contact.
By now, all of you should be aware, either from your own experience or
from attendance at this conference, that organic solvents are very important
chemicals in the graphic arts industry. You have heard Mr. Carpenter (ref. 1)
state that 700 million pounds of organic solvents are used in printing
inks each year. This quantity probably does not include the hundreds of
pounds of press-side diluents and washup solvents that are also used.
One does not have to go to the graphic arts industry to be involved with
organic solvents. Indeed, organic solvents play a very important role
throughout modern society and technology: gasoline, antifreezes, and brake
and transmission fluids to run our autos, trucks and buses; dry cleaning
fluids; after-share lotions and other cosmetics; adhesives, paints, and
paint thinners; and agricultural pesticides.
For many years industrial hygienists and safety engineers have viewed
this growing increase in the use of organic solvents with alarm, because if
used without proper control, the vast majority of them are to some extent
hazardous. These hazards are now being recognized by many Government
*Assistant Research Director, National Printing Ink Research Institute,
Sinclair Laboratory, Lehigh University, Bethlehem, Pennsylvania.
142
-------
agencies such as EPA, which is sponsoring this conference, OSHA, and others
who are promulgating regulations to protect the working man, the consumer,
and our environment.
As a natural consequence, organic solvents were given first priority
when the National Association of Printing Ink Manufacturers commissioned the
Printing Ink Institute at Lehigh to start compiling data on the hazardous
properties of raw materials. The purpose of these compilations is to make
the users of the raw materials, whether it is the inkmaker himself or his
customer or supplier, aware of what the hazards are so that they can take
proper preventive measures.
Volume 1 of the Raw Materials Data Handbook, which was published approx-
imately a year and a half ago (ref. 2), covers 123 nonproprietary solvents.
There are hundreds more proprietary solvents, but these will be the subject
of a subsequent compilation.
The compilation of the 123 organic solvents covers physical and chemical
properties, fire-hazard data, health-hazard data, and other data of interest
to the formulator. The Handbook Data Sheet includes a clear, concise summary
of hazards so that, rather than read through the entire sheet, one can get
an immediate idea of the important hazards for any given solvent. A separate
Data Supplement contains information applicable to organic solvents in gen-
eral. The Supplement, in combination with the individual Data Sheets,
provides all information required for filling out a "raw materials data
sheet."
For added convenience, numerical data from the Data Sheet were tabu-
lated into Summary Tables by chemical family. Of the entire volume, the
Summary Tables are probably the most used. They permit one to examine how
certain properties change with molecular weight. Special codes also indicate
the solvents that are photochemically reactive, serious irritants, and cumu-
lative poisons.
Perusal of the contents of the Handbook readily suggests that the typical
organic solvent possesses the following potential hazards:
1. Flammability,
2. Irritation:
a. skin contact
b. eye contact
c. exposure to vapors,
143
-------
3. Depression of the central nervous system, and/or
4. Organic injury from cumulative absorption:
a. exposure to vapors
b. skin absorption.
In the following summary, it will become apparent that the hazards cited
are capabilities. Given adequate controls and preventive measures, no
solvent need be a source of damage to life or property. It will also become
apparent that the two most important controls are adequate ventillation and
prevention of skin contact.
Flammability
As seen in table 1, only 3 of the 123 solvents covered in the Handbook
are totally nonflammable and nonburnable. All others will sustain combustion
under the "right" set of conditions. At least one-third are Class I flam-
mables, that is, they have flash points below 100° F (37.7° C). This cate-
gory includes all four nitroalkanes, most of the hydrocarbons, and, except
for the glycol derivatives, about 50 percent of the oxygenated solvents.
Added dangers are explosion, which frequently accompanies fires in-
volving highly volatile solvents under cr-.finement, and the toxic nature of
fumes given off as combustion products. The latter is especially true in
the case of chlorinated and nitrogen-containing compounds.
Fire should be by all means avoidable in any industrial operation.
First of all, in order for a fire to occur, there must be three essential
elements:
1. a minimum temperature,
2. proper ratio of oxygen to vapor, and
3. a source of ignition.
Remove any one, preferably two, and the prospects of fire will be essentially
nil. For example, adequate ventilation can do much to eliminate number
two—the proper ratio of oxygen to vapor.
One of the reasons that physical properties must be compiled in addition
to fire-hazard properties becomes very apparent when considering fire ex-
tinguishing methods. According to the National Fire Prevention Association
(ref. 3), water is an effective extinguishing media only if the material:
144
-------
Table 1. Flammability of organic solvents
Chemical family
Flammable Combustible Non-
Total (flash point (flash point burnable
# under 100° F) over 100° F) at 1500° F
Hydrocarbons
Aliphatic
Aromatic
Distillates
Oxygenated
Alcohols
Esters (of alcohols)
Ke tones
Ethers and oxides
Glycol derivatives
Glycols
Glycol ethers
Glycol esters
Other
Chlorinated hydrocarbons
Nitroalkanes
NH compounds
Total
3
4
5
17
13
15
7
9
24
6
6
4
10
123
3
4
2
7
7
6
5
-
1
-
1
4C
-
40
-
-
3
10
6
9
1
9
23
6
3b
_
10
120
-
-
-
-
_
la
-
-
-
2
-
-
3
Water.
No flash point but autoignition temperature below 1500° F.
cMay explode when confined liquid is shocked.
1. has a flash point above 100° F,
2. is insoluble in water,
3. has a specific gravity greater than water.
Condition number one—flash point above 100° F~automatically means that
water is not an effective extinguishing agent for all Class I flammables. Few
of the remaining solvents comply with the other two physical properties. Fur-
thermore, if the solvent has a flash point above 212° F, water can cause
145
-------
spattering. Consequently, rather than water, carbon dioxide or dry chemicals
are recommended for small fires and foam for large fires.
Irritation
Dermatitis. Because of the widespread prevalence of skin contact with
solvents, dermatitis is the most frequent cause for complaint in the graphic
arts industry (ref. 4). It should be pointed out, however, that a solvent is
defined as a substance which dissolves another substance. One of the sub-
stances which organic solvents dissolve is fat or oil. So it is obvious that
the very material used to clean ink off a press will also invariably remove
the natural fats and oils in the human skin. The potential of this and other
types of dermatitis is summarized as follows:
1. Fat and oil solvents. Aromatic and chlorinated hydrocarbons are
excellent degreasers and may therefore be expected to cause a
defatting-type of dermatitis after relatively few exposures.
2. Protein solvents. Since body fluids are slightly acid, alkaline
solvents react with proteins in the skin. Most derivatives of
ammonia (ammonium hydroxide, amides, amines) are highly alkaline
and usually cause serious irritation and even skin burns upon
direct contact.
3. Dehydration. Hygroscopic solvents such as the glycols absorb water
and may eventually cause dermatitis due to skin drying.
4. Allergens and sensitizers. About 10 percent of the organic solvents
in the Handbook are reported to be allergens or sensitizers, defined
as chemicals to which certain individuals are abnormally sensitive
on the first or subsequent exposure, respectively. Included in
the allergens are turpentine, dimethylsulfoxide, benzyl alcohol, the
three butyl alcohols and, though mild, the corresponding three butyl
acetates. The sensitizers are epichlorochlorohydrin, ammonium hy-
droxide and tetraethylene pentamine.
In any event, all organic solvents can be expected to cause dermatitis
sooner or later. The best way to avoid potentially troublesome skin problems
is to minimize, or prevent altogether, direct contact with solvents through
the use of protective creams or rubber gloves.
146
-------
Eye Contamination. Contact of any foreign matter with the eyes is always
a matter of major concern because of their great sensitivity and because im-
pairment or loss of vision is so great a tragedy.
If accidentally splashed in the eyes, the typical organic solvent is
certain to be painful and irritating at the very least, and many are capable
of causing severe eye burns or permanent eye injury. The latter is most apt
to be caused by the excellent degreasers and alkaline solvents mentioned in
the previous section. Rather curiously, among the oxygenated solvents, many
butyl and hexyl derivatives are prone to cause serious eye irritation even
though they are not particular skin irritants.
Damage can be minimized by prompt action in washing out the eyes by
emergency medical treatment. The simple preventative measure of wearing
safety goggles is, of course, far preferable.
Irritation from Vapors. Besides skin and eye contact with the liquid,
irritation of some form may be expected from exposure to solvent vapors. In
most cases, mild irritation of the eyes and other mucous membranes may de-
velop. On the other extreme are the solvents, notably the aforementioned
alkaline compounds, where vapors are so irritating that they would not be
voluntarily tolerated. There are also cases where chronic exposure to vapors
has caused skin problems, serious lung irritation, and even internal organic
injury. Examples are:
Methyl ethyl ketone - Skin dermatoses
Propylene oxide - Lung injury
Tetraethylpentamine - Asthma
Turpentine - Kidney injury.
Another class of irritants are the photochemically reactive solvents,
which have already been mentioned several times during this conference. Such
solvents may or may not be irritating by themselves, but they react with
strong sunlight or other sources of ultraviolet light to form compounds that
are definite irritants. As seen in table 2, only 17 of the 123 solvents in
the Handbook are classed as photochemically reactive. These include all
aromatic hydrocarbons except benzene, several ketones, two chlorinated hydro-
carbons, and one alcohol, and are the ones involved in EPA emmision control reg-
ulations. All other solvents in the Handbook are currently "exempt."
147
-------
Table 2. Photochemically reactive solvents
Class of photochemically
reactive compound
Emission
limitations
(vol. percent)
Identity of solvent
Olefinic unsaturation
Aromatic hydrocarbons
C8 and above
except ethyl benzene
Ethyl benzene
Ketones
(branched hydrocarbon
structure)
Trichloroethy1ene
Toluene
5
8
20
20
20
20
Furfuryl alcohol
Ethylene dichloride
Xylene
Naphtha (3)
Turpentine
Ethyl benzene
Methyl iso-butyl ketone
Methyl iso-amyl ketone
Ethyl sec-amyl ketone
Di-iso-butyl ketone
Diacetone alcohol
Mesityl oxide
Isophorone
Trichloroethylene
Toluene
CNS Depression
After skin dermatitis, the second most common complaint about organic
solvents has to do with depression of the body's highly organized central
nervous system (CNS). CNS depression is the usual result of acute over-
exposure to certain chemicals referred to as "narcotics." In industrial
operations, it may occur from inhalation of excessive concentrations of sol-
vent vapors for part or all of the 8-hour working day.
Examination of the list of symptoms in table 3 may help to understand
better what CNS depression is. It should be noted that the symptoms are
essentially the same as those which may develop from indulgence in alcoholic
beverages. In like manner, the effects depend on the quantity absorbed in
a given time period, the tolerance level of the particular individual, and
the narcotic potential of the solvent.
Hydrocarbons, ethers, and oxides are the most powerful; as a matter of
fact, some of these were once used or have been proposed as anesthetics in
148
-------
Table 3. Depression of central nervous system
Symptoms: Headache Incoordination
Dizziness Weakness and fatigue
Giddiness Light anesthesia
Mental confusion Loss of consciousness
Blurred vision Death
Narcotic potential of solvents:
Hydrocarbons Powerful
Oxygenated
Alcohols Weak
Esters Extremely weak (by hydrolysis)
Ketones Moderate (but hazard minimal
due to irritant properties)
Oxides and ethers Powerful
Glycol derivatives Ineffective due to low volatility
Other solvents
Chlorinated hydrocarbons Powerful
Nitroalkanes Moderate
NH compounds Impossible due to potent
irritant properties
Dangers: Fatalities in confined spaces
Influence other bodily functions
Accident proneness
medical operations. Esters are the weakest; CNS depression which results is
caused by hydrolysis to the alcohol. It is also of interest that the irrita-
ting vapors of certain solvents serve as warning signals.
CNS depression is probably the most potentially dangerous form of toxi-
city for the following reasons:
1. It has caused a surprising number of industrial fatalities. Most of
the cases involved workers who entered empty solvent vats or were
trapped in confined spaces without respiratory protection. Under
such circumstances, depression was so profound that respiration
simply ceased.
2. Frequent or severe incidences cannot help but depress or influence
other functions of the body. Many of you are aware that hexane,
methyl ethyl ketone and methyl n-butyl ketone have been implicated
in peripheral paralysis. The probable reason was a CNS-induced
involvement of the autonomic nerve center in the brain, whereby the
heart was ordered not to pump blood to the ends of the fingers and
toes.
149
-------
3. Examination of the list of symptoms indicates that, even in mild
cases, a worker's well being and alertness are reduced; the inevit-
able result is increased accident proneness.
Every effort should be made to minimize incidences of CNS depression
through adequate ventilation or appropriate respiratory devices.
Organic Injury from Cumulative Absorption
In previous sections, it was pointed out that irritant actions and CNS
depression could both cause organic injury; however, this form of toxicity
is more likely to result from the absorption of chemicals at a faster rate
than they are eliminated. In industrial operations, the principal routes of
absorption are vapor inhalation and skin contact. Considering that the lungs
have an internal surface area of 100 square meters compared to 1-1/2 for skin
over the entire body, it is obvious that vapor inhalation is the more signifi-
cant route, especially with solvents having high vapor pressures. In either
case, cumulative poisoning is extremely difficult to diagnose because it
frequently takes years to develop recognizable symptoms.
Table 4 indicates that 44 of the 123 solvents in the Handbook are be-
lieved capable of causing organic injury from cumulative absorption. Case
histories of adverse experiences in humans were uncovered for only 16 (refs.
5 and 6); as far as could be determined, the other 28 caused organic injury
only in animals. To avoid misunderstanding, the Handbook labels the latter
"possible cumulative poisons."
The most potent cumulative poisons in the Handbook are benzene, which
attacks the blood-forming mechanism, and carbon tetrachloride, which injures
the liver and kidneys. Both are highly volatile, and exposed workers should
be given close medical supervision. Blindness has been caused by the vapors
of methyl alcohol, and, as might be expected, by those of methyl acetate
because it hydrolyzes to methyl alcohol. Most of the other solvents in the
table have been implicated in liver or kidney injury.
There is currently no United States Occupational Exposure Standard (ref.
7) for two proven cumulative poisons having low vapor pressures: ethylene
glycol, which caused kidney abnormalities after a year or two of exposure to
heated vapors; and diethylene glycol n^butyl etny"1 acetate, withdrawn from
150
-------
Table 4. Organic injury from cumulative absorption
Chemical Family
Hydrocarbons
Aliphatic
Aromatic
Distillates
Oxygenated
Alcohols
Esters (of alcohols)
-
Ketones
Ethers and oxides
Glycol derivatives
Glycol s
Glycol ethers
Glycol esters
Other
Chlorinated hydrocarbons
Nitroalkanes
NH compounds
/»
Total
3
4
5
17
13
15
7
9
24
5
6
4
100
Capable
#
0
2
3
3
2
3
5
3
9
5
3
4
4
Proven
-
2
1
2
2
0
1
1
2
1
3
0
1
Identity
Benzene
Xylene
Coal tar naphtha
Methyl alcohol
Amyl alcohol
Methyl acetate
Amyl acetate
Dioxane
Ethylene glycol
Ethylene glycol methyl ether
Ethylene glycol ethyl ether
Di ethyl ene glycol butyl
Ether acetate
Carbon tetrachloride
Ethylene di chloride
Perchloroethylene
Dimethyl formamide
Vapor
Pressure
at 20° C
mmHg
74
5
97
2
170
4
29
0.05
6.2
4
<0.01
92
62
14
2.7
USDS
8-hr avg.
ppm
10
100
100
200
100
200
100
100
--
25 (skn)
200 (skn)
--
10
50
100
10 (skn)
TLV
8-hr avg.
ppm
3
25 (skn)3
100 (skn)
200 (skn)
—
200
100
50
100
25 (skn)
100 (skn)
100 (skn)
10 (skn)
50
100 (skn)
10 (skn)
^(skn) = may be absorbed through vapor inhalation and skin contact.
-------
the pesticide market because of harmful skin absorption. It should also be
noted that existing USOS values, which take legal precedence at the Federal
level, do not always agree with recommended TLV values (ref. 8). Many
changes must be expected as a result of increased activity on the part of
OSHA, NIOSH, and other agencies.
Oral Intake
Although oral intake of most solvents will invariably cause illness or
death, this route is not considered a problem in industry as much as it is
around the household, especially where children are concerned. There are,
however, inadvertent opportunities for oral intake about which industrial
workers should be aware. Swallowing may occur to a minor extent when deeply
inhaling contaminated air. More serious amounts can be introduced into the
body when breathing misted vapors, or when consuming food or drink which
has become contaminated by exposure to vapors or by using hands or containers
which contain solvent remnants. Every effort should be made to avoid such
incidences.
Summary
Organic solvents have achieved importance in modern society and tech-
nology because they possess desirable performance qualities and attractive
economic advantages. A summary of data compilations undertaken by the
printing ink industry has demonstrated that the majority of solvents also
possess properties associated with fire and health hazards. It is not the
intent of the compilations to discourage use of any products, but rather to
point out what the dangers are so that users may take effective preventive
measures. The flammable and toxic potential of the typical organic solvent
can be largely eliminated through adequate ventilation and prevention of
skin contact.
REFERENCES
1. B. H. Carpenter and G. K. Hilliard, Jr., "Environmental Aspects of
Chemical Use in Printing Operations—An Overview," EPA Conference, King
of Prussia, September 22, 1975.
152
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2. J. M. Fetsko, Raw Materials Data Handbook. Volume 1 - Organic Solvents,
National Printing Ink Research Institute, Lehigh University, Bethlehem,
Pennsylvania, 1974.
3. "Fire Protection Guide on Hazardous Materials," National Fire Protection
Assn., Boston, 1972.
4. E. A. Campbell, Safety Manual for the Graphic Arts Industry, Education
Council of the Graphic Arts Industry, Inc., Pittsburgh, Pennsylvania,
1972.
5. F. A. Patty, ed., Industrial Hygiene and Toxicology, Volume II - Toxi-
cology, D. W. Fawsett and D. D. Irish, eds., Interscience Publishers,
New York, 2nd revised edition, 1962.
6. E. Browning, Toxicity and Metabolism of Industrial Solvents, Elsevier
Publishing Co., Amsterdam, 1965.
7. United States Department of Labor, "Occupational Safety and Health
Standards, 1910.93 Air Contaminants," Federal Digest, Vol. 37, No. 202
(Oct. 18, 1975), p. 22139.
8. "Threshold Limit Values for Chemical Substances and Physical Agents in
the Workroom Environment," American Conference of Governmental and
Industrial Hygienists, Cincinnati, 1975.
153
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ANGIOSARCOMA OF THE LIVER AMONG PRINTERS
John T. Herbert, M.D.*
Abstract
Over the past several months, the Cancer and Birth Defects Division
of the Center for Disease Control has been compiling a registry of all
cases of angiosarcoma of the liver occurring in the United States from
1964-1974. Cases have come from death certificates via the National
Center for Health Statistics, from the Armed Forces Institute of Pathol-
ogy j and from direct correspondence with pathologists across the country.
From the death certificates alone, five cases of angiosarcoma of the liver
were identified as workers in the printing industry. Another three cases
were found in printers as additional cases were reported. In light of the
known association of vinyl chloride and angiosarcoma, and the fact that
many printing inks use a vinyl chloride resin, special attention was im-
mediately focused on this group.
Pathology of these eight cases was reviewed by Dr. Louis B. Thomas,
Director of Pathology, National Institutes of Health, and Dr. Hans Popper
of Mount Sinai School of Medicine, but only one of the original five
cases was confirmed as angiosarcoma of the liver. Pathological review of
the other three cases, along with epidemiologic findings of all eight
individuals, is in progress.
Angiosarcoma is a very rare malignant tumor of the liver that we
have been studying at the Center for Disease Control. How did we get in-
volved with printers? I should say from the outset that this is a very pre-
liminary report and that I received my last information by telephone about
20 minutes before the session began.
The Center for Disease Control (CDC) is establishing a registry of all
cases of angiosarcoma of the liver occurring in the United States from 1964
to 1974. CDC became involved shortly after this tumor was recognized in
plastics workers and linked to vinyl chloride exposure. We began setting up
this registry to see if there were other industries and other chemicals that
*Cancer and Birth Defects Division, Bureau of Epidemiology, Center for
Disease Control, Atlanta, Georgia.
154
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could contribute to the development of angiosarcoma of the liver. The center
was Involved in examining the records of the original plastic workers in
B. F. Goodrich plants and several papers were published on this subject.
Without question, vinyl chloride monomer has been recognized as causing
angiosarcoma of the liver and other angiosarcomas in animals.
When the registry was set up, we arranged to get death certificate in-
formation on all cases of "miscellaneous liver tumors" from tumor regis-
tries and from the National Center for Health Statistics. We also sent out
mailings to pathologists all over the country asking if they had seen
cases of angiosarcoma of the liver.
Our purpose and goal was to identify all cases of angiosarcoma of the
liver, regardless of the cause, and then to do some epidemiologic footwork
and look for occupational histories with vinyl chloride exposure or exposure
to other chemicals. I might point out that angiosarcoma has also been
shown to be caused by exposure to arsenic and to thoratrast, which is a
contrast media used in the 1940's for radiographic studies in hospitals.
We looked to see if there were other chemicals causing this tumor,
and we also looked to see if there were other industries previously not
known that were using any of these chemicals. When we began looking through
the thousands of death certificates and receiving trickles of letters from
pathologists, we noted a cluster of six cases of angiosarcoma, which were
reported in printers. This was immediately quite striking.
Table 1 shows the incidences of angiosarcoma of the liver as estimated
from the third National Cancer Survey; 0.014 cases per 100,000 should occur
in the overall population. We estimated approximately 1 million printers,
which may not be a precise figure. According to the International Printing
Pressmen's Union (personal communication) two printers unions claim to repre-
sent approximately 30 percent of the printers in the country. By doing a
little bit of arithmetic, I came up with 690,000 and I rounded it off to 1
million to try and bias the study against our findings.
Applying this rate to the 1 million printers, we would expect 1.4
cases over a 10-year period. We observed six cases in the period 1964 to
1974, and the first thing that came to our minds was that we had an epi-
demic of angiosarcoma in printers.
About this time we began our epidemiologic investigation. We made
155
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Table 1. Observed and
expected number of cases among printers
Incidence - 0.014 cases/1000,000*
x 106 Printers**
Expected -1.4 cases in 10 years
Observed - 6 cases, 1964-1974
*Third National Cancer Survey.
**International Printing Pressmen's Union.
every attempt to trace the families of these individuals, usually through
private physicians who signed the death certificate. We did get pathology
slides and cell blocks for futher review and for confirmation on all
cases. We sought a representative occupational and residential history,
looking mainly for possible exposure to vinyl chloride monomer, since we
know this caused angiosarcoma of the liver. Of course, we looked for other
chemicals as well.
We were puzzled by the five initial cases of angiosarcoma in printers,
and we had no reason to suspect that printers were using vinyl chloride,
even though we know they were using a host of chemicals. It was then
brought to our attention from our colleagues at NIOSH that polyvinyl
chloride, which has not yet been implicated as being carcinogenic, is
used in the manufacture of certain printing inks. We also know that in many
of the plastic end products of polyvinyl chloride, vinyl chloride monomer
lies trapped within the polymers.
We then received notification of three additional cases, which
brought our total to nine printers who had a diagnosis of angiosarcoma of
the liver on their death certificates. We certainly were interested in
this, and we arranged to get the slides. We looked for the occupational
history on these people. I have summarized in table 2 our nine cases. The
first five cases are the original five and the next three are the subsequent
ones that came in.
All of these gentlemen had on their death certificates angiosarcoma
of the liver or some of the synonyms that we use: malignant endothelioma,
etc. They also had on the death certificates "Printer," or in one case,
156
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Table 2. Angiosarcoma of
the liver reported among printers, 1964-1974
Printer
1
2
3
4
5
6
7
8
9
Age
at
death
50
70
84
71
40
20
59
61
59
Years of
exposure
25
?
50
35
24
3
3 (25)
16 (10)
42
Job
description
Offset pressman
Offset pressman
Self-employed
printer
6. P.O. printer
Linotype
operator
Assistant;
cleaner
Printer
(jahitorj
Printing sales-
man (solvent
mixer)
Pressman
Chemicals
Inks, cleaning
fluids
Inks, cleaning
fluids
Inks, cleaning
fluids
Inks, cleaning
fluids
Molten lead, inks,
cleaning fluids
Inks, cleaning
fluids
Inks, cleaning
fluids
ecu
f
Inks, benzene
cleaning fluids
Diagnosis
local
ASL
ASK
ASL
ASL
ASL
ASL
ASL
ASL
Malignant
fibroxan-
thoma
"linotype operator," but all were people working in the printing industry.
When we conducted our epidemiclogic investigation, we noted right
away that some of these people were not really printers. If you look at
case numbers six, seven, and eight, case number six was only exposed to
these chemicals for 3 years and turned out to be a part-time printer and
cleaning assistant in a print shop. Case number seven had been a janitor
for the previous 40 years, and was promoted to a blueprint printer the last
3 years before he became ill. He had been exposed extensively to cleaning
fluids, but again had only been a printer for 3 years.
Case number eight turned out not to be a printer at all, but a sales-
man for a print company, having minimal exposure to the printing industry
itself, and case number nine was indeed a printer for 42 years, but the
157
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hospital diagnosis was fibroxanthoma of the liver. This case was referred
to us because the original pathologists were unsure about the diagnosis.
By telephone, there was a possibility that this may have been an angiosar-
coma of the liver, but on pathologic review it was not. We were left with
the first five cases. When the pathology on these cases came to our attention,
we immediately sent them to Dr. Louis B. Thomas and Dr. Hans Popper at the
NIH to review all of our slides. They have had the opportunity to review
almost every case of angiosarcoma of the liver that has been reported, and
Dr. Popper, of course, is a liver pathologist well known all over the world.
On review by Drs. Thomas and Popper, only case number five was an angiosar-
coma.
By this time, EPA contacted us and wanted a statement on the rash of
angiosarcoma cases that we had been studying in printers. The study was
preliminary at that time and we felt that we had to have pathologic confirma-
tion before we could report any more cases of angiosarcoma.
In summary, on reviewing our nine printers, only one of them turned out
to have angiosarcoma of the liver. This is not to be critical of the local
hospitals; it should be pointed out that this is a very difficult diagnosis
to make. The diagnosis is usually best made following death, when the entire
liver is available. We only expect one out of 10 million deaths to have this
diagnosis, and most pathologists just do not see this tumor.
I do not have the final report on the other cases, but we can tell you
that case number five was the only printer with angiosarcoma of the liver.
I intentionally rushed over cases six and seven. They are believed to be
angiosarcoma of the liver, but with that short, recent exposure, we cannot
implicate chemicals in the printing industry. We expect to have a final re-
port on all of these cases with the conclusion of the angiosarcoma registry.
DISCUSSION
CHAIRMAN SCHAEFFER: A question has been asked, which one was the one?
DR. HERBERT: The one out of five is case number five. He was a lino-
type operator for approximately 24 years. He was exposed to molten
lead and the other chemicals that go into linotype operations. But
158
-------
he also worked in a printing company that was a large warehouse-type
of job shop. All of the printing and everything else was done in the
same room.
JEFFREY D. BOEHLERT (Sun Chemical Corporation, Carlstadt, New Jersey): Is
there not arsenic in molten lead?
DR. HERBERT: Well, we asked about that because of the purity of the lead.
I think there is. The fact is that we have no proof to even guess what
his exposure to arsenic was. I am certain all linotype operators
have had a similar exposure.
I would just say that we just cannot make that statement at
this point. But there is some evidence that all of these chemically
induced angiosarcomas of the liver, certainly all of the vinyl
chloride workers, and probably the arsenic workers have a certain
pattern to their histology. When you review these tumors under the
microscope, the tumor arises from, I believe, the endothelio cell
walls. And as Dr. Thomas and Popper have pointed out, this is not
characteristic of the "spontaneous angiosarcoma," as previously
reported.
CHAIRMAN BURACHINSKY: I just wonder whether you have ever consulted with
the particular printing ink firm involved, which would probably pin-
point for you rather quickly whether any vinyl chloride was used.
It is fact that only about 1 percent or less of printers use vinyl
chloride at all. Very few inks are being made with vinyl chloride.
So you probably won't...
DR. HERBERT: The answer to your question is yes. We contacted five dif-
ferent companies and I think manufacturers in the Atlanta area, two
in the Massachusetts area. No one really knew of vinyl chloride
being used in the prints any more. I only cited the reference from
the book because it was pointed out that it is there, and there was
a possibility of exposures.
DR. HERMAN F. KRAYBILL (National Cancer Institute, Bethesda, Maryland):
As you said earlier, there is a possibility for the PVC monomer leak-
ing out and there is concern about PVC monomer where you have PVC
stored. I was going to ask if it were true that there was PVC
159
-------
present—whether there was any monitoring that took place? Second,
have you looked at any structural analogs of viny chloride?
DR. HERBERT: We have not directly, but other investigators have looked at
them. I think possibly people from NIOSH might be a little bit
better qualified to answer that question than I am. But certainly in
the rubber industry, with some of the synthetic rubbers, there are
structural analogs. And vinyl chloride has been reported in rubber
work. Excuse me. Angiosarcoma has been reported in rubber workers.
MR. RAY NEFF (Department of Health and Safety, Indiana State University,
Terre Haute, Indiana): This does not have anything to do with the
printing industry. What was the average exposure for the cases that
have to do with PVC? Was it pretty long exposure or short exposure?
Could you expect, say, a 3-year exposure to trip-off or cause
angiosarcoma?
DR. HERBERT: In the cases reported on the original vinyl chloride workers,
and I believe most of the subsequent workers, there was certainly a
longer exposure than this. People like to say that it takes 15 to 20
years. Of course, the duration of exposure and the dose and latency
are things that have to be reckoned with. I believe the tumor has
been reported in people who worked less than 15 years. But the tumor
did not arise until 20 years after their exposure. So I cannot answer
that question directly, except that 3 years of exposure with no prior
exposure certainly would be unusual. This is not what has been seen
in the plastics worker.
DR. KINGSLEY KAY (Mt. Sinai School of Medicine, New York): May I ask
what was found out about the cleaning fluid used by the linotype
operator?
DR. HERBERT: We asked the company where he worked and everybody kept
telling us benzene, although we were informed that benzene is no
longer used. So we presumed that it may have been one of the many
solvents being used in the industry now—I cannot tell you exactly
what it was, but we were assured that it certainly was not benzene.
DR. KAY: May I say that in the survey I did, the current solvents used
to clean typeface and in proofpull ing were methyl chloroform and
160
-------
methylene chloride, and they are of great interest because methyl -
chloroform is a cardiac sensitizer, and methylene chloride converts
to carbon monoxide in the body. These are things we now know.
They were, of course, widely used because they were pushed as sub-
stitutes for carbon tetrachloride and triehi orethy!ene. And all the
men on your list in the '20-year category, have been using carbon
tetrachloride. The older ones have been using benzene, and the newer
ones have been using trichlorethylene, methylene chloride, and
methyl chloride almost without any question of doubt, because there is
nothing else that works.
DR. HERBERT: I might point out that one case of angiosarcoma that has
carbon tetrachloride exposure indicated was not a printer, but he
manufactured this stuff in his basement. And for over 15 years, he
made solvents out of a carbon tetrachloride base.
THE FLOOR: I am just wondering where Dr. Kay got his information, because
there may have been one or two people who may be using methyl chloro-
form, but very few people will be using carbon tetrachloride, methylene
chloride, and methyl chloroform as a basic wash. It may be used to
lift the flash point, but essentially they are what we called benzenes.
They are the petroleum aliphatic solvents that are used for cleaning
linotype.
DR. KAY: Well, I did not see anybody using carbon tetrachloride. What I
said was, I was told that carbon tetrachloride had been used many
years ago, and had been replaced with these two solvents.
CHAIRMAN SCHAEFFER: Are there any other questions?
MR. CHARLES WARNER (National Cancer Institute, Bethesda, Maryland): I
wonder if we are not going to change the health picture considerably
by forcing printers to go to nonphotochemically active solvents. I
wonder if we should not proceed more carefully in light of the fact
we may cause a considerable industrial hygiene problem.
CHAIRMAN SCHAEFFER; Dr. Herbert, any comment?
DR. HERBERT: My only answer to that would be to clean them by machine.
I do not know enough about the printing industry to even attempt to
answer that question.
161
-------
CHAIRMAN SCHAEFFER: I think the point that is made is a very interesting
one, because one has to look at what the possibilities are in any
new system that is developed for the industry. And we are talking
new systems very frequently, including the cleaning operations.
162
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LITHOGRAPHY: LABORATORY EVALUATION OF ENVIRONMENTAL RISK
Robert L. Bohon, Ph.D.*
Abe tract
This paper addresses the problem of estimating the potential environ-
mental hazard of lithography from data on the entry level and biological
impact of waste materials from the plate and press rooms. Examples of
ecosystem reservoirs and pathways are related to existing disposal methods
for spent developers, printing inks, driers, fountain solutions, blanket
washes, paper, and discarded press blankets and plates. A laboratory clas-
sification scheme similar to that proposed by the National Academy of
Sciences is used to assess possible environmental hazards from laboratory-
scale tests as well as information contained in the literature on the
Volume and dispersal of these waste materials. From these considerations
it is concluded that under normal use conditions lithography poses a very
minor environmental hazard.
INTRODUCTION
The prediction of potential environmental hazard for any given product
or chemical compound eventually becomes an attempt to extrapolate the re-
sults of short-term tests or observations to very long-range effects in an
ever-changing, complex real-world system. How can we efficiently utilize
environmental toxicological data, in conjunction with expected use and dis-
posal information, to estimate the potential environmental impact of a
given product or process?
Today I will present a brief outline of an assessment of the potential
environmental hazard associated with the practice of lithographic printing,
especially as it relates to the waste materials from the plate and press
rooms. The methods routinely used at 3M Company for such an assessment on
new or modified products closely parallels the suggested protocols of the
National Academy of Sciences, and I shall frequently refer to their recent
*Manager, Environmental Laboratory, Environmental Engineering and Pol-
lution Control Division, 3M Company, St. Paul, Minnesota.
163
-------
report (ref. 1).
We shall first discuss ecosystem models and our present state of knowl-
edge as to how chemicals move within them. Consideration will be given to
those properties of a compound which control its availability to living
systems, as well as to laboratory methods of measuring and predicting bio-
logical toxicity and impact. Finally, the lithographic printing process
will be briefly outlined, the wastes from the plate and press rooms identi-
fied, and an assessment made of the environmental impact of each, using the
concepts of entry level and biological impact.
ECOSYSTEMS AND CHEMICAL MOVEMENT
Figure 1 illustrates the dynamic system of reservoirs and pathways for
chemicals in the global environment (ref. 1). Atmospheric residence times
vary from weeks for small particles to years for gases. It takes 2 to 4
weeks for particles to circumnavigate the earth in midlatitudes, 3 to 6
weeks near the equator. As one might expect, residence times in the ocean
vary from a century (iron, aluminum, or titanium particles) to hundreds of
millions of years (sodium) and depend upon the chemical nature of the sub-
stance. Refractory organic materials have oceanic half-lives of thousands
Stratotphera
Troposphere
LJ
Terrestrial Biosphere
Oceanic Mixed Layer
Marine Bioepherv
Oceanic Deep Layer
Sediments
Figure 1. Reservoirs and pathways of chemicals
in the environment (ref. 1, p. 62).
164
-------
of years, and mixing times range between several hundred years in the Atlan-
tic to a thousand years in the Pacific for materials introduced into the
deep layers. Most dissolved substances pass through the mixed layer in a
matter of years, or a decade at the most.
When an effort is made to model a dynamic system in an aquatic environ-
ment, a very complex, interrelated set of variables must be considered. A
pictorial illustration of such a model by Chen and Orlob (ref. 1) is shown
in figure 2. For each cell there are 23 differential equations, one for
each environmental variable: temperature, total dissolved solids, biochemi-
cal oxygen demand, pH, elemental concentrations (C, N, P, etc.), plus a
variety of biological variables (biomasses of algae, zooplankton, cold-water
and warm-water fish, benthos feeders), and mass balance effects due to proc-
esses such as advection, diffusion, settling, inflow, outflow, decay, chemi-
cal transformation, biological uptake, respiration, growth, mortality, and
grazing.
It is apparent that mathematical modeling of the flow and concentration
MAN-INDUCED
WASTE LOADS
DEAD ORGANISMS
EXCRETE
Figure 2. Definition of an ecosystem
(Chen and Orlob, 1972)(ref. 1, p. 350).
165
-------
distribution of substances in the environment is a difficult and complex
business. Nevertheless, the danger or hazard associated with either natu-
rally occurring or synthetic chemicals depends upon not only their biologi-
cal impact, but also upon their distribution in the environment. A hundred
pounds of salt dumped on my lakeside back yard would have disastrous ecolog-
ical effects, whereas the city maintenance department routinely spreads tons
of salt on our St. Paul city streets with currently acceptable side effects,
thanks to containment and high dilution by natural precipitation.
In considering the movement of compounds through the environnent and
their availability to living organisms, the following indicators of move-
ment are important (ref. 2):
• vapor pressure,
• water solubility,
• octanol-water partition coefficient, and
• soil adsorption/leaching behavior.
As a first approximation, vapor pressure will be related to entry into
the atmosphere, water solubility will control entry into an aquatic ecosys-
tem, and the octanol-water partition coefficient will be a good indicator
of the potential for biconcentration.
Such properties as reactivity with oxygen and water, photodegradation
and tendency toward smog formation, microbial degradation and transforma-
tion, and metabolism by plants and animals are indicators of persistence in
the environment. Note particularly that one must be concerned not only
about the parent compound, but also the amount, location, and biological
impact of materials generated from the parent compound by the environment
itself.
J. M. Wood and coworkers have published widely on the biological mech-
anisms by which toxic elements are cycled in the environment (ref. 3). The
mercury cycle is shown in figure 3 and illustrates the way in which sedimen-
tary microorganisms and enzymes convert inorganic mercury compounds at a pH
of about 4.5 into the deadly poisonous neurotoxin, methyl mercury, which in
turn is readily soluble in lipids and can bioconcentrate in fish. The same
process also produces dimethyl mercury (but at a rate 6,000 times slower),
which is volatile and photolyzed by UV light to metallic mercury plus
methane and ethane.
166
-------
Figure 3. The mercury cycle (ref. 3)
167
-------
Table 1. Classification of elements according to toxicity
(Wood, ref. 3)
Very toxic
and relatively
Noncritical
Na
K
Mg
Ca
H
0
N
C
P
Fe
S
Cl
Br
F
Li
Rb
Sr
Al
Si
accessibl
Be
Co
Ni
Cu
Zn
Sn
As
Se
Te
Pd
Ag
Cd
Pt
e
Au
Hg
Tl
Pb
Sb
Bi
Toxic but
very insoluble
or very rare
Ti
Hf
Zr
W
Nb
Ta
Re
Ga
La
Os
Rh
Ir
Ru
Ba
From such biological cycle considerations, Wood has suggested three
classifications for toxic elements: (1) noncritical; (2) toxic and rela-
tively accessible; (3) toxic, but very insoluble or very rare (see table 1).
It is evident that small disturbances in these dynamic cycles will
affect the natural equilibria for any given element, which in turn will
affect the concentrations of toxic intermediates. We are then faced with
the problem of deciding which species of a toxic element should be monitored
in the environment since chemical, physical, and biological transformations
can have such a profound effect upon the movement and impact of any given
element across boundaries in the biosphere.
Similar arguments apply to organic compounds, and again the persis-
tence, concentration distribution, and transformation processes are impor-
tant in assessing the environmental impact due to introduction of a given
volume of some chemical compound into a biogeocycle at a given time and
place. You are all familiar with the classic case of such synthetic refrac-
tory organics as polychlorinated biphenyls, for which mother nature has not
yet developed mechanisms for detoxification at rates sufficiently high to
prevent an adverse environmental impact through bioaccumulation.
ASSESSMENT OF ENVIRONMENTAL HAZARD
As mentioned previously, the environmental hazard of a given material
depends not only upon its inherent biological impact (e.g., toxicity), but
168
-------
Table 2. Scheme for classification of chemicals
according to biological impact and dispersal
(national or regional problems)
(ref. 1, p. 227)
Entry level
Dispersal
(1) Widespread
(2) Widespread
(3) Localized
(4) Localized
Volume
High release
Low release
High release
Low release
Biological impact
High (1)
1
2
3
4
Medium (2)
2
4
6
8
Low (3)
3
6
9
12
NOTE.-Low number indicates high priority.
also upon its volume and distribution in the environment at any given time.
Table 2 presents a scheme for classification of chemicals according to these
three parameters on a national or regional basis (ref. 1). I have taken
the liberty of combining "dispersal" and "volume" under the general heading
of "entry level," which indicates the combined effects of these two environ-
mentally significant variables. A material with high biological impact and
high entry level would have a top priority rating for environmental concern,
whereas a low-entry-level, low-biological-impact material would receive a
low priority rating.
Table 3 illustrates the factors contributing to biological impact and
includes such items as toxicity, the importance of the receptor organisms,
the scope of the ecological effect (with large-scale and chronic effects
more serious from a testing standpoint than acute effects), the availability
to organisms, the potential for biomagnification, and the stability or per-
sistence of the compound.
In conjunction with the physical and chemical properties of a compound,
application of tables 2 and 3 permit a preliminary assessment of environ-
mental hazard and an objective decision on whether additional laboratory
tests are necessary for reasonable predictions. Figure 4 is a suggested
flow diagram for regulatory decisionmaking (ref. 1). Steps 3, 4, and 5 in-
volve increasingly complicated and expensive laboratory and field testing,
such as now required in varying degrees for pesticides and drugs. This
scheme implies that we can make a reasonable estimate of environmental hazard
169
-------
Table 3. Factors contributing to biological impact
(ref. 1, p. 227)
Level of importance
ractor
Foxicity
Receptor importance
Type of effect
Availability to organism
Potential for biomagnification
Stability and persistence
(1)
High
High
Interference
with eco-
system
functioning
High
High
High
(2)
Medium
Medium
Chronic
effects at
level of the
individual
Low
Low
Low
(3)
Low
Low
Acute effects
at the level
of
the individual
NOTE.-Low number indicates high significance.
1. Characterization
of Pollutant
Regulations
Required
Significant Biological Hazard
r
'
2. Preliminary
Assessment of Hazard
I
3. Short-Term Tests
on Individuals
i
4. Tests for Chronic
Effects on Individuals
5. Tests for
Interspecies Effects
No Restrictions
Required
i
No Significant Biological Hazard
Figure 4. Flow diagram for laboratory investigations
of hazard (ref. 1, p. 225).
170
-------
from a consideration of entry-level information and laboratory or field
tests on biological Impact:
Hazard = rf (entry level, lab tests, field tests).
Furthermore, the degree of testing sophistication required and the
extent thereof will be a function of both the anticipated biological haz-
ard and the social gain expected from use of the substance:
Testing extent = rf (biological hazards, social gain).
The more subtle biological effects, especially those observable only
over spans of many years, present particularly difficult cases where fun-
damental data all too frequently are missing.
Step 3 of the suggested laboratory investigation scheme involves
short-term tests on Individuals and ranges from tests of a few hours to
a couple of weeks. Table 4 summarizes some of the tests which should be
Included in this phase of evaluation.
If the results of short-term tests indicate the need for chronic
tests, long-term indicators such as weight gain, food consumption, lon-
gevity, behavioral response, reproductive effects, and changes in plant
populations must be considered (step 4). For example, accumulative chemi
cals can sometimes be sequestered harmlessly in storage sites and later
Table 4. Short-term tests on individuals
(ref. 1, p. 227)
*Toxicity and tendency for accumulation in organisms.
Plants: seed germination, photosynthesis, transpiration.
Animals: rates of ventilation, heartbeat, oxygen consumption.
*Rates of degradation and transformation.
Short-term bioassay with fish.
*Analysis of body burdens before and after exposure.
No additional testing required if:
rapid degradation,
decomposition products of low toxicity,
minimal bioconcentration,
low entry level rating.
Additional testing required if:
toxic chemical or decomposition products that are persistent,
tendency to accumulate within an organism, or are of high toxicity.
171
-------
released at toxic levels upon utilization of the store (DDT in fat or lead
in bone). Long-term tests, of course, become expensive and time-consuming,
and can only be justified when reasonable hazard is suspected.
Experience has shown that persistent toxic chemicals which can accumu-
late and be magnified in the food chain must be tested for much more subtle
ecological effects (step 5), such as plant-plant interactions, productivity,
plant-animal relationships, transport through food chains, and alteration by
chemical or microbial activity.
R. L. Metcalf (ref. 4) has developed laboratory-scale microcosms con-
taining several species at different trophic levels as a model for studying
biodegradability and ecological magnification of radio-tagged chemicals (see
figure 5). Radiotracer studies are limited, of course, to tracing only the
tagged portion of a molecule, and following the decomposition products from
complex parent molecules can sometimes prove confusing.
Finally, from a very practical standpoint, we are interested in the
acceptability of a material into our existing waste disposal systems with-
out upset or undue strain. For wastewater streams, treatability can be
determined by biochemical oxygen demand (BOD) tests, which are an index of
loading on secondary waste treatment systems or surface waters, and by BOD/
COD* ratios, which indicate the degree of biodegradability. Nondegradable
or difficulty degradable materials will pass unmodified through treatment
Figure 5. Model ecosystem for studying pesticide
biodegradability and ecological magnification (ref. 4)
*Chemical oxygen demand,
172
-------
systems and into surface waters, or be landfilled or incinerated with the
sludge.
LITHOGRAPHY
The lithographic printing process is based upon the ability to form
oleophillc-hydrophilic images on a plate surface, which in turn permits dif-
ferential adsorption of oil-base ink and subsequent transfer of the image
to paper, plastic, cardboard, metal, etc. (see figure 6). Lithography
accounts for almost 55 percent of all commercial printing in this country,
has an annual growth rate of about 10 percent, and has doubled in dollar
volume in less than 10 years. About half of all lithographic printing is
general commercial work and advertising printing (about $1 billion each);
the balance consists of labels and wrappers, catalogs and directories, fi-
nancial and legal printing, and approximately $1/2 billion that is unidenti-
fiable by product (ref. 5).
Within the commercial printing business, over 80 percent of the plants
are small, employing less than 20 people and accounting for about 25 percent
of the total dollar output. Plants employing over 250 persons account for
an additional 25 percent of the business, and the remaining 50 percent of
commercial printing is handled by plants with 20 to 250 employees (ref. 5).
In total, there are approximately 8,400 commercial lithographic printing
plants* and tens of thousands of "captive," or in-house, plants (ref. 6).
As might be expected, the growth in sales of offset inks (9 percent)
has closely paralleled the growth of the offset printing industry. Offset
THE LITHOGRAPHIC PROCESS
IMPMSftlON CTLINDf M
Figure 6. The lithographic process.
*Excludes job printers and 10"-plate industrial graphic printers,
173
-------
ink accounted for 31 percent of the total ink sales in 1973 (ref. 7). A
comparison of the 1967 and 1972 Census of Manufactures shows that the volume
of lithographic and offset inks grew from 80.1 to 159.3 million pounds in 5
years (ref. 8).
We shall restrict our environmental hazard discussion to the wastes
generated in the plate processing and press rooms and ignore waste produced
during the manufacture of lithographic supplies or the use and ultimate dis-
posal of the final printed product.
After UV light exposure of a plate to a film negative, developing
solutions are applied to remove nonlightstruck areas, producing a surface
with both hydrophobic and hydrophilic areas. Developers for negative work-
ing plates are typically acidified aqueous solutions or emulsions of iso-
propanol, gum arabic, and synthetic lacquer resins (ref. 9). Negative-
working presensitized plates may be coated with light-sensitive prepolymers,
light-sensitive diazo resins made from such materials as 4-diazo-l, 1-
diphenylamine
Cl N =
and paraformaldehyde, resin binders, small amounts of organic acids, organic
or inorganic pigments, and indicator or sensitizing dyes.
Positive-working plates contain many of the same or similar materials,
but the diazo materials are usually light-sensitive compounds such as 1-
diazo-2-naphthol
N = N
i i
-o
which, upon exposure to light, give off nitrogen gas forming indene carboxylic
acid. This compound is soluble 1n water solutions containing an alkaline
material and permits removal of exposed areas with appropriate developers.
Development of lithographic plates, therefore, may produce the following
waste materials in the plate room (see figure 7):
1. Developers
a. Acidified aqueous solutions (negative plates): isopropanol,
gum arabic, and synthetic lacquers.
b. Caustics (positive plates)
174
-------
GASEOUS EFFLUENTS
(DEVELOPER ALCOHOLS)
en
i
PLATE
ROOM
DEVELOPERS
PLATE COATINGS
DIRECT DISCHARGE
t
TO WASTEWATER
TREATMENT
PRESS READY
PLATES
SLUDGE TO LANDFILL
OIAZO, RESINS, PIGMENTS
-------
2. Plate coatings
a. Dyes
b. Photopolymers
c. Binders and resins
d. Pigments
e. Organic acids.
Volatile solvents such as alcohols will evaporate to a limited extent
during plate development, but virtually all other wastes have the potential
of entering the plant wastewater system and traveling through a municipal
treatment system, individual septic system, or being discharged directly to
surface waters. Water-insoluble polymers will, in general, be only slowly
degraded and hence persist; the remaining waste materials, with the possible
exception of certain pigments, will be biodegradable and relatively quickly
returned to their respective natural cycles.
In the press room (ref. 10) we are confronted with a more complex sys-
tem (see figure 8). During the printing process itself, alcohols and hydro-
carbons will evaporate from the dampening system and ink fountains at the
press, and in the case of offset printing with heat-set ink, also in the
drying oven. Some plants utilize pollution control systems on the drying
ovens to reduce the entry of hydrocarbon volatiles into the atmosphere, in
which case ultimate disposal is either by afterburning reuse as forklift
fuel, or in some cases recycling as an ink solvent.
The washup and cleaning solvents and ink fountains will introduce
hydrocarbons into the overall volatile emissions from the plant. Some of
these compounds fall into the class of photochemically reactive and hence
contribute to the potential production of smog. Such emissions are already
controlled by Rule 66 type regulations, which in turn vary from location to
location throughout the country. There are lesser amounts of other oxygen-
ated or chlorinated solvents released to the atmosphere, most of which are
classed as nonphotochemically reactive.
Other wastes from the press room that must be considered find their way
into landfills or incinerators via trash-handling systems (see figure 9):
• Waste paper, both with and without ink and other solids from ink and
dampening systems;
• Discarded press blankets (rubber and fabric);
• Rags from cleanup operations, containing solvents and dissolved solids.
176
-------
Oxidative drying
ink, 5 Ib/hr
5% aliphatic solvent
Wash-up
solvents
t
Ink
Fountains
25 x 38" sheets.
coated, 4000 iph
Water and
isopropanol
vapor
Wash-up
solvents
Hydrocarbon
Vapor
two colors
one side.
80% coverage
Press
Cylinders
Heat Set
Oven
Product
plus all
"of initial
solvent
Dampening
Systems
LJ
Water and
isopropanol
vapor
Water
Isopropanol,
0.3 Ib per Ib of ink
Figure 8. Sheet-fed offset—press room (ref. 10).
-------
c»
GASEOUS
EFFLUENTS
PET. SOLVENTS
ALCOHOLS
NAPHTHA
STODDARD SOLVENT
PRESS
ROOM
SOLID WASTE
WASTE PAPER
MACHINERY
BLANKETS
PAPER
INKS
WASTEWATER
SPENT FOUNTAIN SOLUTIONS
co2,
DIRECT
DISCHARGE
TO WASTEWATER
TREATMENT
SLUDGE
Cr, Zn
SURFACE WATER (STREAMS)
PRODUCT
LANDFILL
LEACHING
- GROUNDWATER
(TREATED) EFFLUENT
LAKE OR
OCEAN
Cr, Zn
Figure 9. Flow diagram of press-room wastes.
-------
Used plates are generally recycled to an aluminum fabricator.
The inks constitute a complex array of chemical compounds, including a
wide variety of inorganic and organic pigments, oil resins, vehicles, and
driers. The fountain solutions contain dissolved solids which mostly are
carried over onto the final printed product (some of which is waste). Per-
haps 20 percent of the solutions are dumped down the drain at the end of a
week's run. This liquid waste includes organic acids, ammonium dichromate,
zinc nitrate, and gums.
LITHOGRAPHIC WASTE ENTRY LEVELS
With this background on ecosystem modeling, on an enumeration of the
lithographic processing waste materials, and on some laboratory indicators
for biological impact, we now need to summarize the volumes and dispersal
characteristics in order to assess entry levels. This information, plus
biological impact estimates, will permit an estimate of potential environ-
mental hazard for each waste material, as well as emphasizing where addi-
tional data are needed for an intelligent assessment.
The following tables summarize U.S. information on each type of litho-
graphic waste material, arranged according to:
route of disposal
4-
entry level
4-
biological impact
4-
ultimate sink
4-
estimated environmental hazard.
The tables are further grouped according to the general class of waste
material: inks, plate coatings, fountain solutions, and other.
The disposal route for any given material will be an important factor
in predicting its entry level into the environment. The entry level, com-
bined with information on biological impact, permits some evaluation of the
ultimate environmental sink for the material and, finally, an assessment of
environmental hazard.
179
-------
It 1s obvious, of course, that there are missing data, and we can only
make an educated guess for many of the formulations included under the broad
range of chemicals used somewhere in the lithographic printing process.
Although we have very little specific information on the biological im-
pact of some of the proprietary pigments, indicator dyes, and light-sensitive
polymers used in plate coatings, it is apparent that the volumes discharged
from the plate room processing steps are extremely small and constitute very
little problem as shown in table 6.
A glance at table 7 on inks illustrates that the pigments and driers
include heavy metal components that we know to be potentially detrimental to
the environment.* It is also clear that the total levels of ink used for
lithography run into millions of pounds and are therefore of obvious concern
to our overall environment. We estimate, however, that less than 10 percent
of the Ink components are discharged as waste from the press room, the re-
mainder leaving the plant in the form of finished product. In all cases,
the inks eventually enter the biosphere through either incineration or land-
filling of printed matter on an exceptionally widespread distribution level.
For proper assessment on a global basis, additional information on biologi-
cal impact of ink components will be necessary.
The solids contained in fountain solutions are largely deposited on the
finished product, and probably less than 20 percent is dumped down the
drain. Table 5 shows that the quantities are very small indeed, and the
major environmental concern is with atmospheric discharge of vapors, as dis-
cussed previously.
Table 8 includes data on various other components used in lithography,
as well as a recapitulation of total organic liquid use (solvents and ink com-
ponents), which we have discussed before.
Table 9 summarizes the potential environmental hazard of these materi-
als and emphasizes the necessity of good waste management for materials with
significant biological impact, especially heavy metal compounds.
*Carbon has been omitted from consideration as an environmentally signi-
ficant constituent, although carbon blacks are known carcinogens due to ben-
zene-soluble aromatic hydrocarbon components (Kingsley Kay, "Toxicological
Evaluation of Chemicals Used in the Printing Inks Industries," this
conference).
180
-------
Tabla 5. Fountain solutions
(1,500,000 gal/yr - U.S. usage in litho)
oo
Source In
a lithography
3
2 Collection/
5 storage
o
j» Treatment
O
Dltpotal/ute
Amount
J Frequency
£ Concentration
c
tu
Distribution
Movement
a Partition
— coefficient/bio-
's c concentration
| factor
1 Stability/
pertinence
Joxlclty
Ultimate
sink
Environmont.il
hazard
Gum
Pressroom
80% to printed copy,
20% to drain
20% to WW treatment
To surface water
6,170lb/yr todraln
Dally
Very low
Wide
Water soluble e
Biodegradable
Nontoxlc e
Returned to
natural cycle*
Low
Phosphoric acid
Pressroom
80% to printed copy,
20% to drain
20% to WW treatment
To surface water
38 gal/yr to drain
Dally
Very low
Wide
Moves In P cycle
Essential nutrient
In blosystems
Orl-rat LD, „ : 1630 mg/kg °
Skln-rbt LD, „ :274O mg/kg °
Returned to
natural cycles
Low
Ammonium dkhromate
Pressroom
80% to printed copy,
20% to drain
20% to WW treatment
To surface water
94 Ib/yr to drain
Water soluble a
CrVI tendsto Crlll,
the less toxic form
Highly toxic e
CrVI 96-hr LC,0
Fathead = 33 mg/l '
Crlll 96-hr LC,.
Fathead - 27 mg/l '
Zinc nitrate Alcohol
Pressroom Pressroom
80% to printed copy, 80% evap. to air
20% to drain 20% to drain
20% to WW treatment 20% to WW treatment
To surface water To surface water
Water soluble e Water soluble
vapor press.
33 torr <§> 20° C ••
k
Nitrate = nutrient BOD - 0.16-1.68 g/g
Zinc-accessible e> < 500 mg/i •• f
High Lethal 24 hri flth
600- 1000 mg/l a
Remain* accessible Returned to natural
cycles
Low (based on
entry level)
Low (based on Low
entry level)
-------
TaWe6. Plate coatings
(13,000 Ib/vr - U.S. usage in litho)
oo
N>
§
2
5
I
ui
I
Blologlcel
Source in
lithography
Collection/
storage
Treatment
Disposal/use
Amount
Frequency
Concentration
Distribution
Movement
Partition
coefficlent/bfo-
concentratlon
factor
Stability/
persistence
Toxlclty
Ultimate sink
Environmental
hazard
Diazo
On plates
1 . Plate room to
WW<»*1/3)
2. Pressroom to
plant trash system
(~2/3)
1 . To WW treatment
2. None, Incineration,
or to plate recycle
WW to surface
water, solid waste
to lendf III
346 Ib/yr to drain
694 Ib/yr to landfill
Daily
Very low
Wide In water
Localized In landfills
Water soluble
Unstable to heat, light.
In water Dlezo group
Is replaced with OH.
Further degradation
prods, unknown.
Not well established;
could be carcinogenic
Questionable
Low (based on entry
level)
Resins
On plates
1 . Plate room to
WW (~1/3)
2. Pressroom to
plant trash system
1 . To WW treatment
2. None, incineration,
or to plate recycle
WW to surface
water, solid waste
to landfill
3.240 Ib/yr to drain
6,610 Ib/yr to landfill
(Total - 0.00003% of
U.S. total prod. q)
Dally
Very low
Wide In water
Localized In landfills
Low
Probably low
Polymerized forms
generally stable
Polymerized forms
generally low
Llthosphere
Low
Organic acids
On plates
1 . Plate room to
WW (~1/3)
2. Pressroom to
plant trash system
1. To WW treatment
2. None, Incineration,
or to plate recycle
WW to surface
water, solid waste
to landfill
43 Ib/yr to drain
87 Ib/yr to landfill
Dally
Very low
Wide In water
Localized in landfills
Water soluble
Biodegradable
Low
Returned to natural
cycles
Low
Pigments
On plates
1 . Plate room to
WW (~1/3)
2. Pressroom to
plant trash system
1 . To WW treatment
2. None, Incineration,
or to plate recycle
WW to surface
water, solid waste
to landfill
660 Ib/yr to drain
1,300 Ib/yr to landfill
Dally
Very low
Wide In water
Localized in landfills
Water Insoluble d
Fairly stable
Many are toxic
Variable
Low (based on entry
level)
Indicator dyes
On plates
1. Plata room to
WW (~1/3)
2. Pressroom to
plant trash system
1 . To WW treatment
2. None, Incineration,
or to plate recycle
WW to surface
water, solid waste
to landfill
43 Ib/yr to drain
87 Ib/yr to landfill
Dally
Very low
Wide In water
Localized In landfills
—
—
—
Low (based on entry
Level)
-------
CO
CO
Table?. Inks
(159.000,000 Ib/yrr - U.S. usage in IrtJio, 1972)
(See "Reactive Solvents" for viscosity reducers.)
Pigments (4,300,000 Ib/yr to landfill r)
Source In
3
S
s
o
0
lithography
Collection/
storage
Treatment
Disposal
•
1
£
c
1U
Amount
Frequency
Concentration
Distribution
Movement
2
a
E.
1
*
o
ffl
Partition
coefflclent/blo-
concentratlon
factor
Stability/
persistence
'Toxlcltv
Ultimate sink
Environmental
hazard
Oil vehicles
Pressroom
90% to printed prod..
1 0% to waste
10% waste-plant
trash system
(some to air)
None or Incineration
Landfill or dispersed
In air
11, 000,000 Ib/yr to
landfill r
Dally
Low In solid waste
Localized In landfill.
widespread In air
Low
Not likely
Probably biodegradable
Low
Returned to natural
cycles
Low
Driers
Pressroom
90% to printed prod.,
1 0% to waste
1 0% waste-plent
trash system
None or incineration
Landfill or dispersed
in air
600,000 Ib/yr to
landfill r
Dally
Low In solid waste
Localized In landfill
OH soluble
Probable
Slowly biodegradable
High (most contain Co,
Mn, Pb)
- Organlcs returned to
natural cycles
- Metals remain accessible
Low (besed on entry
level)
Lead chromate
Pressroom
90% to printed prod..
1 0% to waste
10% waste-plant
trash system
None or Incineration
Landfill or dispersed
in air
—
Dally
Low In solid waste
Localized In landfill
5.8 X 10"* g/100 cc water c
Pb: B.F. - 40,000 phytoplankton
4,000 mollusk
Chemically reactive
Highly toxic 8
Scu-rat tdl 1 200 mg/kg g
Irp-gpg LD,0 ° 400 mg/kg 8
U.S. occ. std. air 0.1 mg/M*
(asCrO,)
Remains accessible
Low (based on entry level)
Prussian blue
Pressroom
90% to printed prod..
1 0% to waste
1 0% waste-plant
trash system
None or Incineration
Landfill or dispersed
in air
—
Daily
Low In solid waste
Localized in landfill
Insoluble c
Very low
Stable
Low in this form e
Llthoiphere
Low
Organic pigments
Pressroom
90% to printed prod..
10% to waste
10% waste-plant
trash system
None or Incineration
Landfill or dispersed
In air
—
Dally
Low In solid waste
Localized In landfill
Insoluble d
—
Questionable
So me a re high
Returned to natural
cycles
Low (based on entry
(level)
-------
TableS. Other
Source in
lithography
o>
3
0
^
3
g.
5
Collection/
storage
Treatment
Disposal/use
Amount
I
>
&
Hi
Frequency
Concentration
Distribution
Movement
Partition
cj
0.
E
To
o
?~
_
m
coefficlent/blo-
concentratlon
factor
Stability/
persistence
Toxiclty
Aluminum
plate backing
Plate room,
pressroom
Most to recycle
Recycle
Reused
7.2 million Ib/yr
Dally
Recycled
Recycled
Low
Low
Stabilizes by
formation of
oxide (AljOj) on
surface b
Low
Alcohol
developers
Plate room
Most to drain
some evap. to air
To WW treatment
To surface waters
220,000 gal/yr
« 0.1% of U.S.
total)
Dally
Very low
Wide In air &
water
Water soluble
vapor pressure
33 torr 9 20° C
PC - 0.05
BF=1.41
BOD 0.16-1.68 fl/g
S> < 500 mg/l ••"
Lethal 24 hrs fish
500-1 000 mg/la
appears on pro-
posed EPA list
of hazardous
substances n
Gum coatings
1 . Plate room -
to rags
2. Pressroom -
to WW
1 . To plant trash
system
2. To WW treatment
None, incineration.
or WW treatment
Solid waste to
landfill, WW to
surface waters
563.000 Ib/yr
plate room rags
63,000 Ib/yr
washed to drain
In pressroom
Dally
Low
Wide in water.
localized in
landfill
Water soluble e
Biogradable
Nontoxic e
Blankets
rubber/fabric
Pressroom
To plant trash
system
None, or
incineration
To landfill
or air
5,000 ft5 /yr
to waste
Quarterly
0.3ftV
landfill/yr*
Localized In
landfills
Low
N/A"
Stable
Low
Organic liquids, solvents
Paper
Pressroom
10% to plant
trash system
None, Incineration,
recycle?
To landfill
or air
500,000 tons/
yr to waste p
Daily
28 tons/land-
flll/yr'
Localized in
landfills
Low
Slowly bio-
degradable
Low
Nonreactive
Plate room.
Pressroom
To drain,
to air
None, WW
treatment
1. Dispersed
2. To surface
waters
853,000 gal/yr °
(47% of total
solvents used
in litho)
Continuous during
printing
Low
Wide
High
Bioconcentration
possible
Probably bio-
degradable
Moderate
Reactive
Pressroom
To air or
recovered
None, Incineration,
or recycle
Dispersed in
air or recycle
978,000 gals/yr °
(53% of total
solvents used
In litho)
Continuous during
printing
Low (regulated)
Wide
High
Bioconcentration
possible
Slowly bio-
degradable.
photochemlcally
reactive
Moderate
•Assume 18,000 landfills In the United States.
- not applicable.
-------
Table 8. Other (continued)
Aluminum
plate backina
Ultimate sink Lithosphere
Environmental Low
hazard
Alcohol Blankets
developers Gum coatings rubber/fabric Paper
Returned to Returned to Llthotphere Returned to
natural eyelet natural cycles natural cycles
Low Low Low Contributes to
total solid
waste problem,
but otherwise
Innocuous
Organic liquids, solvents
Nonreactive Rnetive
Returned to
natural cycles
Low (based on
entry level)
Returned to
natural cycles
Low (based on
entry level)
REFERENCES FOR TABLES 5-8
aR. A. Abbott, "Potential Impact on the Aquatic Environment of Raw Materials Used in Chemical Specialties," Ontario Ministry of the Environment,
Toronto, Canada, 1973.
bF. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Third Edition, Interscience Publishers, New York, 1972.
c Handbook of Chemistry and Physics, 49th Edition, The Chemical Rubber Co.. 18901 Cranwood Parkway, Cleveland, Ohio 44128, 1968.
dP. A. Hartsuch, "Chemistry of Lithography," Lithographic Technical Foundation, Inc., 131 East 39th St., New York, 1961.
££ eG. G. Hewley, The Condensed Chemical Dictionary, 8th Edition, Van Nostrand Reinhold, New York, 1971.
01 fG. Heukelekian and M. C. Rand, "Biochemical Oxygen Demand of Pure Organic Compounds," Sewage and Industrial Wastes, Vol. 27, No. 9, 1955.
9(H. E. Christensen, (Ed.), 'The Toxic Substances List," U.S. Dept. of HEW, NIOSH, 1974.
"Staff Report, 'The Top 50 Chemicals," Chem. & Eng. News, p.11. May 6, 1974
'"Recommended Uniform Effluent Concentration," EPA, 1973.
'"Chromium," National Research Council, Washington, D.C., 1974.
^''Physical Properties of Common Organic Solvents," Texas Solvents and Chemicals Company, Box 10406, Dallas, Texas 75207, 1972.
'T. D. Smock, 'The Market for Organic Pigments," American Ink Maker, p. 19, Dec. 1974.
m"Lead-Airbome Lead In Perspective," National Research Council, Washington, D.C., 1972.
""Proposed EPA Regulations on Designation and Determination of Removability of Hazardous Substances," Federal Register, Vol. 39, p. 30466, Aug. 22, 1974.
°R. R. Godomski, M. P. David, and G. A. Blahut, "Evaluations of Emissions and Control Technologies in the Graphic Arts Industries," Phase 1 Final Report,
Graphic Arts Technical Foundation, 4615 Forbes Avenue, Pittsburgh, Pa. 15213, 1970.
PB. Slatfn, "Economic Structure of the Paper Industry," Tappi, Vol. 58, No. 7. July, 1975.
''"Development Document for the Synthetic Resins," EPA 440/1-71/010, Aug. 1973.
r 1972 Census of Manufactures, U.S. Dept. of Commerce.
s"Exclusive Waste Age Survey of the Nation's Disposal Sites," Waste Age, Jan. 1975.
-------
Table 9. Potential environmental hazard
Low Low, based on entry level
Resins Reactive solvents
Organic acids Ammonium dichromate
Gum Zinc nitrate
Phosphoric acid Driers
Alcohols Diazo compounds
Aluminum Indicator dyes
Rubber/fiber blankets
Paper
Nonreactive solvents
Oil vehicles
CONCLUSIONS
The low entry levels and biological impact of waste products from plate
and press rooms make lithography an environmentally-acceptable process.
Control of photochemically-reactive solvents is already recognized as im-
portant in the industry, and should be continued for good environmental
stewardship. Data is incomplete on the biological impact of heavy-metal-
containing components in ink driers and pigments, but their entry levels are
low from the press room and can be adequately handled by conventional waste
management systems.
ACKNOWLEDGMENT
I want to extend my sincere appreciation to R. B. Kincaid, 3M Printing
Products Division, and my coworker, S. K. Welsh, for the extensive informa-
tion contained herein on the lithographic printing industry and estimates
on the levels and biological impact of waste materials.
REFERENCES
1. Principles for Evaluating Chemicals in the Environment, National
Academy of Science, Washington, D.C., 1975, 454 pp.
186
-------
2. "Environmental Behavior of Chemicals," Chemicals, Human Health and the
Environment: A Collection of Dow Scientific Papers. Vol. I; Section I,
1973-74.
3. John M. Wood, "Biological Cycles for Toxic Elements in the Environ-
ment," Science, Vol. 183 (March 15, 1974), pp. 1049-52.
4. R. L. Metcalf, Environ. Sci. & Tech., Vol. 5, No. 8 (August 1971), pp.
709-13.
5. Rodney L. Borum, "Printing: It's Growth and Future," Amer. Ink Maker,
May 1974, pp. 32, 62.
6. "Commercial Printing and Manifold Business Forms," 1972 Census of Manu-
factures, U.S. Department of Commerce, MC72(2)-27B.
7. Editorial, "Sales of Ink in 1980," Amer. Ink Maker, Dec. 1974, p. 16.
8. James E. Renson, "An Analysis of the Census of Manufactures," Amer. Ink
Maker. June 1974, pp. 21-26.
9. Paul J. Hartsuch, "Chemistry of Lithography," 2nd edition, Lithographic
Technical Foundation, New York, 1961.
10. R. R. Gadomski, M. P. David, and G. A. Blahut, "Evaluation of Emissions
and Control Technologies in the Graphic Arts Industries," Phase I,
Final Report, Graphic Arts Technical Foundation, Pittsburgh, Pa. 15213,
1 Z7 /U •
DISCUSSION
MR. FRANCIS M. ALPISER (Environmental Protection Agency, Philadelphia, Penn-
sylvania): I am a little concerned about the ultimate environmental
impact of new chemicals that are developed and coming out each year.
Do you see industry voluntarily trying to monitor the impact of these
chemicals upon our environment and biosphere? Or do you see that not
to be something done voluntarily, but which will have to be required by
legislation passed by Congress?
DR. BOHON: Well, let me speak just for 3M.
In one of my jobs, I am charged with the responsibility of taking
a look at every new and modified product introduced by 3M Company from
the perspective of what the environmental risk will be. We do the best
we can with the data that we can find or develop. We obviously cannot
go into very extensive long-term chronic studies, but if it is a material
187
-------
that shows great promise to our company as an important material, then
we want to be very certain that down the pike we are not going to .get
tripped up with some kind of environmental problem, so we do our best
to try and assess whether or not that material will result in some
kind of an undue environmental hazard.
So in answer to your question, I think that industry, at least our
industry, wants to know how materials we introduce in the environment
are redistributed. That is what it boils down to—redistribution of
materials from one point to another: a concern that they can be
safely disposed of, that the systems exist for their disposal, and
that they will not cause any undue environmental hazard.
CHAIRMAN SCHAEFFER: Dr. Bohon, you were willing to speak for 3M Company
at one stage. I think the question has philosophical problems if we
try to speak for industry generally. So concerning the environmental
impact, we are talking about several levels in terms of industry—from
the prime manufacturer to the user of a chemical in processing or formu-
lating, through an industrial user of a chemical. Now, I believe the
intent here is to talk about the prime source of supply for a given
chemical.
DR. BOHON: (To F. Alpiser) I am not sure whether that is what you had ref-
erence to or not: the prime source of chemical supplted (the prime
manufacturer) or a formulator?
MR. ALPISER: I am concerned with the new chemicals that are introduced each
year. To give you a little bit of a background, I was 25 years in the
chemical industry myself, and worked for a company that produced over
2,000 chemicals. The rate of new chemicals coming out each year is just
tremendous. I do not really think that in most cases the environmental
risk is being assessed in the manner in which 3M describes. I am a lit-
tle concerned about it, and wondered exactly how industry feels about it
versus a mandated requirement, which as you probably know, has been con-
sidered.
CHAIRMAN SCHAEFFER: I think it is a question to be pondered very seriously
about industry, when you have that type of broad-based problem. Dr.
Bohon, do you have any more comments on that?
188
-------
DR. BOHON: Only to say that I think we are willing to consider and apply
whatever kind of test method can really give some vital, significant
information at reasonable cost. We do not want to be forced into
making a bunch of measurements that really have no relevance or sig-
nificance. And so, I guess if I were to make any kind of a comment
at all, it would be a plea for flexibility and the freedom to update
test methodologies and so forth, as science suggests this can be done.
It just does not pay to get locked into some kind of a test that sub-
sequently you find out really has no meaning whatsoever.
MR. THEQPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
As you know, when food additives, new chemicals, are filed, we require
an environmental impact analysis report. This is in order to try and
keep track of just what is going on. One of the most difficult ones
has been the bottle.
CHAIRMAN SCHAEFFER: Very appropriate.
189
-------
MATERIALS OF FLEXOGRAPHY
K. A. Bownes*
Abstract
Flexography is possibly the most versatile of all printing processes.
It is used to print almost any type of substrate. Products printed flex-
ographically are mainly used by the packaging industry.
The inks used for flexographic printing are formulated from a wide
variety of resins3 solvents3 pigments, plasticizers,, and various additives.
The. ink film is required to perform under a wide variety of end-use con-
ditions encountered during the life span of the printed product.
Flexography is a rotary typographic process using a simple ink dis-
tribution system and very fluid inks. The inks dry by evaporation of vol-
atile solvents or, in the case of water-base inks, by absorption into the
substrate. The flexible printing plates are usually molded in natural
rubber. Although flexographic printing is mechanically simple, it is a
very versatile printing method and can print a wider variety of substrates
than almost any other process.
The differences between the flexographic printing unit and convention-
al letterpress ink distribution systems are shown schematically in figure 1.
As many as six print stations may be found on central impression cylinder
(CIC) flexo presses. Fountain covers are used to minimize solvent loss
before ink transfer takes place. Even so, some is lost before entering the
dryer. Modern presses are equipped with high-velocity dryers in which air
literally "scrubs" the solvent from the printed surface at moderate tem-
peratures (generally below 250° F). Air velocities are usually between
6,000 and 12,000 feet per minute while total exhaust can be in the 7,000-
to 15,000-CFM range. A recent survey (ref. 1) indicated that total solvent
evaporation from flexographic plants averaged about 60 pounds/hour. More
accurate figures are difficult to obtain since the industry is so widely
scattered throughout the country.
*Manager, Technical Liaison, Inmont Corporation, Clifton, New Jersey.
190
-------
LETTERPRESS
Distribution
Rollers
Impression
Cylinder
FLEXOGRAPHY
Plate
Cylinder
Plate
Cylinder
Delivery
Cylinder
Distributio
Rollers
Ink Fountain
Figure 1. Ink distribution system.
The major categories of the flexographic market are: flexible packag-
ing and laminates, multiwall bags, milk cartons, folding cartons, corru-
gated paper, paper cups and plates, labels, tags, tapes, envelopes, books,
and gift wrap. The substrates involved in flexography are: paper and
paperboard (all grades), polyethylene, aluminum foil, cellulose acetate,
polystyrene, vinyl and vinylidene chloride copolymers, and laminations of
the above.
It may be concluded then that flexographic inks have to do much more
than be decorative. They must also have flexibility, adhesion, printability,
resistance to heat, cold, sunlight, moisture, abrasion, and must possess
low residual odor. To do all this requires a wide variety of ink vehicle
components which function as shown in table 1.
191
-------
Table 1. Typical flexographic vehicle composition
Component Function
Resin Adhesion, product resistance,
gloss, disperses pigment
Solvent Dissolves resin, controls vis-
cosity, controls drying
Plasticizer Flexibilizes resin
Lubricant Controls rub and coefficient
of friction
Defoamer Controls foam in aqueous ink
When formulating solvent-base inks, there are a wide variety of resins
to choose from to achieve the desired ink properties. The main limitation
is that the resin must be soluble in a solvent that will not be too harm-
ful to rubber. Typical resins are shown in table 2.
A much more limited choice is available when formulating aqueous inks.
Amine salts of acidic resins and polymers form the vehicle system for most
water-base inks. These are shown in table 3. Emulsions or "latices" lack
Table 2. Resins and typical application
Resins Typical application
Nitrocellulose Most solvent inks, particularly
where heat resistance is required
Other cellulose Laminating inks and special purpose
derivatives plastic films
Shellac Water-base inks, milk cartons
Ketone-aldehyde Laminations
condensates
Acrylics Laminations, inks for vinyl and
vinylidene polymers
Rosin derivatives Inks for paper, aqueous inks
Polyamides Polyolefins and other plastics
Phenolics Dye inks
Urethanes Adhesives
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Table 3. Resins for aqueous inks
Resin Types
Resin (acidic) Shellac, modified rosins
Protein Soya protein, casein
Polymeric Styrene-acrylic copolymers,
Ethylene-maleic copolymers
Latex Emulsions of styrene-butadiene
vinyl acetate, acrylics, etc.
the true viscosity or "tack" needed for even distribution of ink and are
only used as modifiers for other resins.
In order for the resin to fulfill its role in the flexographic process,
it must be applied from a suitable solvent system. Normally a combination
of solvents is required to make a satisfactory ink. Many factors must be
balanced, such as proper viscosity, drying speed, gloss of the dried ink
film, and low retention in the print. Table 4 shows typical solvents,
their evaporation rates (ref. 2) related to water = 1, and their Threshold
Limit Values (ref. 3).
A convenient source for a cross section of plasticizers can be found
in the Food Additives Regulations. Plasticizers for flexographic inks
include: acetyl tributyl citrate, acetyl triethyl citrate, butyl phthalyl
butyl glycolate, butyl stearate, dibutyl sebacate, dibutyl phthalate, di-
ethyl phthalate, diisobutyl adipate, diisooctyl phthalate, epoxidized soy-
bean oil, ethyl phthalyl ethyl glycolate, 2-ethylhexyl diphenyl phosphate,
di-2-ethylhexyl phthalate, glyceryl triacetate, propylene glycol, and
triethyl citrate. Lubricants and additives include: paraffin and micro-
crystalline waxes, polyethylene wax, stearamide, erucamide, silicone fluids
(lubricants and defoamers), and octyl alcohol (defoamer).
Because of the vast range of colors demanded by the purchaser of
packaging materials, a wide selection of colorants is needed for color
matching. At the same time, the many performance requirements mentioned
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Table 4. Flexographic solvents
Type
Alcohols
Esters
Glycol
Ethers
Glycol s
Miscel-
laneous
Examples
Methanol
Ethanol
Isopropanol
n-Propanol
Ethyl acetate
Isopropyl acetate
n-Propyl acetate
Cellosolve?
Dowanol PMD
Methyl Dioxitolc
Ethyl ene glycol
Propylene glycol
2-Nitropropane
Hexane
Water
Drying rate
(water-1 )
5.75
3.89
4.00
2.39
10.86
9.50
5.78
1.06
2.30
0.06
0.03
0.03
3.06
24.72
1.00
Threshold Limit
Value (ppm)
200
1,000
400
200
400
250
200
200
-
-
-
-
25
500
aTM, Union Carbide Corp. Mono ethyl ether of ethylene glycol.
TM, Dow Chemical Co. Mono methyl ether of propylene glycol.
CTM, Shell Chemical Corp. Mono methyl ether of diethylene glycol.
earlier, such as resistance to bleed in wax or plasticized films, must
still be met.
The first group of colorants includes white, black, and the inorgan-
ics. These are: titanium dioxide; calcium carbonate; clay (kaolin); alu-
minum powders; carbon black (furnace and channel process); iron oxides
(yellow, red, black); lead chromate yellow; molybdated lead chromate orange;
and iron blue (ferric ferrocyanide).
Many organic colors are azo couplings. This category accounts for
most yellows, oranges, and reds. Table 5 shows the most important of
these with typical color index numbers (ref. 4).
Table 6 shows blues, violets, and greens. For resistance properties,
the phthalocyanine derivatives are most important. Methyl violet, Victoria
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Table 5. Azo couplings with their typical
color Index numbers (ref. 4)
Pigment Color index no.
Hansa yellow 11730
Diarylide Yellow 21095
Dianisidine orange 21160
Diarylide orange 21110
Naphthol red 12315
2B red 15865
Lithols (Ba,Ca,Sr,Na) 15630
BON red 15860
Red lake C 15585
Lithol rubine 15850
Table 6. Blue, violet, and green pigments
Pigments Color index no.
Phthalocyanine blue 74160
Phthalocyanine green 74260
Alkali blue 42750A
Victoria blue 42595
Methyl violet 42535
Malachite green 42000
blue, alkali blue, and malachite green are triphenyl methane derivatives
used as phosphotungstic or phosphomolybdic acid lakes. Other miscellaneous
colors include rhodamines, dioxazines, and quinacridones.
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Flexo inks containing soluble dyes make up a smaller segment of the
market for such applications as envelopes, paper tapes, some glassine
wrappers, and background tints on paper. Basic dyestuff is mainly used,
usually laked with phenolic resin. Typical dyes are shown in table 7.
Table 7. Dyes for flexo inks
Dye Color index no.
Auramine 41000
Rhodamine 45170
Methyl violet 42535
Victoria blue 44045
Brilliant green 42040
REFERENCES
1. Flexographic Technical Association, 1973 Survey of New Jersey Printers,
Jericho, New York.
2. Shell Thin Film Evaporometer Data, Shell Solvent Chart 1C-71-18R, Shell
Chemical Co., Houston, Texas.
3. NPIRI Raw Materials Data Handbook, Vol. 1, NAPIM Technical Institute
at Lehigh University, Bethlehem, Pa., 1974, pp. 12-25.
4. Colour Index, Third Edition (1971), The Society of Dyers and Colour-
ists (England) and The American Association of Textile Chemists and
Colorists, Research Triangle Park, North Carolina.
DISCUSSION
MR. THEOPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
How do you dispose of your resins?
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MR. BQWNES: Are you referring to waste ink?
MR. CARSON: Right.
MR. BOWNES: That is normally taken away by a contractor and disposed of
in a sanitary landfill. Some inks are incinerated. But then of course
the sludge, the residue, the pigment, which do not incinerate, and
whatever is left of the resin, go to a sanitary landfill eventually.
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ENVIRONMENTAL IMPACTS OF CHEMICALS USED
IN SCREEN PRINTING INKS
Charles F. Call, Jr.*
Abe tract
Screen printing is the most versatile of all printing processes be-
cause of its ability to print on any substrate. Next to gravure, screen
printing uses the highest solvent-content inks. This high solvent con-
tent j coupled with the wide range of solvents that must be used bo formu-
late inks for diverse substrates, constitutes the primary environmental
impact of materials used in screen printing inks.
SCOPE
This paper will explore the raw materials used in screen printing inks,
especially solvents, that have the greatest environmental impact. The au-
thor will consider possible environmental impacts from the printer's view-
point. Although many different chemicals will be discussed, it is not
within the scope of this paper nor within the author's expertise to explore
their specific impact or deterimental effects.
Because of screen printing's diverse uses, the industry has divided
itself into many groups, all falling under the auspices of the Screen Print-
ing Association. For the purpose of this paper, the author has divided
screen printing into only two groups: electronics and commercial. The
electronics group covers the use of screen printing for printed circuit
boards. The commercial group covers decorating, display, advertising, tex-
tiles, and other factions of screen printing not connected with electronics.
The division was made because of the end use of the ink film and the possi-
ble environmental impacts of that use.
technical Service Applications Engineer, Wornow Products Department,
Hysol Division of Dexter Corporation, Olean, New York.
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INTRODUCTION
Screen printing is the most versatile of all printing processes. Its
ability to print on any substrate has given impetus to rapid growth over
the past few years. In conjunction with diverse substrate advantages, ink
deposit and color strength have created markets for screen printing in
areas including printed circuit boards, display advertising, textiles, and
decorating.
These advantages of screen printing have promoted the formulation of
many different inks to meet substrate and end-use requirements. The raw
materials used for these inks are chosen by their ability to perform in
relation to the particular substrate and end use. Solvents, our primary
concern, are chosen for their ability to work with the proper raw materials
and for their substrate advantages, as well as their fitting the needs of
the screen printing process.
Much of the information in this paper is based on courses taken by
the author during undergraduate studies in the College of Graphic Arts and
Photography, Rochester Institute of Technology, Rochester, New York. Addi-
tional information was garnered from James Hornburg and Jerry Lutz, Hysol
Division, The Dexter Corporation, and the author's personal experience.
l ^-V
THE SCREEN PRINTING PROCESS
Screen printing is a stencil process. Stencils are made mechanically
or photographically and mounted on precision-woven fabric for support. Ink
is printed through the stencil and fabric by a "squeegee" and deposited on
the substrate. This transfer from screen (combination of stencil, fabric,
and a frame to hold the fabric) to substrate is accomplished by hydraulic
pressure, applied by the squeegee, to ink present in the "holes" of the
fabric, and also by the-affinity of the ink for the substrate—over the
fabric and stencil.
This type of printing requires a fluid ink. Screen printing inks are
usually 50 to 80 percent solid materials; that is, pigment, resin, and
filler make up 50 to 80 percent of the mass, while solvent contributes the
rest of the formulation. Only gravure (and flexography) can claim a higher
solvent content.
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Substrates vary greatly. Many shops specialize in certain types of
screen printing and the substrate they print reflects their specialization.
Poster shops work with paper. Decal shops work with decal paper and re-
cently with pressure-sensitive synthetics. Metal decorating shops fre-
quently use screen printing on aluminum, steel, and other metals. Circuit
shops print on copper laminated on epoxy fiberglass boards. Because of
different end-use requirements, substrates cause special ink selections.
Quality requirements for the end use of the printed piece do not allow for
universal inks.
SCREEN PRINTING INK FORMULATION
Screen printing inks are virtually all "conventional-curing." That is,
the inks cure in either room temperature air or in a heat-generating oven.
Inks are formulated with three primary areas in mind: substrate, end use,
and screenability. Secondary areas of concern include cost, raw material
availability, production feasibility, and competition.
Conventional inks contain resins, fillers, and solvent. "Resin" is a
broad-based term for the raw material that is the film former of an ink.
Resins are chosen for their substrate and end-use advantages. Typical
resins are alkyds, resin esters, epoxies, and vinyls. The compatibility of
a resin with solvents and fillers generally used in screen printing is also
considered.
Fillers are usually inert materials used to bring the formulation to
a screenable thickness or color. Fillers may also to some extent improve
opacity and adhesion to substrates. Typical fillers used are clay, calcium
carbonate, some silicates, and pigments.
When combined with resins, solvents constitute the "vehicle." Sol-
vents, for screen printing, are chosen by their solvent power, flash point,
boiling range, and toxicity. Solvent power is the ability of a solvent to
dissolve a particular resin. While some solvents are excellent for dis-
solving vinyls, this same solvent will not touch an alkyd resin.
The flash point is simply the solvent's ignition point, or more pre-
cisely the mean temperature at which solvent vapor escaping from a liquid
will form a combustible mixture with air and ignite when exposed to an open
flame (ref. 1).
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The boiling range of a solvent is the temperature at which its vapor
pressure equals atmospheric pressure. Simply put, the higher the boiling
range, the slower the solvent evaporates. Solvents for screen printing
generally have boiling ranges in excess of 340° F (ref. 1).
Toxicity is a concern because solvents have multiple accesses into the
human body. Solvents may be taken in through inhalations of solvent vapor,
absorption through the skin, or ingestion through the mouth. Certain sol-
vents produce dermatitis, or inflammation of the skin; some can produce
narcosis, or unconsciousness, and some can affect the kidney, brain, or
other vital organs. Of course, a very high concentration of any solvent
vapor could have serious physiological effects just by depriving oxygen
sufficient for normal activities. Toxicity can generally be prevented by
following handling instructions and, above all by providing adequate
ventilation (ref. 1).
Three solvent types are commonly used in screen printing inks. They
are aliphatic hydrocarbons, aromatic hydrocarbons, and oxygenated solvents.
Of the three types, only oxygenated solvents generally fall under what is
known as "exempt solvent" classifications. Exempt solvents came into
existence through Los Angeles "Rule 66", a stiff antipollution act; they
exhibit lower levels of the hydrocarbon emissions that form photochemical
smog.
While both the aromatic and aliphatic hydrocarbon solvents exhibit the
properties needed for manufacturing screen printing inks, the trend in for-
mulation has been towards exempt oxygenated solvents. This trend has de-
veloped because of the concern of screen printers and suppliers for comply-
ing with Federal and local antipollution regulations.
Oxygenated solvents can be chosen from esters, ethers, glycol ethers,
and ketones.
In addition to the three main ingredients in screen printing inks,
additives such as plasticizers, flow agents, and antiscum agents are used
to improve the printability and film properties of the ink.
POLLUTION CONCERNS
Screen printing inks normally cure, at least partially, by solvent
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evaporation. Secondary curing is by thermosetting, oxidation, polymeriza-
tion, or penetration. Printed circuit board resists or inks generally do
not cure at all, but merely "set up" through solvent evaporation.
Screen printing's major contribution to pollution is through solvent
evaporation. However, very few shops produce large enough volumes of eva-
porated solvent to cause any significant menace. All shops have alterna-
tives. The use of exempt solvent inks is one. Low solvent content, using
exempt solvents, also helps. Some segments of the industry can use water-
base inks; others can use ultraviolet cured, 100 percent solids materials.
Alternate curing methods are being developed.
In short, the screen printing industry is well within current anti-
pollution guidelines, on paper. There are still shops using nonexempt sol-
vent materials and they are polluting. However, as tougher State and local
regulations come into existence, these shops will have to comply, and the
means to comply are close at hand.
REFERENCE
1. Solvents Used in Screen Printing, SP-SOL, J. Lutz, Wornow Products
Department, Hysol Division, The Dexter Corporation.
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23 September 1975
Session II: (con.)
ENVIRONMENTAL IMPACT OF CHEMICALS USED
William D. Schaeffer, Ph.D.
Chairman
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GRAVURE INDUSTRY'S ENVIRONMENTAL PROGRAM
Harvey F. George*
Abstract
Gravure is one of the three major printing processes. It differs from
letterpress and offset lithography in that the recessed or intaglio image of
gravure permits the use of a very fluid ink that can be dried with low-
tempera t- :.:~c. forced-air driers between printing stations. The solvent-laden
air from the driers ideally can be directed through an activated carbon b&d
where tkz solvent is adsorbed and recovered. This paper presents an over-
view of the gravure printing process and industry, reviews the environ-
mental regulations applicable to gravure3 and discusses the gravure industry's
environmental program set up by Gravure Research Institute and Gravure Tech-
nical Association to assist gravure printers and engravers in complying with
these re
Nature of the Gravure Printing Process
Gravure is one of the three major printing processes that may be charac-
terized by the nature of their image formations. The gravure image is a
recessed T intaglio image, as compared to the relief or raised image of
letterpress and the planographic or surface image of lithography. The gra-
vure-image carrier is a copper-plated cylinder or copper plate, and the image
is in the form of cells or cups engraved in the surface. Typically, a gra-
vure cell is 35 y (.0014 in.) deep by 125 y (.005 in.) square, with 22,500
cells to the square in. (150-line screen). The walls between cells are known
as the bridge or doctor blade support, and the intersections between the
walls are called the corner posts. The gravure cylinder is flooded with a
liquid gravure ink. The excess ink is doctored off with a .006- to .010-in.-
thick Swedish blue steel doctor blade. The ink is then transferred to the
paper to be printed by pressing the paper against the cylinder as it turns,
*Executive Vice President and Research Director, Gravure Research
Institute, Inc., Port Washington, New York.
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using a rubber-covered impression roll of 70- to 85-shore A durometer hard-
ness (ref. 1).
Uses for Gravure Printing and Coating
Gravure printing and coating applications fall into three major cate-
gories, i.e., publication, packaging, and specialties. In the publication
field, magazines, mail order catalogs, brochures, newspaper supplements,
comics, and other types of commercial printing are printed by the gravure
process. Folding cartons and flexible packages, including such items as soap
cartons, ice cream cartons, flip top cigarette packages, frozen food wraps,
composite foil cans, 1-1/4-mm polyethylene bread bags, etc., are typical
gravure printed packaging products.
In the specialty field, gravure is used for producing wall and floor
coverings, decorated household paper products such as towels and tissue,
cigarette filter tips, vinyl upholstery, wood grains, and a wide variety of
other products. Gravure is also used for applying accurately metered quanti-
ties of coatings to paper and other kinds of webs in various manufacturing
operations where the fast-drying inks used in gravure and the ability to
print well on a wide variety of surfaces are advantageous.
i •
Nature of the Gravure Printing Industry
Gravure-printed products are roughly 31 percent in the specialty field,
26 percent in packaging, and 43 percent in publication (ref. 2). The esti-
mated volume of gravure printing in all categories was about $4 billion in
1974 (ref. 3).
Publication printing is done by a relatively small number of companies
with large printing plants, numbering less than 50 in total. Package and
specialty printing by gravure is done by a considerably larger number of
companies, ranging from large integrated packaging companies with many gra-
vure press units to small captive operations with only one or two press units.
It is estimated that there are from 13 to 14 thousand gravure printing units
in the United States (ref. 4).
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A printing unit consists of a gravure cylinder and an impression roll,
with associated inking and doctoring mechanisms. A gravure press may
consist of from 1 to 8 or more units that are coupled together with
associated paper feeding and roll-or-folder-deli very arrangements. One
or more gravure units may run as an in-line operation coupled together
with other printing, coating, or converting operations.
The gravure industry is served by two industry-supported organizations:
the Gravure Technical Association, a trade association, which is concerned
with customer and trade relations, standardization, and education; and the
Gravure Research Institute, a not-for-profit cooperative research organiza-
tion, which is concerned with research on gravure printing and related opera-
tions, and with materials such as paper and ink.
Preparation of the Gravure Printing Surface
Preparation of the gravure printing surface starts with copper plating
the gravure cylinder, which may range in size from a cylinder only 3 in. in
diameter and 1 in. wide for printing on Pharmaceuticals, to a cylinder 17 or
18 ft long and 3 or more ft in diameter, for printing on linoleum. Publica-
tion and larger packaging or coating cylinders are usually integral-shaft
steel bases that are centrifugally cast with a .060-in.-thick deposit of
cyanide bath copper, followed by a .006-in.-thick strippable layer of copper
from an acid copper sulfate bath. After plating, the copper surface is
polished to a 6- to 10-pin.-finish and to close dimensional tolerances on
diameter, e.g., +.001 in. diameter and .001 in. TIR concentricity. Smaller
cylinders for packaging or specialty printing may have integral shafts or may
be of the sleeve type, using a mandrel or cone and a removable shaft. Cylin-
der base material may be steel or aluminum tubing. Copy to be engraved on
the gravure cylinder must be converted to photographic positives typically
made to a density range from 0.35 to 1.65 density units. The photographic
steps of color separation, color correction masking, etc., are common to all
printing processes and need not be discussed separately for gravure.
Either of two methods is used to screen the gravure images in order to
form the gravure cells or cups: 1) a cross-line screen with clear lines and
opaque dots is used to expose the resist together with the continuous
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positive (conventional gravure); or (2) a half-tone positive with variable
dot size is made from the continuous-tone positive with a density range from
.05 to .30 integrated density units (lateral hard-dot gravure). The contin-
uous-tone positive controls the cell depth, while the screen or half-tone
positive determines the cell area. Consequently, conventional gravure has
constant area variable depth cells, while half-tone gravure has cells that
vary both in area and depth.
Etching resists may be either of the diffusion type or stencil type.
Publication printing and process color printing for packaging and specialty
items is most often done with a diffusion resist, which may be either a
potassium bichromate, light-sensitized, pigmented, gelatin-coated paper
called carbon tissue, or a silver halide gravure-resist photographic film.
The diffusion resist is exposed with a high-intensity light source in regis-
ter to the continuous-tone positive and half-tone positive, in succession.
The resist is hardened or made water-insoluble in proportion to the amount of
light passing through the positive. After exposure, the resist is trans-
ferred to a "water-wettable," clean, polished, copper, gravure cylinder by
wetting the surface and rolling the resist face down in contact with the
copper. For publication work, the resist is in page size sheets, while for
packaging or coating cylinders, a single large sheet of resist may be used.
After transfer of the resist to the cylinder, the cylinder is soaked in hot
water for approximately 15 to 20 min. This is done to remove the backing
paper and to dissolve away the unhardened gelatin. A variable-thickness
gelatin resist thus remains over the entire surface of the cylinder, with
the resist thickest in the nonprinting and highlight areas and thinnest in
the shadow areas. After drying and staging with asphaltum varnish (to
protect the cylinder ends and other areas of bare metal), the image is
etched into the,copper surface in a ferric chloride etching bath of approxi-
mately 40° Be specific gravity that diffuses through the gelatin resist and
penetrates first the thinnest areas or shadows, and finally the lightest
areas or highlights. Single- or multiple-bath etches of varying Baumes may
be used to obtain the desired range of cell depths. After etching, the
resist is removed and the cylinder may be chrome plated for longer wear-
life if desired.
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With the stencil resist process, the gravure cylinder is coated with a
light-sensitive photopolymer such as KPR (Kodak Process Resist), or a bi-
chromated colloid such as gum arabic or PVA. The sensitized cylinder is
exposed to a half-tone positive only, and after development may be etched
with a single bath of ferric chloride. Engraving with a stencil-type resist
process, which is also known as Direct Transfer Engraving, produces an
essentially constant cell depth. Tonal variation results are obtained mainly
from differences in cell diameters, and as a consequence, a limited tonal
range is achieved. However, for line work and coating cylinders where uni-
form cell volume is required, a Direct Transfer process with a stencil resist
is economically advantageous.
Michael (ref. 5) lists 15 processes where water contacts metals in the
plating and engraving of gravure cylinders as outlined above and waste treat-
ment is required. These 15 processes are grinding and polishing, film proc-
essing, etching, alkaline cleaning, acid pickling, copper cyanide plating,
boiler water chromate processing, chromium stripping, chromium strip heating
and cooling (coils), acid copper sulfate plating, carbon tissue sensitizing,
chromium plating, chrome plating heating and cooling (coils), and chromium
exhausting. Among the processes involved in treating waste from these proc-
esses are mechanical separation of effluent, silver recovery, cyanide oxida-
tion and destruction, reduction of hexavalent chromium to trivalent chromium,
neutralization, and precipitation. Batch treatment systems, as opposed to
continuous systems, have been found to be economically practical in small- to
medium-size plants, according to Michael. The safe disposal of solid waste
from such treatment systems must also be considered.
Lubell (ref. 6) describes the waste water treatment system for the
Newspoint Rotogravure plant of the New York News, where the total maximum
average daily (design) waste water treatment has been calculated at 8,700
gallons, of which 8,000 gallons require neutralization and precipitation
while the remaining 700 gallons require dilution before discharging to the
city sewer.
Gravure cylinders may also be imaged by electromechanical engraving on
an electronic scanner-engraving machine such as the Hell Helio-Klischograph.
In this process, the copy is mounted on a scanning drum and signals from a
photoelectric pickup are used to control an electromechanically driven
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diamond stilus that cuts pyramidal-shaped gravure cells into the surface of
the gravure cylinder at the rate of 4,000 cells a second. Electronic gravure
cylinder engraving machines, which were first introduced about 1958, are
becoming more widespread in use and have found application in publication
printing, package printing, and in specialty printing for wood grains and
other seamless patterns for decorative laminates. Coating cylinders using
the gravure ink transfer method may also be made by mechanical knurling.
These cylinder engraving methods, while in themselves involving no water
pollution problems, still require treatment for the plating and other
operations.
The Gravure Printing or Coating Operation
Installation of the engraved gravure cylinder in the gravure press unit
and adjustment of doctor blade, impression pressure, web-guiding rolls,
unwind tension, folder, etc., constitutes the "makeready" of a gravure press.
Once the various press settings are made and the proper ink viscosity
and drying conditions are achieved for proper ink transfer and printed film
characteristics, the gravure printing or coating operation is relatively
simple to control. Maintenance of ink viscosity is the major requirement.
This is achieved by the addition of a solvent to the ink, in order to make up
for evaporation. The makeup solvent should be blended to maintain the pri-
mary solvent resin mixture in the original ink formulation. The gravure
cylinder, if chrome plated, can run for millions of impressions.
Gravure Printing and Coating Equipment
The basic gravure printing or coating unit consists of the engraved
gravure cylinder at the bottom, with a rubber-covered impression roll at the
top. The gravure cylinder is geared to, and driven by, a motor-driven shaft
which drives the other gravure units or converting units in the line. The
impression roll is friction-driven through the web by the gravure cylinder.
For wide presses, such as are used in publication printing, the impression
roll may be backed up by a steel backup roll to minimize bending. Mechanical
impression screws or hydraulic or pneumatically operated impression pistons
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apply impression pressure to the end journals of the impression roll or back-
up roll, pressing the rubber against the gravure cylinder with a pressure of
50 to 250 lb/linear in.
The gravure cylinder runs in an ink fountain or trough. In addition,
spray nozzles may also be used to apply ink at a point close to the exit side
of the nip. The ink fountain on high-speed presses using volatile inks is
totally enclosed, except for a small area between the doctor blade and the
nip and on the exit side of the nip. Enclosure of the ink fountain minimizes
solvent evaporation and permits the use of fast-drying solvents which are
required in high-speed printing operations.
A doctor blade holder is provided, together with an oscillating mecha-
nism that permits adjustment of the doctor blade angle, as well as the hori-
zontal and vertical positions of the doctor blade. Gravure press speeds
range from approximately 500 to 1,000 ft/min in packaging and specialty
printing, from 1,200 to 1,800 ft/min in magazine and supplement publication
printing, and up to 3,000 ft/min or more in some printing operations running
in line with paper machines.
Inks and Coatings for Gravure
A typical gravure ink consists of pigment, binder, and solvent in the
following approximate proportions: 10, 50, 40. Pigment provides color to
the ink and may consist of such materials as clay, titanium dioxide, carbon
black, lithol red, red lake C, lithol rubines, chrome yellows, cadmium
yellows, diarylide yellows, iron blue, phthalocyanine blue, as well as many
other compounds including metal lies and flourescents. Chrome yellows
are being phased out because of their lead content and cadmium yellows are
generally used only in some specialty products like decorative laminates
because of their extreme light-fastness. Toxicity concerns in gravure inks
are discussed in greater detail by Surgeon (ref. 7), Bassemir (ref. 8) and
Zak (ref. 9). The basic requirement of a gravure ink is that it be free
flowing. This is necessary so that it can be pumped through the ink lines
to the ink fountain, in order to readily enter and leave the etched cells of
the gravure cylinder, and be wiped cleanly under the doctor blade. Gravure
inks must transfer readily to the paper or film, without mottle, and have
adequate opacity or transparency and coverage. The ink must dry completely
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on the substrate under normal press operating conditions, but must not dry in
the cells of the gravure cylinder. The dried print must fulfill the specific
requirements determined by the nature of the printed product, whether it be
a magazine, a food package, a gift wrap, etc.
The binder is the solid component of the gravure ink vehicle. It serves
to lock the pigment to the substrate, as well as to protect the pigment from
heat, moisture, and abrasion. Resins of various types, both natural and
synthetic, are generally used as binders. In brown or black inks, gilsonite
serves both as a binder and coloring agent. Zinc calcium resinates are
generally used as binders for low-cost, high-speed publication inks, using
inexpensive aliphatic hydrocarbon solvents. Ink for packaging, specialty
printing, and coating may be formulated from a wide variety of resins
including nitrocellulose, ethyl cellulose, polyamides, chlorinated rubbers,
and water emulsions or latices.
The solvent, which together with the binder makes up the ink vehicle,
is chosen for its ability to dissolve the binder and to provide the fluid
properties necessary for good inking, doctoring, ink transfer, and drying.
The solvent must dry rapidly by evaporation, leaving a dry pigment
binder film on the surface of the paper. Typical gravure solvents include
alcohols, aliphatic naphthas, aromatic hydrocarbons, esters, glycol-ethers,
ketones, nitroparaffins, and water.
Forced air dryers operating at low temperature (100° to 250° F) between
the printing units of the gravure printing press are used to dry the ink.
The solvent-laden air ideally can be directed through an activated carbon
bed where the solvent is adsorbed and recovered for further use. This is the
avenue for control of air pollution that is favored for publication gravure
presses. A large system has been in operation at Triangle Publications,
Inc., in Philadelphia for more than 25 years and in recent years has been
expanded to recover over 10,000,000 pounds of solvent annually (ref. 10).
While a number of publication gravure plants continue to operate temporarily
by reformulating inks with Rule 66-type exempt solvents, a considerable num-
ber of solvent recovery systems have been installed in the last few years
and others are being installed or are planned for installation in the near
future (ref. 11). All new publication gravure plants are being designed to
include solvent recovery, which is ecologically sound, and with increased
hydrocarbon costs, economically justifiable.
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In contrast to publication gravure where the same ink-solvent formula-
tion is used routinely day after day, the packaging and specialty gvavure
printer must contend with a wide range of solvents depending on the substrate
to be printed. Fume incineration may be required to dispose of solvent
emissions in this case, as discussed by Rappolt (ref. 12). Packaging and
specialty gravure printers are proceeding with programs to attain compliance
with emission regulations, but the technological, economic, and energy prob-
lems being encountered are considerable, as indicated by Sallee (ref. 13).
Some of the smaller gravure printers, although willing, may have neither
the technical expertise nor the economic resources to come into compliance
within the scheduled deadlines. The gravure industry's environmental pro-
gram was set up in recognition of their possible need for assistance.
GRAVURE INDUSTRY'S ENVIRONMENTAL PROGRAM
In response to the challenges presented to the gravure industry by the
Clean Air Amendments Act of 1970, the Federal Water Pollution Control Act of
1972, and the OSHA Act of 1970, a joint gravure environmental control and
occupational safety program was set up in an agreement entered into on
July 12, 1972, by the Gravure Technical Association and the Gravure Research
Institute. The agreement recognized the two very different characteristics
of GTA and GRI and capitalized on the strength of each organization. The
program had as its objective initially the accomplishment of six goals
(ref. 14).
1. Gravure Environmental and OSHA Newsletter
First we wanted to set up an information clearinghouse and library for
all the relevant environmental information, publications, data from the
government, and other sources that might be of concern to gravure printers
and engravers. Among the many references and periodicals now available in
the Gravure Environmental OSHA Library, established at the GRI laboratories
in Port Washington, L. I., New York, are the Federal Register and publica-
tions from EPA, both Federal and State; NIOSH; OSHA; ACGIH; AIHA; ASTM; ANSI;
NFPA; HEW; ECB; BNA; CCH; NSF; and others. These publications are reviewed
continuously by a full-time librarian and the GRI technical staff for devel-
opments of concern to the gravure industry. The output of this effort is the
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Gravure Environmental and OSHA Newsletter, which serves as the communications
link between the information clearinghouse and the members of 6TA and GRI
within the gravure industry. To date, six issues of the Gravure Environ-
mental and OSHA Newsletter, totaling 430 pages, have been published and the
Newsletter is serving a very useful purpose. Some examples of the variety
of subject matter covered in the Newsletter are hearing conservation, noise
control on the gravure press, electrical equipment in hazardous locations,
solvent storage in the gravure pressroom, etc.
2. Gravure Environmental Control and OSHA Seminars
Our second goal was to organize and conduct seminars and meetings on
environmental and safety matters. Four well-attended seminars and a
Materials Shortage Roundtable have been held to date. Speakers from EPA,
OSHA, NIOSH, and the gravure industry itself and its suppliers have
contributed to the success of these meetings. The full proceedings of each
meeting have been published in the Newsletter together with other articles
relating to important developments in the environmental and worker safety
and health fields.
3. Environmental Laboratory and Technical Service Program
Our third goal was to set up a gravure environmental laboratory at
Gravure Research Institute with the instrumentation needed for the environ-
mental control and worker safety-related measurements required in current.
and anticipated future legislation. Incladed in the environmental labora-
tory equipment are a Perkin-Elmer model 900 gas chromatograph, Model 107
atomic absorption spectrophotometer, sampling tube instruments, explo^imeter,
various personal monitoring pumps for hazardous conditions, stack emission
sampling apparatus, audiodosimeters, an octave band analyzer, noise measur-
ing instruments and various other instruments. Using this unique laboratory
facility, a technical service program for the gravure industry has been
established and is functioning in the following areas described by Shah
(ref. 15).
a. Occupational exposure to hazardous materials such as organic sol-
vents and metallic air contaminants.
b. Air pollution studies of solvent vapor emissions from gravure
press stacks and from other plant areas.
c. Waste water analysis for metallic pollution, organic solvents,
and other pollution.
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d. Noise level measurements and audiodosimeter surveys of worker
exposure to noise.
Among the technical services that have been performed are measurement
of hydrocarbon emissions from packaging and publication gravure plants to
provide data required for installation of solvent recovery systems, personnel
monitoring for exposure to chromic acid in gravure plating operations,
personnel monitoring for exposure to toluene and other solvents, personnel
monitoring for exposure to noise, consultation on air pollution regulations,
solvent storage, electrical equipment in hazardous locations, and a wide
range of other environmental and OSHA questions.
4. Environmental Research and Development
Our fourth goal was for GRI to conduct research and development directed
toward finding solutions to environmental and safety problems faced by
gravure printers. Development of an organic solvent emission sampling and
analysis procedure for gravure, as described by Shah and George, is an
example of this activity (ref. 16). While GRI is not in a position to
evaluate health effects of various toxic substances used in gravure, it is
encouraging medical studies done by gravure printers here and abroad in
these areas, such as that reported by Kunz on the influence of toluene on
the health of rotogravure workers (ref. 17). Development of water-base inks
is another active research area.
5. Spokesman for Industry
A fifth and most important goal of the program is to act as a spokesman
for the gravure industry on environmental and OSHA matters. In this connec-
tion GRI and GTA representatives have participated in regulatory hearings in
various areas and both organizations have actively supported the work of the
Environmental Conservation Board of the Graphic Communications Industry,
which was organized to represent the entire printing and graphic arts indus-
try in such matters and has responded in a number of vital areas, such as
toluene exposure criteria, proposed noise regulations, and others.
6. Joint Steering Committee
The sixth and final goal of the agreement was to establish a joint
steering committee to guide the five activities mentioned previously. We
were fortunate to have an outstanding individual, a chairman of this commit-
tee, Donald C. Cieber, of The Denver Post, Inc., who encouraged and guided
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the program from its inception. Mr. Cieber is now President of Gravure
Research Institute.
In conclusion, I think you can well agree that the gravure industry has
a substantial commitment toward providing a safe and healthy workplace for
its employees and to controlling the byproducts from its operations to avoid
environmental contamination.
REFERENCES
1. "Gravure Printing," Harvey F. George, Kenneth W. Britt. Handbook of Pulp
and Paper Technology, Van Nostrand Reinhold Company, 1970, pp. 683-688.
2. "Survey of Gravure Printing Through 1971," Gravure Magazine, April 1972,
pp. 30-38.
3. "The Gravure Industry—Size, Growth and Forecast," Charles R. Cook,
U.S. Bureau of Domestic Commerce, GTA Bulletin, Vol. XXV, No. 2,
(Summer 1974), pp. 62-67.
4. "Gravure Survey," Robert P. Long and Warren R. Daum, Package Printing
and Diecutting, January 1975, pp. 12-14.
5. "Heavy Metals in Water Pollution," John Michael, Armotek Industries,
Inc., Pollution Advisory Service, Gravure Environmental and OSHA News-
letter, No. 2 (February 1973), pp. 63-75.
6. "The New York News-Newspoint Wastewater Treatment," A. M. Lubell,
Pollution Control Division, The New York News, Gravure Environmental
and OSHA Newsletter, No. 5 (June 1974), pp. 65-70.
7. "Toxicity Concerns in Publication Gravure Inks," Walter R. Surgeon,
General Printing Ink Division, Sun Chemical Corporation, Gravure
Environmental and OSHA Newsletter. No. 2 (February 1973), pp. 75-82.
8. "Toxicity Concerns in Printing Inks," Robert W. Bassemir, General
Printing Ink Division, Sun Chemical Corporation, Gravure Environmental
and OSHA Newsletter, No. 2 (February 1973), pp. 82-85.
9. "Packaging Inks and Lead—A Brief Status Review," William J. Zak, Thiele
Engdahl, Inc., Gravure Environmental and OSHA Newsletter, No. 2 (February
1973), pp. 85-88.
10. "Solvent Recovery Systems," W. J. Barth, Inmont Corporation, Gravure
Environmental and OSHA Newsletter, No. 2 (February 1973), pp. 99-101.
11. "Air Pollution Control Program at Standard Gravure," James K. Anderson,
Gravure Environmental and OSHA Newsletter, No. 4 (November 1973),
pp. 36-37.
12. "Conservation and Incineration," J. R. Rappolt, Bobst Champlain, Inc.,
Gravure Environmental and OSHA Newsletter, No. 4 (November 1973),
pp. 37-43.
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13. "Air Pollution Control Program at American Can Company," Dr. Elgin D.
Sal lee, American Can Company, Gravure Environmental and OSHA Newsletter,
No. 4 (November 1973), pp. 43-49.
14. "What 6RI and GTA Are Doing To Help Gravure Printers Comply With Environ-
mental Legislation," Harvey F. George, Gravure Research Institute,
Gravure Environmental and OSHA Newsletter, No. 4 (November 1973),
pp. 22-26.
15. "Gravure OSHA and Environmental Technical Service Program," Jay Shah,
Gravure Research Institute, Gravure Environmental and OSHA Newsletter,
No. 6 (May 1975), pp. 31-37.
16. "Organic Solvent Emission Sampling and Analysis Procedure for Gravure,"
Jay Shah and Harvey F. George, Gravure Research Institute, 1974 TAGA
Proceedings, pp. 103-115.
17. "The Influence of Toluene on the Health of Rotogravure Workers," Dr.
Werner Kunz, Burda GmbH, Gravure Congress 1975, Berlin, Germany,
Gravure Environmental and OSHA Newsletter, No. 6 (May 1975), pp. 58-60.
DISCUSSION
MR. E. J. HEISER (Dow Chemical, U.S.A., Midland, Michigan): What is the
status on the water-base inks?
MR. GEORGE: Water-base inks are in regular production use in some packag-
ing and specialty applications, such as sugar bags, for example. How-
ever, for long-run publication-type work, water-base inks have not yet
been developed to the point where they are as suitable as the hydro-
carbon-type inks in terms of their usefulness, their ability to run at
high production speed and to give the desired film properties, and
their cost. However, this is a very active research area. And it has
the obvious potential of eliminating a big source of air pollution.
MR. W. N. FINGLAND (International Paper Company, Clinton, Iowa): You
mentioned, very briefly, wastewater analysis by GRI. Are you doing
this for members?
MR. GEORGE: Yes, we are.
MR. FINGLAND; I would like to learn more about that. Can you comment some
more on it.
MR. GEORGE: We have the equipment and the capability to do wastewater
analysis for our members, particularly for heavy metal contamination.
This is done on a technical service basis. I will certainly be glad
to talk to you about it in further detail.
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STORAGE AND HANDLING OF FLAMMABLE AND TOXIC CHEMICALS
Josef F. Heller*
Abstract
With the 1975 Fire Prevention Week (October 5-11) nearly upon us,
we felt this subject would be appropriate for most of our plants, but
also at home. The National Fire Protection Association defines a flammable
liquid as any liquid having a flash point below 140° F and a vapor pressure
not exceeding 100° F. On the other hand, combustible liquids have flash
points between 140° F and 200° F. These liquids vaporize and form flammable
mixtures when in open containers, when heated, or when leaks or spills occur.
The vapors are what burn if ignited; therefore, closed containers (safety
cans) should be used when storing small quantities of the materials, and
should have adequate ventilation and grounding.
Many flammable liquids and their vapors can create health hazards
from surface contact and inhalation of toxic vapors. These vapors are
heavier than air, and therefore seek the lowest levels possible—for
instance, tanks. Tanks should always be checked for combustible and toxic
vapors prior to entry. Adequate measures must be taken to reduce exposures.
The following 10 questions provide a checklist for the storage and
handling of combustible or flammable mixtures: 1) Are control valves
identified by color, tag, or both on all equipment containing flammable
liquids? 2) Are safety cans labelled of contents and do they include flame
arrestors? S) Are dispensing drums equipped with a bung vent, spring-
loaded safety faucet, and drip cans with flame arrestor screens? 4) Are
containers and equipment grounded and bonded? 5) Are downspouts long
enough to reach tank bottom used when loading and unloading operations?
6) Are Hazardous Work Permits used for tank entry, welding, and forklift
entry? 7) Is floor clean of drips, spills, and trash? 8) Is grounding
integrity OK to earth ground? 9) Are oily waster or solvent-soaked rags
stored in a self-enclosing metal container? 10) Are explosion-proof
*Safety and Security Engineer, Safety Division, Borden Chemical,
Division of Borden Inc., Columbus, Ohio 43215.
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electric switches and equipment in good condition?
Should any of the items in the checklist above occur in your plant,
please advise your immediate supervisor. To protect your home, plant,
and job, let us continue to perform our jobs in a safe manner. You have
a lot at stake to protect—your job...your life.
Introduction
In just a few weeks, we will be contributing our ideas and concerns
to the 1975 National Fire Prevention Week, October 5-11. For this reason,
I feel my topic should lend spme interest to the seminar and hopefully
provide some safeguard measures you can take back to your work environments,
whether it be printing ink manufacturing or the printing industry.
It is probably appropriate to first give you a few definitions. The
National Fire Protection Association defines a flammable liquid as any
liquid having a flash point* below 140° F and a vapor pressure not exceed-
ing 40 psia at 100° F. Flammable liquids are usually subdivided into
classes. Combustible liquids are those with flash points in the range of
140° F to 200° F. Although they do not ignite as easily as flammable
liquids, they can ignite under certain conditions or circumstances, and so
must be handled with caution.
Flammable liquids vaporize and form flammable mixtures when in open
containers, when leaks or spills occur, or when heated. The degree of
danger is determined largely by the flash point of the liquid, the concen-
tration of vapors in the air, and the possibility of a source of ignition;
at or above a temperature sufficient to cause the mixture to burst into
f1ames.
It is not the liquids themselves that burn or explode, but rather the
vapor/air mixture formed when they evaporate. Therefore, handling and
storing these liquids in closed containers and avoiding exposure of low-
flash liquids in use are of fundamental importance.
*A flash point of a liquid is the lowest temperature at which it gives
off enough vapor to form flammable mixtures with the air and to produce
a flame when a source of ignition is brought close.
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The extremes of vapor or gas concentration with air which, if
ignited, will just propagate flame, are known as the "lower" and "upper"
flammable limits and are commonly expressed in terms of percentages in the
lower or upper explosive limits (LEL or UEL). I doubt that any one of
you here today has a plant atmosphere entirely free of fire and explosion
hazards involving flammable liquids.
Earlier I spoke of classifications of flammable liquids and these
are as follows:
Class I - Liquids with flash points below 100° F:
Class 1A - Flash point below 73° F and having a
boiling point below 100° F (I.e., rotogravure and solvent
flexographic inks).
Class IB - Flash point below 73° F and having a
boiling point above 100° F.
Class 1C - Flash point at or above 73° F and below
100° F.
Class II - Liquids with flash points at or above 100° F and below
140° F (I.e., make-ready inks or specialized inks).
Class III - Combustible liquids with flash point above 140° F and
below 200° F (i.e., a few offset inks).
General Safety Measures in Storage and Handling
Accidental mixture of flammable liquids should be prevented, for it
may, upon later use, release vapors of its lower flash point and act as a
fuse to ignite the higher flash point material.
Control valves on equipment containing flammable liquids should be
Identified by color, tag, or both. Color coded piping, as directed by
Federal or State OSHA agencies, indicating direction of flow is most
Important so as not to cause confusion or a serious incident. Manifold
lines from tanks of different products should not be used; separate pumps
for different products should be provided.
Portable containers of Class I and II liquids should be provided
1n the form of approved safety cans with flame arrestors in the vent or
opening. Safety cans should also be provided, with yellow bands and
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identification lettering placed on them so as to reserve certain containers
for their respective liquids and to help reduce the chance of liquids being
mixed. Drums dispensing flammables should also be equipped with flame
arrester bung vents and spring-loaded safety faucets and drip cans.
Flammable liquid drum storage, both indoor and outdoor, presents a
serious fire and explosion hazard. It is crucial to provide safe storage
facilities. The safest practice is to store flammable liquids in buried
tanks out of doors and to pump the liquid through a closed piping system
to the point of use with an approved pump equipped with an automatic flow
control to stop liquid flow in case of emergency. In the case of above-
ground tanks, diking would be necessary. This is standard recommended
practice where liquids are delivered by tank truck or tank car. Flammable
liquids in unopened, containers offer a moderate hazard, but when metal drums
are exposed to fire, they become dangerous and could burst with explosive
violence. Fifteen percent of all industrial fires and explosions involve the
storage and handling of flammable liquids.
Indoor storage should include:
1. Automatic sprinklers—extra hazard pipe schedule
or 25 gal/min per 5,000 sq. ft;
2. Curbing, ramps, or grating--covered trenches at
floor opening in walls;
3. Low-level exhaust ventilation;
4. Explosion-proof electrics and adequate bonding; and liquids a
5. Adequate drainage leading to a safe disposal point.
Smoking and carrying matches, lighters, and other spark-producing
devices should not be permitted in a building or area where flammable
liquids are stored, handled, used, or where loading and unloading opera-
tions are performed. The extent of the restricted areas depends on the
type of products handled, the design of the building, and, of course,
State and local conditions.
Static Electricity
Static electricity is a motionless charge generated by the contact
and separation of dissimilar material. For example, static electricity
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is created when a fluid flows through a pipe or from an orifice into a tank.
The principal hazards created by static are those of fire and explo-
sion caused by spark discharges of accumulated electric charges in the
presence of flammable or explosive vapors or gases. A spark between two
bodies occurs when there is not a good electrically conductive path
between them. Therefore, it is necessary to ground and bond flammable
liquid containers in order to prevent static electricity from causing a
spark. Points of great danger from a static spark are those places where
flammable vapor may be present in the air, such as the outlet of a
flammable liquid fill pipe, a delivery hose nozzle, near an open container
of flammable liquid, and around a tank truck fill opening or barrel bung-
hole.
The terms bonding and grounding are often used interchangeably because
of poor understanding of their functions. Bonding is done to eliminate a
difference in potential between objects. The purpose of grounding is to
eliminate a difference in potential between an object and ground.
To avoid a spark from discharge of static electricity during filling
operations, a wire bond should be provided between the storage container
and the container being filled. For additional safety, it is advisable to
have the bonding wire on one of the containers grounded. When loading or
unloading tank cars through open domes, it is best to use a downspout long
enough to reach the tank bottom.
Friction sparks from metal tools are also possible. Spark-resistant
tools should be used in the presence of flammable vapors.
Ventilation
Ventilation is an essential safeguard against flammable liquid fires
and combustible explosions. With many flammable liquids, ventilation is also
a vital health safety measure. Usually, the ventilation required for health
safety is more than enough for fire and explosion safety.
Toxic Effects
Flammable liquids and their vapors may create health hazards from
both surface contact and inhalation of toxic vapors. Inflammation results
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from the solvent action of many flammable liquids on the natural skin oils
and tissue. A toxic hazard of varying degree exists in practically all
cases, depending on the concentration of the vapor.
Many flammable vapors are heavier than air and will seek low points
such as elevator pits, tank openings, and confined areas, which then con-
taminate the normal air and cause a toxic atmosphere. Oxygen deficiency
occurs in containers that have been closed for a long time, e.g., tanks.
All containers should be air- and gas-tested before entry.
Combustible Gas Indicators
Unless tests prove otherwise, flammable and toxic mixtures should be
assumed to be present in all tanks that at any time have contained or have
been exposed to flammable liquids. Tests for flammable vapor-air mixtures
in tanks or other vessels may be made by chemical analysis of samples or
with a combustible gas indicator, and usually may be read in terms of lower
explosive limit (LEL).
A tank, tested before being cleaned, may be found vapor-free. However,
if it contains scale or sludge, flammable liquids and vapor may be released
as soon as the sludge or scale is disturbed. A safe rule to follow is that
no tank should be considered free from the possibility of dangerous vapors
as long as it contains scale or sludge.
Many companies use a written permit form when it is necessary for men
to enter vessels that have contained flammable liquids or to do "hot work"
repairs in them. We at Borden call our forms Hazardous Work Permits.
The criteria of safety relating to toxic hazards are not so strictly
defineable as limits of flammability. Threshold Limit Values (TLV) based
on past experience are published by many authorities. One of the best
sources is Documentation of the Threshold Limit Value for Substances in
Workroom.* Threshold limit values refer to airborne concentrations of
substances to which nearly all workers may be repeatedly exposed day after
day without adverse effect. Whereas the lower limits of flammability of
most organic vapors are not less than 0.5 percent by volume, many substances
*Third edition, 1971, American Conference of Governmental Industrial
Hygienists, P.O. Box 1937, Cincinnati, Ohio 45201.
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are toxic in the parts per million range. Threshold limit values refer to
time-weighted airborne concentrations of substances for an 8-hour workday
and 40-hour work week. They should be used as guides in the control of
health hazards.
One way to aid in this control is through the use of ventilation. To
some, the placing of a fan to blow the vapors around and disperse it or to
put a window fan near the location where the vapor is produced means venti-
lation. Generally, a ventilation system means exhaust fans with hoods and
ductwork and makeup air to replace that being exhausted. It is wise to
check when a ventilation system has been installed and to keep a running
record of how it works. This can be done by periodically remeasuring air
velocities at designated points and noting whether the system is functioning
as well as it did when it was installed. Fans get dirty and lose blades;
ductwork gets holes punched in it; fan belts loosen or break; all these
lessen the efficiency of a ventilation system. Caution must be taken
during cleaning, renovating, and reinstalling of fan motors as often mis-
wiring occurs and fans push rather than pull. Watch for location of ex-
haust and intake for air conditioning or makeup air. Where ventilation
cannot reduce air contaminates, it may be necessary to use respirators,
self-contained breathing apparatus, or continuous-flow air supply.
Federal and State standards determine the levels of air concentra-
tions an employee may be exposed to, at or above the action level, where
action level is defined as one-half the permissible exposure level. If
dealing with toxic materials like VCM and operating above the action
level, recordkeeping and monitoring are required.
Recently, the Federal Government has issued proposed rules for toxic
substances involving ketones. The proposed standards, if adopted, will
establish requirements for measuring employee exposures, medical surveil-
lance, methods of compliance, handling and use, employee training, record-
keeping, and so on.
Methyl ethyl ketone (MEK) is one solvent probably used in some quantity
by each of you. If the proposed rules are approved, employer controls
would be required for employees exposed to average airborne concentrations
of MEK in excess of 200 ppm over an 8-hour work shift. These controls in-
clude exposure determination and measurement training and information,
medical surveillance, personal protective equipment, improvements in the
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prevention and cleanup of spills and in monitoring disposals, and of course,
recordkeeping. Approval of the proposed rules could also involve the use
of engineering and work practice controls to reduce exposures to the per-
missible exposure levels or below. These are just a few of the proposed
controls for toxic substances, and you can be sure there will be more.
Conclusion
I have tried to keep this simple and to the point. I hope you can
benefit from what has been said on toxic and flammable chemicals used in the
industry. There is a big job to be done, and it is time to get on with the
job.
REFERENCES
1. Fire Protection Handbook, revised 13th edition, National Fire
Protection Association, Boston, 1969.
2. National Electrical Code, National Fire Protection Association,
Boston, 1975 edition.
3. Printing and Litho Inks, 5th edition, MacNair-Dorland Co., New
York, 1957.
4. Bulletin No. 3, Flammable Liquid Hazards in the Plastics Industry,
Committee on Safety & Loss Prevention, The Society of the Plastics
Industry, Inc., New York, 1973.
5. Handbook of Industrial Loss Prevention, Factory Mutual Engineering
Association, McGraw-Hill, Inc., Hightstown, NJ.
DISCUSSION
DR. WILLIAM S. BE6GS (New Jersey Department of Environmental Protection,
Trenton, New Jersey): I wonder if you could tell us what adverse
effects the ketones have been found to provide. You mentioned methyl
ethyl ketone.
MR. HELLER: Right.
MR. BEGGS: Can you tell us something about the effects of it?
MR. HELLER: The question is, what are the effects of methyl ethyl ketone?
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To date, there has not been, to my knowledge, any substantial infor-
mation to pinpoint the exact effects of ketones like those of the
standards of VCM, vinylchloride monomer. There are hearings going on
in Washington at the moment on the full ketone standards being pro-
posed. Industry is really going back and forth with this as to what
will be done. Who really knows? I think that there are going to be
some limitations on the MEK, but what the standard outcome will be, I
cannot say at this point. I expect that probably we will hear some-
thing around the first of the year or right after the first of the
year.
MR. ALVIN SALTZMAN (New Jersey Bureau of Solid Waste Management, Trenton,
New Jersey): With regard to methyl ethyl ketone, is the problem mainly
with breathing or does it affect the contact with skin?
MR. HELLER: It is both. It is contact with the skin and also the breath-
ing atmosphere that the proposed standard is referring to.
MR. SALTZMAN: Thank you very much.
MR. HELLER: Some people in industry are presently almost bathing in the
MEK material. And what they are proposing there is a protective cream
and gloves to use instead of--
MR. SALTZMAN: Yes, I am aware of that. That is why I posed the question.
I know that everyone—a lot of people—are using it. They have their
hands right in it. They are doing it every day.
MR. HELLER; You should have either a protective cream or probably both
protective cream and gloves, but some gloves will break down with the
solvent material.
MR. WILLIAM A. MA6IE (Magie Brothers Oil Company, Franklin Park, Illinois):
I think that in the Federal Register they have changed the definition
of flammable to 100°, and combustible under 200° instead of 140°.
MR. HELLER: You are right. I'm sorry. I was citing the definition by the
NFPA. That was OSHA. Those who may be familiar with the Department
of Transportation regulations, these are also a little bit different.
They are trying to be all brought into one particular standard, which
I foresee in the near future.
CHAIRMAN SCHAEFFER: Any other questions?
MR. JOHN H. SOMMER (General Formulations Co., Div. of General Research,
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Inc., Sparta, Michigan): I'd like to add a little something about
static. We do a lot of dissolving and pre- and post-mixing from
milling operations. We find that when we put a can under the dissolver,
we develop a high rate of static electricity, probably on the order of
30,000 to 50,000 volts. So we ground the mixing tank.
MR. HELLER: Grounding the mixing tank will do it. If you are flowing
anything from that tank to another container, you can break down the
static charge by using some nonconductive material or hose to drop
it through rather than a gravity flow; you can drop it through a
closed system. There are flexible materials that will move from one
area to another.
CHAIRMAN SCHAEFFER: Are there any other questions?
MR. A. MERLE SCHNITZER: (Phillips Petroleum Company, Bartlesville,
Oklahoma): There are some additives that are available which can be
added to some of the combustible material; I am not sure about the
flammables, which tend to overcome the static electricity. There are
agents that are used in jet fuels for fueling of aircraft. So this
might be an angle you might want to look into if you have a problem
in that respect.
The draft standards for ketones were mentioned, and although this
is an EPA meeting, I think that everyone should be aware of the re-
quirements that are being proposed in the OSHA area. They eventually
will cover all of the materials that are listed in OSHA's table, in
Section 1910. This is about 300 or 400 chemicals. It is going to be
an enormous administrative task to keep up with. And everyone who
handles these chemicals is going to be involved.
You have the opportunity of commenting upon these draft standards
and it might be worth your while to look into them. The costs are
going to be rather sizable, particularly if they apply to materials
they really do not present that much of a problem. It is important
that we concentrate on the real hazards and not spend a lot of time
and effort and money where the problem really is not that great.
The vinylchloride thing is a real problem, and attention is being
given to that but the costs in complying with these are going to be
substantial. I don't think that industry or printing companies are
226
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going to be able to bear the entire burden. So the costs are going to
have to be passed on to the consumer. That needs to be understood.
Another point is that in these draft standards you are required
to set up certain surveillance at a level of half the TLV value. In
other words, if you are at half, say, you are going to have to go
into a surveillance program. And there are people who think this
should not be required until you are at the TLV value, which is con-
sidered to be the safe value.
MR. HELLER: Half the TLV value or permissible exposure value is usually
referred to as the action level.
227
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HEAVY METAL CONTAMINATION IN PRINTING PAPERS
Robert W. Praskievicz*
and S. S. Y. Subt
Abe tract
A method is described in which samples of printing papers are analyzed
for trace contaminations of selected heavy metals. Three major categories
of paper samples were tested, one of which was paper made entirely from
or partially from recycled fibers. Recycled papers showed higher levels
of chromium, copper, lead, and nickel contamination than did papers made
from virgin pulp. Kraft wrapping papers made mainly from unbleached kraft
pulp showed the highest levels of cadmium and manganese contamination. A
"typical" printing paper is defined in terms of ranges of impurities.
About 80 percent of the samples tested fall within these limits. Pre-
cision studies showed chromium, copper, manganese, and lead to be evenly
distributed in the samples, while cadmium and nickel were not distributed
uniformly.
INTRODUCTION
Work has been published treating separately the topics of determin-
ing the inorganic impurities in cellulose by atomic absorption spectros-
copy (ref. 1) and of the use of the graphite furnace atomizer and atomic
absorption spectroscopy to detect and measure metallic elements.
In this study, trace amounts of selected metallic impurities in
printing paper are determined by the use of the graphite furnace. This
investigation utilizes the general method of preparing the paper samples
for analysis as described in a proposed revision of the Technical Associ-
ation of Pulp and Paper Industry (TAPPI) Standard Method, T-436. This
proposed revision expands the procedure to include other metals.
Use of the graphite furnace offers the ability to detect minute
amounts of heavy metal contaminants by using samples only a few tenths
*Robert W. Praskievicz, Chemist, Quality Control and Technical
Department, U. S. Government Printing Office, Washington, O.C.
228
-------
of a gram in size. In this study an attempt is made not only to measure
the amount of contamination but also to observe the distribution of the
types of metals found in different kinds of paper.
Of particular interest are the heavy metal contaminants in the in-
creasingly used recycled papers. The trend today is to define recycled
papers as those which contain "post-consumer waste," i.e., paper that
has been through its intended purpose, as distinguished from reclaimed
fibers, which are obtained from waste collected as a result of an agri-
cultural or manufacturing process and which include materials generated
from and reused within a paper mill as part of its own papermaking process
or as waste from a printing plant. Before most waste papers are suitable
for recycling into printing papers, they must be treated to remove ob-
jectionable ink and other foreign materials.
In this project we investigated several recycled papers for foreign
materials, specifically the heavy metals Cd, Cr, Cu, Mn, Ni, and Pb, and
compared their concentrations to those found in other groups of printing
papers.
EXPERIMENTAL
Sample treatment
All glassware used in this study was washed with concentrated or 1:1
nitric acid and then received successive rinsings with distilled and
deionized water. A.C.S.-grade reagents were used throughout. The sample
size used was 0.25 g. Pieces of each sample approximately 1 cm2 in size
were soaked in 5 ml of 30 percent hydrogen peroxide solution. They were
then carefully added, using polyethylene tongs, to a heated mixture of
10 ml concentrated sulfuric acid and 5 ml 30 percent hydrogen peroxide.
After the entire sample was dissolved, it was heated to dense fumes and
allowed to cool. If the residual liquid was brown or cloudy, an extra
2 to 3 ml of 30 percent hydrogen peroxide solution was added, and the
sample was reheated to dense fumes. This procedure was repeated until
the residual liquid was clear or colorless. The sample was then cooled
with ice and diluted with approximately 40 ml of deionized water. Then
20 ml of concentrated ammonium hydroxide were added dropwise to raise the
229
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pH to approximately 2. After filtering through #541 filter paper to re-
move any Si02 present, the sample was diluted to 100 ml with deionized
water.
Ash determinations were made by heating 2-gram samples in porcelain
crucibles to constant weight in a muffle furnace at 900° C.
Equipment
The instrument used was a Perkin-Elmer model 403 double-beam atomic
absorption spectrophotometer equipped with a model H6A-2100 graphite
furnace and a strip-chart recorder. Hollow cathode lamps were used for
each element. Introduction of the sample and standards was by means of
a 10-yl Eppendorf pi pet.
Instrument parameters
Instrumental parameters used were essentially the same as those recom-
mended by the manufacturer (ref. 2). Table 1 summarizes the conditions
used.
Table 1. Instrument parameters
Element
Hollow cathode
current
Wavelength
Slit width
Drying
temperature
Drying time
Charring
temperature
Charring time
Atomization
temperature
Atomization
time
Optimum working
range observed
Cd
8 ma
2288 A
0.7 nm
100° C.
10 s
500° C.
30 s
2100° C.
10 s
0.01
+0.10 ng
Cr
30 ma
3579 A
0.2 nm
100° C.
10 s
1100° C.
20 s
2700° C.
10 s
0.05
+1.0 ng
Cu
30 ma
3247 A
0.7 nm
100° C.
10 s
900° C.
20 s
2700° C.
10 s
0.05
+0.50 ng
Mn
30 ma
2795 A"
0.2 nm
100° C.
10 s
1100° C.
20 s
2700° C.
10 s
0.05
•+1.0 ng
Ni
30 ma
2320 A
0.2 nm
100° C.
10 s
1100° C.
20 s
2700° C.
10 s
0.20
-••1.0 ng
Pb
8 ma
2833 A
0.7 nm
100° C.
10 s
500° C.
30 s
2300° C.
10 s
0.05
+3.0 ng
230
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Standards and Calibration
Most standard solutions were prepared by diluting atomic absorption
standards of 1,000-ppm concentration available from Fisher Scientific
Company. The exceptions were lead, prepared from Pb(N03)2, and chromium,
prepared from K2Cr207.
Ideally, the graphite furnace response is calibrated using known con-
centrations of metals in aqueous or in very dilute (< 1 percent) acid
solution. The peak height or area of the recorder response is plotted
versus the concentration of the element being analyzed. However, when a
direct comparison is made between dilute aqueous standards and samples
having a complex matrix, as in this investigation, chemical interferences
may occur. Therefore, the calibration curve is run by adding known amounts
of each element to the sample. This is called the standard additions
method and is illustrated in figure 1 for chromium. If the slope for the
Response, mm
/ S^
* Standard )»
additions/
curve /
/
/
® •*• aqueous standards
14- sample /
alone /
0 0.2 0.4 0.6 0.8
ng Cr
Figure 1. Method of standard additions.
1.0
231
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standard additions curve is the same as the slope for the "standards only"
curve, then the samples can be analyzed by direct comparison with aqueous
standards. This relationship was studied for each of the six elements.
All results reported were obtained by comparing the sample solutions
directly with aqueous standards. In addition, the quantity of sample and
standard solutions injected into the graphite furnace was always 10 yl to
prevent any variations in signal due to volume effects.
RESULTS AND DISCUSSION
The results of analyzing 26 paper samples are grouped and shown in
tables 2 through 5.
These (4) groups include:
Group I One hundred percent bleached chemical wood paper.
This group of printing papers includes offset book
papers made from 100 percent virgin chemical wood
pulp.
Group II Recycled or partially recycled papers. This group
includes paper made from 100 percent recycled fibers
or some combination of recycled fibers with virgin
chemical wood pulp or with cotton fibers.
Group III Groundwood papers. In this category the papers are
made from a mixture of groundwood pulp, which is a
mechanically processed fiber, and chemically treated
chemical woodpulp.
Group IV Miscellaneous. This is the catch-all category con-
taining kraft papers (similar to grocery bags), a
hardened ashless #541 filter paper, and a 100 percent
cotton fiber paper. The outstanding feature in kraft
paper is that it contains some amount of unbleached
chemical wood pulp treated by the kraft process, which
gives this type of paper its strength characteristics.
Besides analyzing for the six heavy metals, the ash content was also
determined for each of the samples. The ash is indicative of the noncellu-
losic material or inorganic fillers found in each paper.
On examining the results, note that these heavy metals occur in de-
tectable quantities in every type of printing paper and that their concen-
trations vary over a large range. This is true even for the high-grade
100 percent rag content paper. Since a blank, ashless, acid-hardened
232
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Table 2. Group I: 100 percent bleached chemical wood papers
Element
(ppm or
yg/g sample)
Cd
Cr
Cu
Mn
Ni
Pb
Ash
Table 3.
Element
(ppm or
yg/g sample)
Cd
Cr
Cu
Mn
Ni
Pb
1
<0.2
5.9
5.1
2.1
8.8
2.3
10.0%
Group
9
<0.2
35.1
76.6
4.3
37.6
76.9
2
<0.2
6.9
6.4
1.0
11.0
1.0
3
<0.2
13.5
3.7
3.6
6.7
7.2
9.5% 12.0%
II:
10
<0.2
13.3
1.4
4.2
7.2
8.4
Recycled
11
<0.2
19.7
11.0
3.5
7.2
58.5
4
0.2
8.9
2.4
11.9
5.4
7.7
7.0%
5
<0.2
1.0
7.3
1.1
5.3
11.5
9.5%
6
<0.2
13.2
3.0
<1.0
15.5
2.9
12.0%
or partially recycled
12
<0.2
2.1
<1.0
21.8
<1.0
<1.0
13
<0.2
7.9
3.4
2.2
4.4
3.9
14
<0.2
20.0
<1.0
2.1
17.4
2.0
7
<0.2
14.5
2.6
2.8
14.9
5.5
16.5%
papers
15
<0.2
10.8
4.0
7.6
5.4
6.4
8
<0.2
10.8
1.8
10.6
16.2
5.8
14.5%
16
<0.2
3.1
2.5
<1.0
5.9
3.1
Ash 7.5% 9.5% 9.5% 9.0% 6.5% 21.5% 2.0% 3.0%
233
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Table 4. Group III: Groundwood papers
Element
(ppm or
pg/g sample)
Cd
Cr
Cu
Mn
Ni
Pb
Ash
22
<0.2
16.6
<1.0
13.0
14.7
<1.0
18.0%
23
<0.2
19.4
<1.0
12.1
10.5
<1.0
13.5%
24
<0.2
14.3
2.2
8.6
8.2
<1.0
8.5%
25 26*
<0.2 <0.2
<1.0 22.1
3.2 2.9
19.1 6.7
<1.0 6.2
<1.0 96.5
0.5% 5.5%
*26 can also be classified with the recycled papers.
Table 5. Group IV: Miscellaneous papers
Element
(ppm or
yg/g sample)
Cd
Cr
Cu
Mn
Ni
Pb
17
Kraft
3.5
10.7
2.2
51.5
1.3
35.9
18
Kraft
0.9
3.7
20.0
36.4
4.5
14.2
19
Kraft
0.2
1.8
8.4
37.4
4.1
3.0
20
Filter
paper
<0.2
<1.0
<1.0
<1.0
1.7
2.6
21
100%
rag
<0.2
4.3
5.2
<1.0
<1.0
2.4
Ash 2.0% 1.0% 0.5% <0.02% <0.5%
234
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filter paper was analyzed and found to contain some of the same heavy
metals, we suspect the impurities found in this paper may be from the acid-
hardening process (table 5, sample #20).
In table 6, the low, high, mean, and standard deviation are shown for
the contaminants of Groups I, II, and III, and an "overall" result is
given for the 26 samples analyzed. The results may not show any definite
or obvious conclusions, but with a closer examination there are some
interesting trends to be obtained from this study.
In general, for any group of paper samples containing inorganic fillers,
the nickel and chromium content is proportional to the filler content.
These fillers are added to improve the brightness and opacity. Except for
a few instances, these results are summarized in table 7.
Table 6. Summary of contaminants
Overall
Ash
Cd
Cr
Cu
Mn
N1
Pb
Low
<0.02
<0.2
<1.0
<1.0
<1.0
<1.0
<1.0
High
(ppm)
21.5
3.5
35.1
76.6
51.5
37.6
96.5
Mean
8.0
10.8
6.9
10.3
8.6
14.0
Std.
dev.
5.9
8.2
14.8
13.1
7.7
25.0
Group
Low
7.0
<0.2
1.0
1.8
<1.0
5.3
1.0
I: 100% bleached
chemical wood
High
(ppm)
16.5
0.2
14.5
7.3
10.6
16.2
11.5
Mean
11.4
9.3
4.0
4.3
10.5
5.5
Std.
dev.
3.0
4.6
2.0
4.4
4.6
3.4
Group II:
Low High
(ppm)
2.0 21.5
<0.2
2.1 35.1
<1.0 76.6
<1.0 21.8
<1.0 37.6
<1.0 76.9
Recycled
Mean
8.6
14.0
12.6
5.8
10.8
20.0
Std.
dev.
6.0
10.8
26.1
6.8
11.8
29.9
Group' III:
Low High
(ppm)
0.5 18.0
:0.2
<1.0 22.1
<1.0 2.9
6.7 19.1
<1.0 14.7
<1.0 96.5
Groundwood*
Mean
9.2
14.6
2.1
11.9
8.1
20.1
Std.
dev.
6.8
8.2
1.0
4.8
5.1
42.7
Mncludes sample #26, which may also be classified as a recycled paper.
Table 7. Offset book papers
Contaminants, average concentration, ppm
Ash content Cu Mn Pb Cr Ni
0-10%
> 10%
5.3
2.8
4.0
4.5
5.6
5.4
5.7
13.0
7.6
13.3
235
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Also, on the average, the higher quality printing papers (100 percent
bleached chemical wood fibers) contain the least amount of the sought-for
heavy metals except nickel (see table 6).
The cadmium levels were numerically low, only 4 out of 26 samples
showing a concentration of 0.2 ppm or better. Of particular interest is
that three of these four samples are kraft paper samples. These same
samples are also consistently high in manganese. Each was higher than the
maximum manganese concentration of 21.8 ppm observed in the other 22
samples.
Besides kraft papers, two other samples having a high manganese con-
tent are duplicator papers. One is composed of groundwood fibers and the
oth?r of recycled fibers. Excluding the kraft and duplicator-type paper
samples, the remaining 21 samples show a maximum manganese contamination
of 13.0 ppm.
Based on our results, a "typical printing paper" has heavy metal con-
taminants in the following concentrations: Cd, <0.2 ppm, Cr, <15 ppm,
Cu, <10 ppm, Mn, <15 ppm, Ni, <15 ppm, and Pb, <15 ppm. Approximately
80 percent of the paper samples analyzed fall within these limits.
But what about the remaining 20 percent of the papers? The high
concentrations of manganese and cadmium in kraft paper were noted earlier.
High concentrations of the remaining impurities—chromium, copper, nickel,
and lead--seem to be distributed among the papers with recycled fibers.
The heavy metal contamination among the recycled papers appears to
decrease as these papers are subjected to bleaching or other refining
processes that make the paper visually appealing. Samples #9 and #26
have low brightness and specks of foreign material giving a spotty "re-
cycled" appearance. These samples show some of the highest levels of Cr,
Cu, and Pb of all the samples tested. Conversely, samples #13, #14, #15,
and #16 had high brightness, a clean appearance, and low amounts of the
above impurities.
Studying the results for the nine recycled papers,* an interesting
observation is that none of these samples shows both a high manganese and
a high lead contamination. These elements were once commonly used in
^Including sample #26, which is composed of recycled and groundwood
fibers.
236
-------
combination in ink formulas as driers and one might suspect high concen-
trations of these two elements in recycled paper. Sample #10 is known
to be composed of de inked stock and had neither high Mn nor high Pb con-
centrations. Returning to samples #9 and #26, these two recycled papers
were detected to have the highest Pb contamination but to have a low con-
centration of Mn. Strangely enough, the combination of high Mn and high
Pb only occurs in the kraft paper samples.
Precision
Five replicate samples were wet-ashed and analyzed for each of the six
elements. A 100 percent recycled paper was selected for Cu, Cr, and Ni
precision studies. For Mn and Cd, a kraft wrapping paper was used. The
results obtained are shown in table 8. The precision for Cr, Cu, and Mn
Table 8. Results of five replicates
of the same paper sample
(ppm)
Replicate
sample
1
2
3
4
5
Cd
4.04
7.39
4.42
4.04
3.52
Cr
35.1
34.6
37.1
34.2
34.6
Cu
74.8
78.5
76.6
72.9
80.4
Mn
49.8
47.2
51.9
53.4
55.0
Ni
8.03
7.02
7.69
6.35
13.6
Pb
78.0
66.0
80.5
86.9
73.1
mean = x 4.682 35.12 76.64 51.46 8.538 76.90
variance = s2 2.394 1.327 8.743 9.348 8.423 61.86
standard
deviation = s 1.547 1.152 2.957 3.057 2.902 7.865
coefficient
of variation 33.1 3.28 3.86 5.94 34.0 10.2
= 100s
"x
(parts per
hundred)
237
-------
was relatively good, indicating that these elements are evenly distributed
throughout the samples. The relatively high variance for Cd, Pb, or Ni
indicates that these are not as uniformly distributed. To further impede
precise Ni determinations, the observed Ni content approaches the detection
limit of the instrument, where the signal to noise ratio is high. Under
the experimental conditions, the observed detection limit for a 0.25-g
sample is approximately 4 ppm, as compared to less than 0.5 ppm for copper.
CONCLUSION
This investigation was undertaken at the U. S. Government Printing
Office for several reasons, not the least of which was to develop data on
possible toxic materials in our products in order to provide answers to
increasingly numerous questions from Congress and Governmental agencies.
While some results may be surprising, they must be viewed in perspective.
The results of some of the heavy metal contaminants are numerically high
but the units are small. In the extreme case, it would require more than
10 kg (over 22 Ib) of paper to provide 1 g (1/28 ounce) of lead. For
comparison, the amount of lead permitted in coatings for children's toys
and furniture is 0.06 percent or 600 ppm (ref. 3). There is no question
that sources of toxic materials should be investigated, but all that one
can conclude from this study is that it would be prudent to investigate
how lead and other heavy metals get into consumer papers.
REFERENCES
1. 0. Ant-Wuorinen and A. Visapaa, The State Institute for Technical
Research, Finland, Determination of the Inorganic Impurities of
Cellulose by Atomic Absorption Spectrometry, reprint from Paperi Ja
Puu. Vol. 48, No. 11 (1966), pp. 649-656.
2. Analytical Methods for Atomic Absorption Spectrophotometry, Perkin-
Elmer Corporation, Norwalk, Connecticut, 1968.
3. "Rules and Regulations," title 16, chapter II, Consumer Product Safety
Commission, Part 1500 - Hazardous Substances and Articles; Adminis-
tration and Enforcement Regulations, Federal Register, Vol. 39,
No. 237 (December 9, 1974), p. 42902.
238
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DISCUSSION
MR. THEOPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
What was the sensitivity, if you can remember, for cadmium and lead?
MR. PRASKIEVICZ: In the case of cadmium, for a .25-g sample, we could
detect with pretty good precision down to about .2 ppm. We diluted
our samples to 100 ml. You could dilute some to a smaller volume
and increase your sensitivity. Or you could easily go to a larger
size sample. In fact, when we started the study, we were using 1-g
samples or higher, but we found that we had to dilute the samples for
most of these elements, to get them into the proper working range.
So, you could easily get down. I would not want to venture a guess,
but I would say maybe .02 ppm. I would say you could easily go 10
times below that with a scale expansion factor of 10.
MR. CARSON: I asked you that because we have seen much lower values from
a food additives standpoint than what you have given here.
MR. PRASKIEVICZ: Well —
MR. CARSON: Certainly for the safety of food additives we could not
tolerate that kind of a lead content.
MR. PRASKIEVICZ: As I say, this type of paper is not used for wrapping
food. These are strictly printing papers. This technique would
definitely be applicable to papers that do come in contact with food.
MR. JOHN SANDEFUR (Hallmark Cards, Kansas City, Missouri): The first
point was simply that the Consumer Products Safety Commission on
lead in coatings is a half-percent at this time, I believe.
MR. PRASKIEVICZ: Okay. Well, the figure that we used was out of the
Federal Register that appeared February 9, 1974. It did list .06
percent.
MR. SANDEFUR; That was dropped. I wanted to ask if on your initial paper
sample the weight was recorded on a dry basis?
MR. PRASKIEVICZ: The samples were equilibrated at a 50 percent relative
humidity. So they were not on a dry basis. They were at equilibrium
moisture.
MR. SANDEFUR: So you may be carrying several percent moisture?
239
-------
MR. PRASKIEVICZ: Probably. Another thing that could have affected some
of the precision results that we did have...
MR. SANDEFUR; Was background friction required?
MR. PRASKIEVICZ: No. We started out running with background correction,
but we found that most of these elements ran pretty well without it.
With this sample matrix there does not seem to be any problem with
background. At least we did not run into it.
MR. RONALD G. RAYNER (Department of Environmental Protection, Coventry,
Connecticut): In the industries that employ the inking process, did
you happen to notice the tendency toward fewer metals in those that
had the inking?
MR. PRASKIEVICZ: Well as I say, the only sample that we knew was actually
made from Dean stock, was that one sample that I pointed out to you.
The levels were fairly low. We are assuming that most of these other
recycled papers did use a certain amount of deinked stock. But of
course, this kind of information is not that easy to come by. For
the purpose of this study, we did not really go into any great details,
MR. RAYNER: You say for recycled paper. We have several industries that
employ recycling of papers, and one of them makes a filler for cor-
rugated medium, for cardboard boxes—a very cheap grade of paper,
not employing the kraft process. Did you also happen to notice a
tendency there for your IDS increase in being recirculated throughout
the system to develop into a higher metal concentration?
MR. PRASKIEVICZ: No, we did not investigate that.
MR. FRANCIS M. ALPISER (Environmental Protection Agency, Philadelphia,
Pennsylvania): I wonder if you analyzed any money? We have had
requests from the Treasury Department about burning money. That is
a fact in Washington, D.C. They want to burn it in an incinerator
with no kind of control. And I wonder what the metal content of
money is.
MR. PRASKIEVICZ: We do not print the money. That is the Bureau of En-
graving and Printing, but it would make an interesting study.
THE FLOOR: What category would you expect to find it in?
MR. PRASKIEVICZ: As I understand it, it is a ragtype of paper.
240
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MS. JACQUELINE M. FETSKO (Lehigh University, Bethlehem, Pennsylvania): I
gather that your measurements are on total lead. Are you planning any
studies of soluble lead? Leads must be acid-soluble to be absorbed into
the digestive tract of the body.
MR. PRASKIEVICZ: Right. That is definitely something to consider.
THE FLOOR: What was the question?
CHAIRMAN SCHAEFFER: Will you paraphrase, Bob?
MR. PRASKIEVICZ: I think the point she was trying to make was that some
forms of lead may not be soluble in the particular acid mixture that
we use here. So, that in--
CHAIRMAN SCHAEFFER: This was really an analysis of total lead. Have you
attempted to differentiate between soluble lead as opposed to total
lead, because of the acid involvement in the extractability for lead
ingestion and that potential danger?
MR. PRASKIEVICZ: No, we have not investigated that as yet.
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PROCESSING EFFLUENT CHARACTERISTICS OF DYCRIL*
PHOTOPOLYMER PRINTING PLATES
Ellen G. Mellingert
Abstract
The Du Pont Photo Products Department markets a whole family of letter-
press print-ing plates based on photopolymer technology. A photopolymer is
an organic plastic material that hardens and becomes insoluble when exposed
to UV radiation and which3 in the case of Dycril plates* has been bonded to
a rigid or flexible support* depending on the application. After exposure
Dycril plates are washed in dilute aqueous alkali. Several years ago a
program was undertaken to characterize the water pollution potential of the
Dycril washout effluent. The paper describes photopolymerization in general
terms and the Dycril printing plate exposure and washout process. The re-
sults of the Dycril effluent analysis are given and reviewed in light of
Federal regulations and municipal sewer system codes. It is concluded that
Dycril does not present a pollution problem when discharged to a municipal
sewer system.
INTRODUCTION
The Du Pont Company Photo Products Department sells Dycril platemaking
processes to various customers throughout the world. The processes are
based on photopolymer technology, representing a distinct environmental ad-
vantage over the metal-etching process and its attendant problems with zinc,
copper, and their salts. With increasing and continuing concern for the
environment, the Photo Products Department several years ago undertook a
program to characterize the water pollution potential of its Dycril photo-
polymer effluent.
*Dycril is a registered trademark of E. I. du Pont de Nemours & Co., Inc.,
Wilmington, Delaware.
tTechnologist, Photo Products Department, E. I. du Pont de Nemours & Co.,
Inc., Wilmington, Delaware.
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POLYMERIZATION/EXPOSURE STEP
In order to more fully understand photopolymer effluent, let us dis-
cuss in general terms what a photopolymer is, how it reacts, and what the
processing conditions are. A photopolymer is an organic plastic material
that is sensitive to UV radiation. In the cross section of a Dycril photo-
polymer plate (illustrated in figure 1), the photopolymer is the solid
layer, which has been bonded to a suitable support. The choice of support
is determined by the end use: rigid for flat bed or rotary letterpress and
flexible for wraparound letterpress and letterset printing. Thickness of
the photopolymer is also a function of the end use and varies from .010 in.
to .150 in.
The polymer layer in a typical plate contains an inert organic material
to give film-forming properties (this is the solid binder), a plasticizer
monomer (capable of forming a polymer), and a photoinitiator or catalyst to
give the required photo speed, plus other organic compounds in lesser amounts,
such as polymerization inhibitors for storage stability.
Dycril
Photopolymer
Bonding Layer
Metal or Polyester
Film Support
*Dycril is a registered trademark of E. I. du Pont de Nemours & Co.,
Inc., Wilmington, Delaware.
Figure 1. Dycril plate cross section.
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Synthetic polymers are formed by chemical reactions in which a large
number of small units (monomers) combine to form one large unit (the poly-
mer) as shown in figure 2. The source of energy for this reaction in Dycril
is ultraviolet radiation. When the plate is exposed the photoinitiator
triggers the linking and cross!inking of monomers to form a crosslinked
polymer with different physical properties, such as hardness and durability.
These modifications allow the polymer to withstand high pressure during
matting in the newspaper process. In other applications it provides the
plate with the necessary wear characteristics for long press runs. The
hardened area is also inert to most inks and solvents used in the press
room. The exposure step requires a high contrast film negative with high
density (D-max of 3.7-4.0) in the black nonimage areas and with low density
or D-min in the clear image area. A matte surface is also necessary to al-
low proper draw-down in the exposure unit, thereby eliminating trapped air
pockets and obtaining good contact between plate and film. Without matte,
the relief image will be distorted. This high-contrast negative is placed
on top of the plate, which is then exposed to a UV source. The radiant
energy is transmitted through the clear area and triggers the polymerization
and hardening, while the monomer in the unexposed areas remains unchanged.
photoinitiator & photoinitiator fragment
small monomer molecules ^^ crosslinked polymer
binder 9^ binder
Figure 2. Photopolymer composition.
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WASHOUT
The nonaxposed areas are then washed away while the exposed areas re-
main in relief. The preexposed Dycril plate is sprayed with a dilute solu-
tion of sodium hydroxide at a temperature of about 85° F within a closed
washout unit. Concentration of the solution is approximately 0.2 percent
NaOH (about 0.036N), which is equivalent to about 6 fluid ounces of 50 per-
cent caustic in 25 gallons of water and illustrates the dilute nature of
this washout mixture. The concentrated caustic solution is typically stored
in a 55-gallon drum and is pumped into the washout unit where it mixes with
the proper amount of water. An automatic control minimizes operator expo-
sure to the washout solution.
Each washout unit can handle two plates per washout cycle, resulting
in an effluent of 3 to 4 gallons/minute or about 15 gallons/washout. De-
pending on plate production (see table 1) the flow from a Dycril installa-
tion can be as low as 100 gallons/day to as high as 2,000 gallons/day
Total flow/day, then, is dependent on whether use is continuous or in-
termittent, as well as on the number and size of plates processed. To gain
perspective let us relate gallons/day to number of washouts and number of
plates. Most Dycril installations fall in the lower volume category of 100
gallons/day, which corresponds to about seven washout cycles and to the
Table 1. Dycril* installation
(flow 100 - 2,000 gal/day)
Gallons
100
750
2,000
Washouts
7
47
125
Plates
14
94
250
*Dycril is a registered trademark of E. I.
du Pont de Nemours & Co., Inc., Wilmington,
Delaware.
245
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processing of 7 to 14 plates. Probably a more realistic situation with most
Dycril newspaper operations would be 750 gallons/day washout effluent cor-
responding to approximately 47 washouts or 94 plates. In the case of a
large 24-hours-a-day, 7-days-a-week newspaper operation, maximum figures
would be 2,000 gallons/day—equal to 125 washouts and 125 to 250 plates.
DYCRIL EFFLUENT
Visually, the Dycril washout effluent is an aqueous, colorless suspen-
sion of settleable solids that are very light and fluffy, much like a bulky
activated sludge. Slight turbulence keeps the solids in suspension.
Samples taken directly from the washout unit after processing different
plate types were sent to outside laboratories for analysis. In reviewing
the results it was apparent tha the effluents were very similar regardless
of the plate type, as would be expected since all plates are of approximately
the same composition.
Table 2 presents the results from analyses of several washout solutions.
The data in the table show that the washout solution has relatively high pH
(11.0-11.5) as well as high BOD, COD, and suspended solids concentrations.
Table 2. Results from analyses of several Dycril* washout solutions
(pH 11.0 - 11.5)
BOD5
COD
SS
Total solids
Heavy metals
Flow
mg/1
1,700-2,600
7,000-11,000
2,500-3,000
7,500-8,500
None
750-2,000 gal /day
1b/day
11-43
44-183
16-50
47-142
*Dycril is a registered trademark of E. I. du Pont de Nemours &
Co., Inc., Wilmington, Delaware.
246
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However, it.should be pointed out that these relatively high concentrations
yield low quantities (Ibs/day) of the pollutants being discharged.
Routine operation of the washout unit yields an effluent with no resid-
ual heavy metals. However, it should be noted that periodic acidic clean-
ups of the unit have resulted in residual copper and zinc levels during the
cleanup period (about 20 minutes/month). The source of copper and zinc is
believed to stem from acidic corrosion of brass fittings in the washout
unit. These intermittent discharges of copper and zinc are considered to
be negligible and result in a total of only 0.0003 Ibs of copper or zinc
being discharged during the acidic cleanup of a 35-gallon washout unit.
Table 3 presents some other parameters that might be of interest and that
were analyzed in the washout solution. The parameters are alkalinity, TOC,
percent solids in suspension,* and settleable solids.
Table 3. Additional parameters analyzed in the
Dycril* washout solution
mg/1 lb/day
Alkalinity
Phenolphthalei n 215 1.3-3.6
Methyl orange 275 1.7-4.6
Total organic carbon (TOC) 3,200-3,500 20-58
% Solids in suspension - 30-40%
Settleable solids - 600-700 ml/I
How - 750-2,000 gallons/day
*Dyeril is a registered trademark of E. I. du Pont de Nemours, &
Co., Inc., Wilmington. Delaware.
*The ratio of suspended solids to total solids.
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REGULATIONS—FEDERAL
What do these numbers mean with respect to water pollution regulations?
Most Dycril users discharge to municipal sewer systems, and to gain
perspective let us suppose that a relatively large-volume Dycril newspaper
operation--!,000 gallons/day—discharges into a small municipal treatment
system handling 1 M (Million) gallons/day. The flow, COD, BOD, and SS load-
ing of the Dycril operation represents 0.1 percent, 5 percent, 2.0 percent,
and 2.7 percent of the municipality's flow, COD, BOD and SS loadings, re-
spectively. It should be noted that these calculations represent an extreme
case of a large newspaper in a small town. A more typical situation would
be the discharge of 1,000 gallons/day into a 10 M gallons/day municipal treat-
ment operation. This case would reduce the Dycril effluent contribution by
an order of magnitude, yielding 0.01 percent, 0.5 percent, 0.2 percent, and
0.3 percent for flow, COD, BOD, and SS loadings, respectively.
Even in the worst case of the operation contributing 2,000 gallons/day,
it is not a major contributing industry as defined in EPA's Pretreatment
Standards (40 CFR Part 128.124). However, it is important to remember that
each situation must be analyzed separately and that these calculations
should be done for each customer, based upon the figures specific to his
case, in order to determine the magnitude of his contribution relative to
the total municipal load. Dycril effluent also does not fall into any of
the prohibited-wastes categories, as defined in the Pretreatment Standards.
It is not a fire or explosion hazard, is not corrosive, is not solid or
viscous, and is not discharged at a flowrate that is so excessive as to
cause treatment process upset or loss of treatment efficiency.
REGULATIONS—STATE AND LOCAL
Municipal treatment plant discharges are subject both to Federal regu-
lations and possibly to water quality standards. Thus, in addition to Fed-
eral pretreatment standards, most municipalities establish their own pre-
treatment limitations to protect their treatment system performance levels.
The analysis of Dycril effluent, when compared to allowable limits
established in the past by some municipalities, suggests a violation of
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maximum limitations for some parameters, such as pH, BOD, and SS. However,
most municipalities are modifying their sewer codes to accept compatible
effluents. Compatible pollutants, as defined by EPA (Pretreatment Standards-
40 CFR, Part 128.121) include BOD, suspended solids, and pH, plus other
pollutants such as COD and TOC in appropriate situations. Pretreatment for
removal of compatible pollutants is not required by current EPA regulations.
Laboratory tests clearly show that the Dycril effluent contains biodegradable,
compatible pollutants that can be treated and, therefore, accepted by a
secondary municipal sewer system and which do not contain prohibited waste
categories of materials.
Thus industrial compatible pollutants can be treated by a municipal
treatment plant, but the discharger must pay his fair share of the treat-
ment cost in the form of a surcharge. Surcharge schedules can be obtained
upon request and are usually based on formulations, which take into consid-
eration flow, suspended solids, and BOD above certain levels.
Typical surcharges might be $0.03-0.05/lb of BOD and suspended solids
and $0.04/1,000 gallons of hydraulic flow. Thus, in the case of a 1,000
gallon/day Dycril operation, total daily surcharge cost would be on the
order of $2.20. This calculation again points out the small contribution
that a typical Dycril operation would have on a municipal sewer system.
Should a customer require more specific data on Dycril effluent,
table 4 presents an appropriate formula and factors that can be used to
compute the parameters for total solids (TS), suspended solids (SS), COD,
and BOD5 from both 25- and 35-gallon washout units. The pollutant param-
eter expressed in mg/1, is equal to (the factor for that pollutant) X
(percent washout) X (plate area) X (plate thickness). The effluent char-
acteristics, then, of the washout of any Dycril plate can be easily calcu-
lated and are readily available to anyone.
CONCLUSIONS
In conclusion, we think it is reasonable to say that the Dycril system
does not present a pollution problem when discharged to a municipal sewer
system. Dycril operations yield low-volume, intermittent discharges that
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Table 4. Specific data on Dycril* washout effluent
Pollutant Factor
Parameter a 25-gal tank 35-gal tank
Total solids 220 157
(TS)
Suspended solids 130 102
(SS)
Chemical oxygen
demand (COD) 280 200
Biochemical oxygen
.demand (BOD5) 130 102
*Dycril is a registered trademark of E. I. du Pont de Nemours
& Co., Inc., Wilmington, Delaware.
aPollutant parameter (mg/1) = factor x (% washout) x (plate
area) x (plate thickness).
are biologically degradable, contain no heavy metals, and are therefore
compatible with secondary municipal water treatment systems.
DISCUSSION
MR. ROBERT MASIULIS (Case-Hoyt Corporation, Rochester, New York): On these
compatible pollutants, can you tell me what figures you are basing the
allowable concentrations on? Because in my area, you would be over.
They have a maximum five times, let's say, allowable BOD and COD for
surcharge. And looking at the figures you had, you would be well be-
yond that, and that would require pretreatment.
MS. MELLINGER: I believe current EPA regulations do not require pretreat-
ment. And secondary municipal sewer systems will charge for BOD and
COD above a certain level. Is that your question?
MR. MASIULIS: I guess I am really referring to local regulations, because
especially in our area, they have a limit of five times. BOD is 300
mg/1 and COD is 600 mg/1. And five times would bring it above that.
So I was curious as to what figures you were using—standard Federal
regulations or any specific local regulations?
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MS. MELLINGER: The figures presented were based on 100 percent washout of
the plates and on the effluent as it comes out of the washout processor.
The figures do not take into account that the amount of photopolymer washed
out can vary with each plate and would never be 100 percent but rather
would average about 50 percent. Therefore, the figures presented would
be 50 percent less. Also, the figures do not take into account other
wastewater sources in a building and possible dilution from them.
The surcharge figures as well as percent contribution figures were
based on conservative (low) concentrations of BOD, COD, and SS considered
to be acceptable to an average municipal treatment plant.
CHAIRMAN SCHAEFFER: I think we have the authority in the audience to answer
the question as to EPA versus local agency requirements. Mr. King.
MR. ROBERT L. KIN(S (Environmental Protection Agency, Denver, Colorado): I
think the difference between what this gentleman suggested and what you
are referring to is that the Federal regulations are as you stated it.
The local regulations can be more stringent, but not less stringent
then the proposed rules and regulations.
One caveat, I think, on your data is that 50,000-gallon limit is
total flow. So, you may not be exact just because you use a Dycril
plate. If you happen to be discharging any combinations greater than
50,000 gal/day in the municipal sewer, including noncontact cooling
water, you can still be considered a major discharger. So, the Dycril
plate is not going to save you from that possible problem. It is a
very minor detail.
I am not trying to detract from the data, except that the fact
that you have a Dycril plate does not make you a nonmajor discharger.
It is total flow, regardless of the contaminant level.
MS. MELLINGER: Total building flow?
MR. KING: Right.
GENERAL CHAIRMAN FISHER: I just cannot resist making a comment here be-
cause it seems to me that this industry or any other is going to get
in trouble if the game it is going to play is going to be to try and
sneak under the regulations by a hair. The regulations will, change
with time. The Government may not be as bright as you are, but it
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eventually catches up.
I think what you really have to ask is whether this material en-
vironmentally is safe and whether our wastewater system is going to be
able to handle it in the long run, rather than whether we can get
around the regulation that happens to be in force today and go ahead
and use it.
MS. MELLINGER; The intent is presenting this paper was not to "get around
the regulation. . .in force today" but to share with you the charac-
teristics of the Dycril effluent and to examine them in light of the
regulations. Pretreatment studies of the Dycril effluent have been
extensive but the expenses involved in setting up pretreatment facilities
have not been justified at the present time due to the biodegradability
and relatively small impact of Dycril effluent.
MR. K. C. 60EL (Richardson Associates, Dover» Delaware): I notice that pH
on our effluent was 11.0 to 11.5. That seems pretty high. Can you
comment on that?
MS. MELLINGER: Well, I did say in my paper that it had high pH. So we
recognize that.
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PLATEMAKING AND ITS EFFECT ON THE ENVIRONMENT
Steven Latus*
Abstract
Processing offset printing plates involves the use of various
chemicals that can be detrimental to the environment. This paper
will discuss the steps involved in making surface, deep-etch3 hard
metal, and wipe-on plates and those chemicals that are commonly used.
It will also cover methods by which printing shops can pretreat their
wastes before the wastes are discharged into sewer lines or otherwise
disposed of.
Although there are many presensitized plates on the market today,
this paper will concern itself mainly with surface, deep-etch, hard
metal, and wipe-on plates. A step-by-step description of how each
type of plate is processed will show us which chemicals are involved.
Surface plates, like deep-etch plates, are made of either zinc
or aluminum. In the making of a surface plate, the plate is coated
with a light-sensitive coating. When exposed through a negative, the
image areas are hardened so that they will accept ink. The coating is
then washed off of the nonimage areas, and these areas are made water-
receptive by treatment with a desensitizing etch.
The first step in the making of a surface plate (and a deep-etch
plate as well) is to counteretch it. This is essentially a cleaning
process and usually involves the use of a dilute acid solution, although
alkaline counteretches are occasionally employed. Phosphoric, acetic,
hydrocholoric, and sulfuric acids are commonly used in dilutions of 1 to
4 oz/gal water. In the whirler or sink, the counteretch is poured
onto the plate surface and is kept agitated by a bristle brush. After
about a minute, the plate is rinsed liberally with water.
*Project Leader, Lith-Kem Corporation, Lynbrook, New York.
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The next-step, preetching, is used primarily on zinc plates. The
preetch solution is brushed over the plate surface, left on for about
a minute, and then rinsed off with water. This solution usually is an
acidified solution of gum arabic to which ammonium bichromate has been
added. Preetching facilitates even spreading of the light-sensitive
coating and also makes the plate develop out easier later on in the
process.
After preetching, the plate is coated in the whirler with the
surface-coating solution. This coating consists of a water solution of
ammonium bichromate, a small amount of ammonia water, and a protein type
of colloid such as egg albumin, casein, a modified casein, or soybean
protein. The combination of ammonium bichromate and protein colloid makes
the coating light-sensitive, while the ammonia water raises the pH of the
solution to about 9. This high pH considerably slows down the natural
reaction between the colloid and the ammonium bichromate and acts to
preserve the useful properties of the coating while it is in the bottle.
After exposure in the frame, the coating is often covered first with
a surface lacquer in order to give a longer run on press. This lacquer
is a solution of resins in an organic solvent. Then the plate is covered
with a developing ink, which increases the ink receptivity of the image
areas of the plate.
To develop the plate, a dilute ammonia solution is used (about
1 oz ammonia water/gal water). This removes the unhardened nonimage
areas. The plate is then washed off with water and squeegeed dry.
After development, a desensitizing etch is applied and allowed to
dry. This desensitizing etch is an acidified solution of gum arabic,
which may also contain dissolved salts such as ammonium bichromate or a
nitrate. After the desensitizing etch is dry, a plain solution of gum
arabic in water is applied and allowed to dry. The plate is now ready
for the press.
It is plain to see that there are quite a few chemicals used in this
process, which are undesirable from an ecological standpoint. The
bichromate solutions contribute hexavalent chromium, a suspected carcinogen.
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Many of the solutions contain acids or ammonia. During development,
coating plus surface lacquer and developing ink are washed down the
drai n.
One obvious solution to prevent these various pollutants from
reaching the municipal water supply is to hook up holding tanks to the
sink and whirler drains. The hexavalent chromium can be reduced by
lowering the pH of the tank to about 2 with a strong mineral acid (sulfuric
or hydrochloric) and then adding a strong solution of reducing agent,
usually ferrous sulfate or sodium bisulfite. This transforms the hexa-
valent chromium to the trivalent form. Mixing should be constant during
the entire process in order to make the reactions take place as fast and
as thoroughly as possible. Some companies use motors and some use com-
pressed air to keep the solution in the tank thoroughly agitated. Before
proceeding with the next step, you must determine that the hexavalent
chromium level is below allowable limits for your area.
The Hach Chemical Company, Ames, Iowa, sells many different types
of water analysis kits, which are moderately priced and easy to operate.
After you have reduced your hexavalent chromium sufficiently, you can
then proceed with neutralization of the tank waste. This involves adding
a base such as caustic soda solution. You can raise the pH to a 6 or
so and then contact a special scavenger service to properly dispose of
the waste. The pH could also be raised to between 8 and 9, which will
cause all of the metal.s in solution to precipitate out as hydroxide.
Let the waste settle for a minimum of 8 hours, and filter it if necessary.
The resulting liquid can be discharged into the community sewer system
and settlings can be removed by special scavenger services.
The deep-etch process uses even more chemicals than does the surface-
plate process. Deep-etch plates are exposed through a positive and are used
when a long-running plate is desirable.
Like a surface plate, deep-etch plates are first counteretched with
a dilute acid solution and rinsed with water. The plate is then coated
in the whirler with deep-etch coating, which usually consists of a water
solution of gum arabic, ammonium bichromate, and ammonium hydroxide.
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After the coating is dried and the plate is removed from the whirler,
it is exposed in the frame. After exposure, the plate is checked for
blemishes or unwanted marks where light has been held back by dust, lint,
etc. These areas will develop under the deep-etch developer unless they
are covered with a stop-out solution. The stop-out solution consists of a
shellac, varnish, or similar material dissolved in an organic solvent
along with a dye or pigment. This solution must be able to withstand the
developing and etching steps but dissolve readily in the alcohol wash,
which is applied after etching.
After the stop-out has dried, the plate is developed. Deep-etch
developer consists of a concentrated aqueous solution of metallic salts
plus organic acids. This solution will remove the unhardened coating
without attacking the exposed or hardened areas.
When development is complete, the next step is to deep-etch the
plate. Usually this deep-etch solution contains ferric chloride along
with other chlorides and a small amount of acid. This solution dissolves
some of the metal in the image areas and thus makes these areas slightly
depressed.
After etching for about a minute, the deep-etch solution must be re-
moved completely from the plate. This is accomplished by three washings
with an anhydrous alcohol, either ethanol or isopropanol.
Many deep-etch plates are copperized today with a copperizing solution,
which chemically deposits a thin layer of copper in the image areas. This
layer of copper forms a very ink-receptive base and also extends the life
of a deep-etch plate considerably. The copperizing solution is mainly an
alcohol solution of a copper salt with a small amount of acid. It is
applied to the plate right after the final alcohol wash, which was used
to remove the deep-etch solution. After the copperizing solution has done
its work, it is in turn rinsed off with three alcohol washes. The plate
is then dried down in preparation for the application of the deep-etch
lacquer.
The deep-etch lacquer consists of a vinyl resin dissolved with a dye
in an organic solvent. A small pool of lacquer is applied to the plate
and then spread over the entire surface. The plate is then dried down with
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a fan. This lacquer provides a chemically resistant, ink-attractive base
for the image areas.
After application of the lacquer, some shops apply a litho asphaltum
solution to further increase ink receptivity and to make washing out easier
when the plate must be stored for any length of time. This solution mainly
consists of gilsonite and an ink base in an organic solvent. When the
asphaltum has been thoroughly dried down, developing ink is applied. This
ink is usually a carbon black-pigmented litho vamish in petroleum solvents,
which further increases the ink receptivity of the plate.
After the ink has been fan-dried, the plate is brought to the sink
for removal of the stencil, which is the light-hardened coating in the
nonimage areas. The plate is either placed under warm running water or in
a trough of warm water for a few minutes. The stencil can then be removed
by scrubbing the plate with a brush.
The plate is now given a final etch and gumming, just like a surface
plate, so that the nonimage areas will repel ink and accept water. Many
shops also apply a combination wash-out and asphaltum solution after gum-
ming. This makes washing out easier if the plate is to be stored for any
length of time. The plate is now ready for press.
The pollutants contributed by the deep-etch process fall into three
general categories:
1. Toxic metals,
2. Aci ds,
3. Certain organic compounds.
Metals present in solution would be hexavalent chromium, iron, zinc,
calcium, copper, and magnesium. Copper, iron, and chromium in sufficient
concentrations are toxic to bacteria in secondary treatment plants. As
mentioned previously, hexavalent chromium may be reduced to trivalent
chromium with ferrous sulfate or sodium bisulfite in an acid medium. Then,
upon addition of caustic soda or lime, the heavy metals will precipitate
out as hydroxides.
The acids present include hydrochloric acid, which is usually present
in copperizing solutions; certain organic acids, which come from the
developer and etch; and the acid used in counteretching, which could be
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phosphoric, acetic, sulfuric, hydrochloric, etc. All of these acids can
be neutralized by the addition of an alkaline substance such as caustic
soda or lime.
The organic wastes consist of gum arabic, vinly resin from the lacquer,
ink, alcohol, and solvents from the asphaltum solution and lacquer, etc.
The biggest solvent problem in terms of volume is the alcohol, which is
used in washing the plate and is also contained in the copperizing solu-
tion. It would be useful if the alcohol could be kept separate from the
other waste by separate drainage into its own holding tank. A lot of the
other organic waste might be filtered out with the aid of ferrous sulfate,
which acts as a coagulant and thus is a good filter aid for suspended
organic and inorganic matter.
The next type of plate to consider is the hard metal plate, which is
used for exceptionally long runs. These plates consist of two or three
layers of different metals so that, after processing, the image areas are
resting on one metal while the nonimage areas are covered with a different
metal. These plates can be either positive- or negative-working.
A bimetal plate consists of a base of aluminum, aluminum laminate,
or stainless steel, which has been plated with a layer of copper. It is
first counteretched, coated with deep-etch coating, and then exposed
through a negative. The plate is developed with deep-etch developer, which
removes the unexposed coating from the nonimage areas. A copper etch is
applied, which removes the copper from the nonimage areas but does not touch
the chrome. The etch is then flushed from the plate with water, and the
hardened stencil is removed with the aid of an activator solution. The
plate is flushed again, fresh activator is applied, and the plate is inked
up with rub-up ink. After inking, the plate is flushed again to remove
excess ink and is finished with gum and asphaltum.
Trimetal plates usually consist of chromium electroplated on top of
copper, which has been plated on a base of mild steel, aluminum, or aluminum
laminate. Such plates are positive-working and are processed much like
deep-etch plates. During the etching step, though, a chromium etch dissolves
the chromium away in the image areas, leaving the copper exposed. Then the
stencil is removed with the help of an activator solution, and the plate is
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finished up like the bimetal plate described earlier.
Since many of the chemicals used to process a hard metal are used
in deep-etch work, the waste products are similar. The only different
chemicals used are the etches and the activating solutions. The copper
etches for bimetal plates often contain either ferric chloride or ferric
nitrate, some other metallic salts, and sometimes an acid. The chromium
etch used for trimetal plates usually consists of a concentrated solution
of metallic salts, such as calcium chloride, together with hydrochloric
acid. The activator solutions generally contain sulfuric acid, some sol-
vents, and a fatty acid.
The wipe-on plates are simpler to develop and process than any of
the previous ones. Not only are they easily processed by hand, but they
also can be run through a processor, which performs all of the steps
automatically. The plate is usually anodized aluminum.
The first step in making a wipe-on plate is to apply a light-sensitive
diazo coating. A typical diazo compound consists of the condensation
product of formaldehyde and para-diazodiphenylamine. This powder is
dissolved in a mixture of about 80 percent water and 20 percent methanol.
Most of this coating adheres to the plate so there is not much pollution
of water involved. Some chemicals will go down the drain, if the applica-
tor sponge is rinsed in the sink.
After the diazo coating has been fan-dried, the plate is exposed
through a negative. The plate is developed and the image lacquered in one
step with a lacquer developer. A typical lacquer developer is a pigmented,
two-phase emulsion, one phase being an aqueous gum arabic (or gum substi-
tute) solution and the other being a polymer dissolved in an organic sol-
vent. The aqueous phase develops the nonimage areas while the lacquer
phase makes the light-hardened image areas ink receptive. Only 2 to 3
ounces of lacquer developer are used on a 40-by-48-inch plate. The plate
is rinsed with water, and the excess water is squeegeed off. The plate
is then gummed up with 8° Baume gum arabic or a specialty finisher. If
the plate is processed through a processor, waste collection is simplified.
The discharge unit can be hooked directly to a holding tank. Wastes from
this process would include diazo and alcohol from the coating. The lacquer
259
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developer would contribute gum arable or gum substitute, pigment, filler,
organic solvent, resin, and some add.
Presensitized plates I will only touch on very briefly. Many different
ones are on the market today, so it is hard to be specific about what
chemicals are involved. All presensitized plates, of course, are coated
with special light-sensitive materials, and they can be either positive-
or negative-working. The developers vary with the plate they are intended
for; some are water-base, some contain solvents. The waste problem thus
depends on just whose plate you are using.
But no matter what process a plant is using, it is plain that the waste
products from platemaking cannot be ignored. My company and, I am sure,
many other companies are busy trying to come up with new, less toxic
chemicals to replace those now in use in some of our products. We also
offer our customers advice on how to comply with their areas' sewage
laws, and we point out which sections apply to them when using our chemicals.
We also give them advice on how they can treat their wastes. Pretreatment
of wastes by printing shops will go a long way toward easing the burden of
municipal water treatment plants.
BIBLIOGRAPHY
1. Hartsuch, Paul J., Chemistry of Lithography, Graphic Arts Technical
Foundation, Inc., Pittsburgh, 1969.
2. Lith-Kem Corporation, Chemical Catalogue No. 971.
3. Nordell, Eskel, Water Treatment for Industrial and Other Uses, second
edition, Reinhold, New York, 1961.
4. Various company memos and letters.
DISCUSSION
MR. ROBERT L. KING (Environmental Protection Agency, Denver, Colorado):
Have you done any water balance studies on the amount of water used
for these rinseoffs?
MR. LATUS: No, we have not.
260
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CURRENT STATUS OF
WEB HEATSET EMISSION CONTROL TECHNOLOGY
Joseph L. Zborovsky*
Abstract
The industry has tried many control methods to comply with Federal*
State, and local air pollution regulations. This report outlines all "known
methods that were used or showed promise through the first half of 1975.
Information is provided to identify the advantages and disadvantages of
each method. Recommendations are also made to evaluate the costs of in-
vesting in the various control devices.
INTRODUCTION
The desire of every printer using heatset inks (web offset or letter-
press) is for a pollution-free ink equivalent in price and performance to
conventional heatset inks, one which allows him to continue operations
without making any additions or changes in the present hardware. Thus for
the printer, the least burdensome solution to his problem is ink reformula-
tion.
Extensive research by ink manufacturers has shown progress in this
direction; however, no heatset ink formulation (or reformulation) will meet
all regulations in every part of every State. Several formulations have
been developed through substitution of ink vehicles (solvent) and reduction
of their quantity. Experience with reformulated inks (ref. 1) has shown
that some reduction is achieved in smoke, odor, and the total quantity of
hydrocarbons emitted (table 1).
Low-temperature drying inks with "exempt" (photochemically unreactive
as defined in Los Angeles Rule 66) solvents usually cost 50 percent more
but use only 60 percent of the heat required for conventional heatset inks
and produce less odor. However, when tested under operating conditions,
low-temperature drying inks produced more smoke.
*Environmental engineer, Graphic Arts Technical Foundation, Pittsburgh,
Pennsylvania.
261
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Table 1. Web offset inks for emission control
Ink Type
Heatset
Low-smoke
Low-solvent
a*
Low- temp, dry
b*
Low- temp, dry
c*
Low- temp, dry
Heat-reactive
UV cure
Percent
solvent
40-45
40-45
25-30
45-50
25-30
25-30
0-15
0
Relative
cost
100
105
120
150
125
105-110
140-200
200-300
Web Relative
temp. gas usage
(5F)
300
300
270
210
230-250
220-250
340
120
100
100
85
60
60
87
115
0
Plume
opacity
(percent)
15-20
10-15
5-10
10-25
15-20
none
0-5
0
Relative
odor
100
60
40
35
slight
slight
20
trace
*a = ref. 1; b ref. 2; c re*. 3.
Low-solvent Inks, e.g., 25-30 percent, appear to be the system that
best satisfies the printer's needs, although the price generally runs 20
percent more than for conventional Inks. The heat required is 15 percent
less, and smoke and odor are significantly lower. Modification of dryer
operation can further enhance this picture. Many printers have been using
low-solvent Inks where only smoke and odor regulations exist and the sol-
vent 1s not photochemically reactive. Others have employed low-solvent
inks as a temporary measure until a more permanent means of control is in-
stalled or available.
Attempts to reduce visible emissions by substituting different vehi-
cles yielded no significant reduction in smoke. The heating requirements
remain unchanged compared to conventional heatset inks. The price of the
reformulated Ink was 5 percent greater.
One novel approach to eliminating emissions from high-speed web opera-
tions is being used at Meredith Company (ref. 4). Instead of a heatset ink,
an oxidative-drying ink is used, and a coating (a low concentration of a
polymeric ester in ethanol and water) is applied and dried at 140°-150° F.
The coating acts as a protective film to avoid setoff while the ink film
dries underneath at its normal rate. No ink oil is emitted, as is the case
262
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1n a conventional heatset Ink, and the opportunity for visible emission
and nuisance odor 1s virtually eliminated. The alcohol in the coating is
recoverable and recyclable. Costs vary widely, depending on whether cover
stocks or an entire magazine are printed this way. However, ultimate po-
tential savings would include savings from paper as well as from drying
operati ons.
The above control methods are the least burdensome for the printer,
even though some changes 1n operating procedures and/or additional costs
are involved. Unfortunately, however, more stringent control is necessary
in some areas of the country, and more sophisticated, expensive, and exten-
sive measures are required. These more extensive methods—unconventional
or innovative Inks and control equipment with conventional inks—are sum-
marized 1n figure 1 and discussed in the sections that follow.
CONTROL TECHNOLOGIES
Heat-reactive Inks
Because the printer desires to maintain his present, drying system,
ink manufacturers investigated Inks with different heat-drying mechanisms.
Thermally catalyzed (heat-reactive) inks, an entirely different system
chemically, require a 15 percent Increase in gas and cost 40 to 100 percent
more. However, a noticeable emission reduction was observed when the inks
were submitted to analysis
UV Inks
Ink manufacturers have recognized the need for a new ink-drying proc-
ess for many years. Although they realized the complexity of the printer's
immediate demands, they decided to concentrate some of their efforts on the
longer-term development of a pollution-free ink (no solvent, no emission)
using a different process to dry the ink film. Today their research ef-
forts have produced a commercial success with UV (photoreactive) inks.
UV ink systems meet all the emission regulations and produce good
print quality. UV inks appear to be the pollution control method present-
ly closest to the ideal. The high costs of ink and hardware are a major
consideration, but in certain circumstances are economically feasible. If
263
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METHODS OF AIR EMISSIONS CONTROL
ro
,,„„_ ,„,.
Change Ink System Change Ink Drying Process
1 111
Low Temperature Thermally Catalyzed Electron Beam
Drying Heatset Ink Heat-reactive Ink UV Drying ink Drying Ink
, , v Heat Recovery System
Low-Solvent Ink Low-Smoke, Low-Odor Ink (Heat Excnan9ers)
(Exempt Solvent) (Exempt Solvent) ~[
.,. ,j ^ |
Destructive Oxidation of Hydrocarbon Emissions Non-Destructive Capture or Recovery of
Dlr!l^ame lnClneratl°n Carnation Wet Scrubbing Coalescence /
or Afterburner wei acruooing Pack Towers i
Catalytic Oxidation Condensation J£
Emissions
set Ink •
Hydrocarbons
1 r
Adsorption
Activated Carbon
trostatic
ipltation
Figure 1. Pollution control techniques applicable to web offset.
-------
costs can be justified and some performance problems eliminated, the UV
system, considered revolutionary by some in the industry, may become a
very widely used drying process.
Electron Beam Drying (EBD)
Electron beam drying 1s another of the new drying systems. Although
it has not yet achieved commercial acceptance, this process has no pollu-
tion potential and can dry (cure) ink films which are too thick to be cured
UV. Tests are anticipated for both gravure and offset in 1975. This sys-
tem may be most practical for screen printing (ref. 5). Some developers
of EBD systems feel that its potential is fairly unlimited in all areas
of printing.
Destructive Oxidation
Within the past 4 years thermal and catalytic oxidation of hydrocar-
bons has been used successfully to control emissions in the printing in-
dustry. Incineration techniques now available can control the emission of
almost every known hydrocarbon by converting it into carbon dioxide and
water (ref. 6). The various Incineration processes differ only in reaction
mechanisms and temperatures. Process designs differ primarily in control
of temperature, turbulent mixing of gases, and kinetic reaction contact
times (ref. 7).
Optimum operational design of equipment is extremely important in in-
cineration processes. Insufficient temperature: nonhomogenous mixing of
hydrocarbons, gas, and air: and/or insufficient time in the reaction zone
contribute to Incomplete combustion, which yields carbon and carbon monox-
ide. These unwanted reaction products can be generated in sufficient con-
centrations to cause smoke, hydrocarbons, and/or carbon monoxide to be
emitted. Some companies, in a false economy move, reduce the fuel feed to
the afterburner, leading to incomplete combustion, visible emissions, and
citations.
A problem common to all combustion systems is the possibility of oxi-
dizing atmospheric nitrogen at high temperatures into nitrogen oxides,
which also are an air pollutant.
265
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Direct flame Incineration (afterburners); Many direct flame incinera-
tion processes differ only in the design of fuel burners, baffling, and con-
striction devices employed to optimize turbulent mixing of gases before
combustion. Automatic fuel and air flow controls are available to main-
tain stoichiometric flow rates to achieve complete combustion. Incinera-
tion requires oxidation temperatures in the 1,100°-!,200° F range (ref. 8)
and sufficient time in the reaction zone. Proper contact time is depend-
ent upon the kinetic rate of reaction (oxidation) for that organic compo-
nent in the effluent having the slowest reaction rate.
Within the past year, printers have been extremely cautious about
installing afterburners because of fuel shortages. Fuel requirements for
afterburners depend on the air-handling rates of press dryers. Theoreti-
cally, a typical afterburner for a press dryer operating at STP would use
about 105 cfm of natural gas (100 percent methane) per 1,000 scfm of spent
dryer gases. Based on September 1974 rates in Pittsburgh (ref. 9), the
natural gas costs for this afterburner would be about 14 cents per 1,000
scfm of spent dryer gases.
Some printers using afterburners are now considering replacing them
with other control devices requiring less energy. Over the last year, as
many as 20 afterburners have been Installed and equipped with heat ex-
changers that can reclaim as much as 40 to 60 percent of dryer and after-
burner heat.
The prime advantages of direct flame incineration are essentially com-
plete oxidation of all organlcs, no smoke or odor, moderately priced hard-
ware, and minimum maintenance. The major disadvantage has become recently
apparent with short fuel supplies and soaring costs. Current domestic
production of natural gas is predicted to be 75 percent lower by 1985 with
prices increasing twofold to fourfold (ref. 1). Economists have been project-
ing shortages 1n domestic supply and Imports of expensive liquid natural
gas—unless Industry reduces consumption, new gas reserves are found, and/or
synthetic gas processes are developed. Gas suppliers have already reduced
allocations to some companies by 15 to 60 percent while others require 1- to
2-year waiting periods for either new customers or for increased allocation.
The use of regenerative heat exchangers may recover as much as 70 per-
cent of the waste heat, but the severity of temperature and ink solvents,
266
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resins, dust, etc., all detract from the life and performance of this type
heat exchanger (ref. 11). The use of heat exchangers and/or the replace-
ment of Inefficient gas dryers, however, can save as much as a 76 percent
(ref. 12) 1n natural gas costs.
Given unlimited fuel supplies, the overall air quality performance
of direct flame Incineration would have to be rated as excellent.
Catalytic oxidation processes: Like direct flame incinerators, the
catalytic oxidlzer also converts hydrocarbons into carbon dioxide and water
but uses a different reaction mechanism and at a lower reaction tempera-
ture (ref. 13). The oxidation rate accelerates in the presence of an
appropriate catalyst, and the temperature required is lower, the optimum
depending upon the catalyst used. Reports have been made that optimum
hydrocarbon oxidation could be accomplished at reaction temperatures as
low as 650°-700° F (ref. 14).
Typical catalysts are the transition metals or their oxides: iron,
cobalt, nickel, platinum, palladium, copper, and silver. Catalysts are
usually manufactured by coating an Inert support material with a finely
divided metal or metal oxide. The catalyst usually used in the industry
1s a platinum and/or palladium coating on a ceramic cylindrical pellet.
The catalyst bed is usually located in a temperature-controlled heating
zone where premixed stoichiometrie quantities of atmospheric oxygen, fuel,
and hydrocarbon (organlcs) react to form carbon dioxide and water. Con-
trol of temperatures and contact time with the catalyst bed are especially
Important to Insure complete oxidation.
Improper temperature or contact time can cause incomplete oxidation,
yielding carbon, carbon monoxide, and side reactions such as resin polym-
erization. Polymerized resins condensed on the catalyst surface can de-
activate the catalyst or plug the catalyst bed.
Catalysts are susceptible to substances that inhibit or destroy (poi-
son) their activity, even 1n minute amounts or very low concentrations.
Certain heavy metals, halogenated hydrocarbons, and organosilicon com-
pounds 1n trace quantities will poison many catalysts. In practice, cata-
lyst cost, life, physical strength, resistance to thermal shock, and re-
sistance to poisoning are factors that must be considered in addition to
267
-------
activity and specificity. All catalysts are expensive, especially those
using precious metals: platinum, palladium, and silver. In considering a
catalyzed system, evaluations of catalyst replacement or regeneration must
be made.
A distinct advantage of this process is that less natural gas is con-
sumed than in the direct-flame afterburner incinerators because of the
lower reaction temperatures. However, catalytic systems can waste fuel
and energy, just as the afterburner, unless heat recovery is employed with
heat exchangers.
Qzonation: Ozonators produce ozone by applying a high voltage alter-
nating current to an air space between two insulated electrodes. Permeating
the air space is a charge which converts atmospheric oxygen to ozone. The
spent dryer gases are mixed with the ozone, creating oxidation products
frequently soluble in water or in a slightly basic, aqueous solution.
Ozone generators produce 0.1 pounds of ozone per kilowatt hour of electri-
city consumed.
Ozonators have been equipped with catalysis beds and with wet scrub-
bers to optimize oxidation and to remove water-soluble carboxylated hydro-
carbons from the stack effluent (ref. 15). But the use of afterburners
with ozonators cannot reduce afterburner gas consumption significantly be-
cause reaction temperatures must be maintained at 1,100° to 1,200° F (ref. 8)
to oxidize all those molecular sites not oxidized by the ozone.
The major use of an ozonator is only to oxidize the most odorous hydro-
carbons into a less objectionable form, though without any change in the
rate of hydrocarbon emissions (pounds of carbon per hour). The process has
not gained wide acceptance because ozone reacts very slowly or not at all
with saturated hydrocarbons. (Ozone readily oxidizes unsaturated hydrocar-
bons.) Ozonators have been used successfully with other incineration proc-
esses to speed up oxidative reactions. Pilot tests in our industry, how-
ever, indicate that ozonatlon will not effectively eliminate odorous emis-
sions from web dryers (ref. 13).
Nondestructive Control Processes
Petroleum derivatives make up about 80 percent of conventional heatset
inks (55 percent solvent). Last year, the price of ink solvents increased
268
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by 340 percent (ref. 16). This year, Ink vehicles are expected to In-
crease 1n price an average of 25 percent. No relief is foreseen from
these spiral ing costs (ref. 17).
Clearly, Incineration destroys a prime raw material—one expected to
continue to Increase 1n value Into the foreseeable future. Even in Incin-
erators equipped with heat exchangers, the market value of the solvent
lost exceeds the market value of the heat recovered. (Ninety-five gallons
of solvent 1s equivalent 1n heating value to about 0.5 tons of coal or
10,000 cubic feet of natural gas. See table 2.)
Nondestructive recovery control devices may not only offer an accept-
able means of emissions control, but also help conserve these ever more-
expensive petroleum derivatives. Ink solvents have been successfully re-
covered from these types of devices and substituted for No. 2 fuel oil 1n
dlesel engines and oil heaters. Last year, recovered ink solvents were
sold for 20 to 50 cents per gallon. The use of recovered solvents in ink
manufacture, however, has not yet been proven successful.
Many nondestructive recovery control processes have been developed or
are under development. As yet, most have had limited success in meeting
Taole 2. Value of ink solvent loss in incineration
Fuels
Ink solvent
Natural gas
Propane
No. 2 fuel oil
Kerosene
Coal (bitumi-
nous)
Equivalent elec-
trical energy
*Heat conversi
Market price
0.50/gal
1.40/103ft3
0.32/gal
0.37/gal
0.385/gal
35.50/ton
0.06/kWh
on factor.
Heat of
combustion
11,250 Btu/lb
1,100 Btu/ft3
91,500 Btu/gal
140,000 Btu/gal
135,000 Btu/gal
13,000 Btu/lb
* 3,413 Btu/kWh
Quantity to
produce
l.lxlO7 Btu
95 gal
10*ft3
120 gal
80 gal
81 gal
0.445 tons
3223 kWh
Cost of
equipment
heat
47.50
14.00
38.40
29.60
31.37
15.60
193.34
269
-------
air quality standards and in recovering ink constituents. Even so, there
can be little question that the philosophy behind the approach is fundamen-
tally sound. Solvent emissions into the atmosphere should be viewed as a
"misplaced resource," a resource to be conserved in a time of shortages and
Increasing prices.
Wet-scrubbing processes: Wet-scrubbing systems are used successfully
1n the chemical Industry to clean and purify gas streams from manufacturing
processes. Vapors are removed from the gas stream by a series of steps in
which the stream is sufficiently cooled to condense and form microscopic
colloidal particles. These particles enlarge through impingement on drop-
lets of water or wetted surfaces. The liquified chemical particles either
diffuse Into the water droplets or agglomerate and become large enough to
separate out of the gas stream by gravity.
Some wet scrubbers use only water or aqueous solutions of water-solu-
ble organic chemicals or inorganic salts to improve efficiencies and insure
dissolution or emulsiflcation of the hydrocarbons into an aqueous phase.
The aqueous scrubbing liquor readily absorbs heat from the spent dryer
gases and saturates the air with water vapor (steam). Wet scrubbers that
do not adequately precool spent dryer gases (such as those with a heat ex-
changer) produce a characteristic white steam plume, which eventually dis-
sipates.
The disposal of the aqueous scrubbing liquor may be a problem because
the dissolved water-soluble hydrocarbon or organic material will contribute
to the pollutants 1n the aqueous effluent.
Aerosols' wet scrubber: The pollution control device manufactured by
Aerosols Control Corporation (figure 2) is a combination of two basic proc-
esses where hydrocarbon vapors are scrubbed with an aqueous solution. A
fiberglass filter bed backs up the system by coalescing liquid chemical
particles that have not enlarged enough to separate from the gas stream by
gravl ty.
The scrubbing liquor contains sodium hydroxide and dioctylphtalate
(OOP) to dissolve and emulsify the hydrocarbon vapors, and surfactants to
prevent the buildup of foam 1n the system. A sump tank containing 100 to
150 gallons of the scrubbing liquor traps about 8 pounds of emulsified
hydrocarbons per hour. The liquor 1s dumped and replenished weekly.
270
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l75aF
Mist "•
Eliminators
Disposal
8 Ib Hydrocarbon
per hr
Emulsified in H2O
1
" 425°F
Water Recirculation
Pump
Figure 2. Aerosols Control Corporation web scrubber.
When this unit was in operation in the industry, it processed 2,500
scfm of exhaust gases from a Ross combination dryer on a M-1000 web offset
press.
The manufacturer claims the unit can remove as much as 99 percent of
the hydrocarbon emissions and reduce the visible emissions to 0-5 percent
opacity. A State air inspector reported that, although the total hydrocar-
bon emission was held below the 0.8 Ib/hr State requirement, the maximum
efficiency of the Aerosols scrubber was only 83 percent. The manufacturer
also reports a normal 90 percent efficiency with normal ink coverage. If
isopropanol 1s present in the fountain solution, the efficiency drops to 87
percent.
The State inspector said the scrubber permits as much as 30 percent
visible emissions and does not meet the State requirement of 0 percent
271
-------
opacity. Operational problems could cause this discrepancy. The inspector
suggested that adequate precooling would normally control visible emissions.
We believe a heat exchanger before the scrubbing unit would meet this need.
But because the Aerosols wet scrubber was not complying with the local
visible emissions standard, the printing plant where it was installed was
pressured by the local regulatory agency to replace the Aerosols unit with
a device such as an electrostatic precipitator (which is known to provide
compliance only with the visible emissions standard).
The capital costs and installation costs of the Aerosols unit are com-
parable with incineration. The only "real savings," perhaps, lies in lower
operational costs in water consumption, chemicals in the scrubbing liquor,
and the use of electrical energy as opposed to natural gas.
CVM Fume Eliminator; The Fume Eliminator manufactured by the CVM
Corporation (figure 3) does not significantly differ in principle from the
t
I05°F
10% Opacity
0.53 Ib Hydrocarbons/hr
2500 actm
3IO°F
50-60% Opacity
3.15 Ib Hydrocarbons/hr
2.62 Ib Hydrocarbons/hr
Figure 3. CVM Corporation fume eliminator.
272
-------
Aerosols wet scrubber but shows significant differences in hardware design
and power requirements. The system 1s equipped with a water scrubber tower
that cools the hydrocarbon vapors to below their boiling point to facili-
tate the enlargement of colloidal droplets. Suspended droplets are passed
through a bed of fine fibrous jnaterial (fiber glass wool) sandwiched be-
tween supporting grids. As the droplets pass through the fibrous bed, they
coalesce by the impingement of larger droplets and the bed packing. As the
droplets grow larger, they collect on the bed packing and drain off into a
sump for removal from the system. (There are no reports of the recovered
Ink solvents being sold. However, they have been used successfully and
experimentally as a heating fuel oil.)
The power requirements of the exhaust blower and the water recycle
pump are about 4 to 5 horsepower for every 1,000 cubic feet of spent dryer
gas processed per minute.
Periodically, the fiber glass bed elements may require replacement.
There 1s no reported evidence of element fouling if used in continuous ser-
vice for 6 months. Expected element life can exceed a year with a minimum
service of 18 turns per week. Element replacement cost and labor would be
about $400 per 1,000 scfm capacity.
The manufacturer claims 83 percent removal of hydrocarbons, and the
opacity of the plume has been consistently less than 10 percent. The State
air quality inspector quoted earlier reports that with medium to heavy ink
coverages, the CVM device will reduce emissions by 83 percent and occasion-
ally perform in compliance (85 percent). According to him, visible emission
(20 to 5 percent opacity) is the only serious problem and appears to be
attributable to inadequate cooling in the first stage of the unit.
The plant 1n which the CVM unit was Installed has since terminated the
unit's operation. Consideration was given to transferring the device to a
plant in another State within the corporation. After extensive studies com-
paring Its performance with other pollution control devices, it was decided
that the CVM unit could not provide compliance with either the hydrocarbon
or visible emissions regulations.
Elbalr wet scrubber. The Elbair wet scrubber (figure 4), marketed by
Peninsula Lithograph Company (PenLitho), is a simple water-scrubbing system
1n which the spent dryer gases pass horizontally through two high-pressure
273
-------
340 F
6000 acfm
Exhaust
Blower
5H.P.
2.0" W.G
Water Recirculation Pump (60 H.P.)
H?O - 180 gal/min, 200 psi
4,714 acfm
115°F
HiO Vapor
(Equivalent to 2.1 gal/min)
Organic, Water-insoluble Phase
Aqueous Phase with Water-
soluble Organics
HiO Disposal
2.0 gal/min
HiO Make-up
4.1 gal/min
Hydrocarbon
Recovery
• - 9-12lb/hr
Figure 4. Elbair wet scrubber (Peninsula Lithograph Co.).
jet streams of water that precool the vapors. The precooled vapors condense
and then pass through a series of three horizontal, 10-gallon housings, each
of which is equipped with four high-pressure spray nozzles. The spray noz-
zles are directed to patented vertical Impinging plates. The recovered Ink
solvent and scrubbing water liquor is collected from a drain tn each housing
and transported to a phase separation tank. The aqueous phase is recycled
and the water-soluble ink solvent periodically drawn off.
The Elbair wet scrubber has been accepted by the San Francisco Bay Area
Air Pollution Control Agency. PenLitho claims their scrubber recovers as
much as 95 percent of the hydrocarbon emissions. Although a white steam
plume 1s always visible, the plume opacity (5 to 15 percent) is acceptable
to the regulatory agency.
The maximum energy requirement for this system is 65 horsepower for the
exhaust blower and the water spray pump.
274
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PenUtho claims they can operate this pollution control device for
only 50 cents an hour and recover 1.5 gallons of Ink solvent per hour for
resale. They claim that they will pay off this scrubber 1n only 22 months.
The only disadvantage we could perceive 1s the heat losses that might
be salvaged with heat exchangers. The evaporation rate of water lost (2.1
gal/m1n) alone accounts for a heat loss of 17,900 Btu per minute which is
equivalent to heat from 978 cubic feet of natural gas per hour ($1.39/hr).
To our knowledge, there are only two printers using the Elbalr wet
scrubber to control hydrocarbon emissions. One of the two replaced after-
burners with the Elbalr unit because of reduced natural gas allocation in
the area. Using limited gas supplies for incineration became a luxury the
company could not afford.
Electrostatic precipitation. United A1r Specialists, Inc., has been
manufacturing an electrostatic precipitation control device called a "Smog-
Hog" (figure 5). The "Smog-Hog" is a rather simple operating system. A
heat exchanger or heat wheel is used to cool and condense spent dryer gases
Into liquid droplets. The airborne droplets then pass through an electro-
Roof Outlet
80-90°F
0.032 Ib Hydrocarbons/hr
Preheated
Fresh Air
70-80".
Heat
Recovery
6 KV 1/2 ma
Collection
Cell
lonization
Cell
12 KV -1/2 ma
Inlet
From Web
Dryer
400°F
0.33I Ib Hydrocarbons/hr
465 scfm
Recovered Hydrocarbons
(Organics)
Figure 5, United Air Specialists "Smog Hog."
275
-------
static Ionizing cell that places an electric charge on each droplet. The
charged droplets are then collected 1n the next electrostatic cell where
the droplets agglomerate on the vertical cell plates, draining off by
gravi ty.
The manufacturer claims at least an 85 percent removal of all hydro-
carbon emissions with no smoke and odor.
No evidence has come to light refuting the recovery efficiency of the
"Smog-Hog." Reports of many observers Indicate no visible emissions and
only slight traces of odor.
The only electrical power demands are for the motor drive of the heat
wheel, electrostatic cells, and the exhaust blower. The precipitation
power is only 20 to 50 watts per 1,000 cfm of exhaust.
The manufacturer claims operating costs rarely exceed 0.1 cent per
1,000 cfm. They also claim that the heat wheel recovers 70 to 80 percent
of the heat loss. According to reports, no printer has taken advantage of
this recovered heat.
The Betran electrostatic predpltator differs from the UAS "Smop-Hog"
only in design, and eliminates visible emissions equally well. However, in
a recent GATF performance study during a Beltran pilot test, this device
demonstrated that the hydrocarbon emissions were not significantly reduced.
Its major performance problems appear to be temperature control of the in-
coming gases and the residence time in the electrostatic cell. Thus, its
application for compliance appears limited to areas where high reductions
in organic emissions are not required.
Activated carbon adsorption: The power of activated charcoal to re-
move or adsorb many different hydrocarbon gases, vapors, and odors has been
known for over 100 years. The adsorbing power of activated charcoal differs
for each adsorbate and depends on the physical and chemical properties of
the adsorbate.
The Los Angeles Lithograph Co., Inc. (L.A. Litho), is currently mar-
keting a patented activated-carbon pollution control device (figure 6),
which they have demonstrated at their plant as an efficient means of com-
plying with the Los Angeles air quality standards.
In the L.A. Litho system, spent dryer gases pass through a manifold
plenum, which evenly distributes the gas flow into three of the four
276
-------
Clean Air .
\
18" Automatic
Valves "-v^^
Activated
Charcoal"^-^^^
Automatic
Controlled ~__^^
Damper <
Dlnuiar . ,
!
Rpnlafpshlp SJ».
Filters — f |
Plenum
3 k 8
^ r\ s^\ r
*-f \ i t
^_S5
' M j
. ' 1 1 I
i Ploniirn
i
i i — r
_^^^_ I i^- ' „
15,000 cfm
Optional^, ^, x
- » v Oarhon '' ' I
! Dioxide; , j
® Fire I '
\ S*\ Control
~j '" — ^ System
"Y-^i
o ,;a 1 2
"!T-
'^ Vacuum Line
*i *
_ .j.
Automatic
_, Controlled
"Ti i^ Dampers
'M | /^\ Replaceable
1 Cilfarc-
riiiers
' i •
3 4 Presses
Vacuum Pump
Condensers
Solvent Tanks
Figure 6. L.A. Litho activated carbon adsorber.
activated charcoal beds. While three beds are adsorbing hydrocarbons, the
fourth 1s being regenerated. It remains on automatic standby until one of
the other three beds reaches its maximum loading capacity of adsorbed hy-
drocarbons .
During the regeneration cycle the adsorption bed is sealed off from
the intake and exhaust manifolds. An electrical heating element in the bed
heats the adsorbates on the charcoal, while a vacuum pump produces a vacuum
of 1 Torr (1 mm Hg). This reduced pressure allows the adsorbed hydrocarbons
to be flashed off at a temperature much lower than the boiling point of the
hydrocarbons at atmospheric pressure. The distillate hydrocarbon is re-
covered, and the adsorption bed is reactivated. The hydrocarbon vapors
condense 1n a water-cooled condenser and a refrigerated trap. The water-
cooled condenser separates the high-boiling hydrocarbons (ink solvent) „ and
the freeze trap recovers the low-boiling and low molecular weight hydro-
carbons .
The regeneration process of the adsorption bed is unique because flash
evaporation processes have not been developed commercially to desorb high-
boiling hydrocarbons from activated charcoal. L.A. Litho reports hyuro-
carbon recoveries of 90 to 95 percent with no visible emissions and only
very slight traces of odor.
277
-------
The Los Angeles Air Pollution Control Department has monitored the
emissions from L.A. Litho, and no objections have been reported.
The only electrical demand 1s the 75 horsepower blower and the 2-hours-
per-day use of the regeneration equipment such as bed-heating element, vacu-
um pump, and the refrigeration unit. L.A. Litho claims that this system
processes 15,000 scfm of spent dryer gas for less than 15 cents per hour.
The estimated initial cost of this system is 1n the neighborhood of $7.00
per cfm.
The high-boiling hydrocarbon is recovered as a dark "tarry" liquid,
which after suitable filtering may be used as a diesel fuel oil. Ink manu-
facturers attempted unsuccessfully to utilize this recovered solvent as an
ink vehicle or press wash-up solvent. Last year, L.A. Litho marketed the
recovered hydrocarbon as a fuel oil. (However, during the oil embargo they
discovered they could use this oil more economically in their own diesel
trucks.')
Although this activated charcoal adsorption process appears to be a
viable system to combat hydrocarbon, smoke, and odor emissions, L.A. Litho
has been troubled with many operational and equipment malfunctions. A rede-
sign of hardware and addition of adequate process control devices may be
necessary to eliminate the temperature and pressure control problems encoun-
tered.
DISCUSSION
Equipment Costs
Estimates of the initial costs of pollution control hardware are diffi-
cult to correlate because prices vary with the size of the unit, volume of
air-handling capacity, and the date of the price quote. The estimates pre-
sented in table 3 do not Include the cost of Installation.
Operating expenses Include the consumption of gas, water, and electri-
cal utilities; and these have been calculated from a common rate for all
three utilities. The operating expenses of labor and replacement parts are
unavailable.
The table also designates the major source of energy (natural gas or
electricity) for each process. The processes that recover potentially sale-
able hydrocarbons and the processes which may present a water pollution
problem also are indicated.
278
-------
Table 3. Comparison of pollution control processes
Costs:
Hardware ($/cfm)
Operation ($/Mcfm)
Major energy
consumed:
Natural gas
Electricity
Systems with:
H20 disposal
Recovery of hydrocarbon
TEC After-
burners
A1 B2
6-13 8-18
X X
Incin-
erator
3-6
2.42
X
Cata-
lytic
3-8
0.53
X
Aero-
sol
5
1.20
X
X
Pen-
Li tho
4-7
0.001
X
X
X
CVM
4
0.001
X
X
X
L.A.
Li tho UAS
7-10 4-6
0.01 0.001
X X
X X
'With 40 percent heat recovery.
2With 60 percent heat recovery.
Performance and Compliance
With the exception of afterburner incinerators, most newly installed
pollution control devices have had some difficulty being totally accepted
by the local regulatory agencies. Regulatory agencies have been cautious
in accepting any unproven control device that might establish a precedent.
Recovery of Heat Losses
The use of heat exchangers to cool spent dryer gases will improve re-
covery efficiencies of all pollution control devices with the exception of
the UV and electron beam systems. Fuel reduction can also be accomplished
with these systems to reduce the operating costs of gas dryers and after-
burner incinerators.
The use of afterburners, even with heat exchangers, does not appear to
be an economical means to control emissions. Afterburners incinerate $47.50
worth of ink solvent to produce the same quantity of heat as $14 worth of
natural gas.
The value of natural gas saved through heat exchangers and the resale
value of recovered ink solvent suggest that each printer should consider
some of the advantages of recovering heat and/or ink solvents to help meet
future needs.
279
-------
New Ink Systems
The UV inks and drying systems appear to be one of the most promising
methods of eliminating hydrocarbon emissions. The deterrent for most
printers is absorbing the high costs of ink and hardware. The low-smoke,
low-solvent, and low-temperature drying inks show some reduction in emis-
sions and fuel consumption; however, all show some increase in cost over
conventional heatset inks.
Recommended Approach to Pollution Control
Before a printer invests in a method of pollution control, he must
evaluate the immediate and long-range economic factors that will affect the
initial capital outlay, operational overhead, and the advantages of pay-
back features.
When considering the various alternative control methods, the effects
of inflation on the cost of equipment and the cost of labor to install that
equipment may make it necessary to determine a time-price relationship.
Overhead expenses must also be approached with caution. Energy, man-
power, raw material consumption, and parts replacement must all be given
equal weight. The printer will have to ask himself some critical questions.
Will the addition of this control technique reduce or add to present over-
head costs? Can the printer withstand possible reductions in future fuel
allocations and increased costs of natural gas and critical raw materials?
The printer must consider whether heat and hydrocarbon recovery have
real payback features. With the high cost and the availability of natural
gas and petrochemicals such critical factors, loss of heat and ink solvents
must be considered as "misplaced resources."
In many regions of the country there are tax incentives available
where pollution control equipment must be installed. The printer should
investigate this. Some offer exemptions from sales taxes, others increased
rates of depreciation or other "tax-breaks" on new control equipment. The
cost of pollution control is, of course, passed on to the consumer ulti-
mately.
Some companies in other industries have investigated all the above
economic factors associated with pollution control and discovered that be-
sides complying with the air quality regulations, the control equipment
280
-------
can offer a reduction of energy requirements, a "tax break," and an event-
ual payoff of the Investment with a recovered, saleable product.
REFERENCES
1. J. F. Ackermn, "Technological Vulnerability - Ink and Drying Tech-
nology", presented at INTERTECH '74, Chicago, November 20, 1974.
2. W. C. Pfelfer, Xerox Education Center, personal communication, May 30,
1975.
3. G. Swlnford, The Richardson Ink Co., personal communication, May 19,
1975.
4. W. A. Rocap, Jr., "Press Coatings," Proceedings of the Second Graphic
Arts Technical Foundation Conference on A1r Quality Control 1n the
Printing Industry, Graphic Arts Technical Foundation. Pittsburgh, Pa.,
1972, pp. 90-97.
5. R. L. Benemelis, Sun Chemical Corp., personal communication, November
8, 1974.
6. R. R. Gadomski, M. P. David, and G. A. Blahut, Evaluations of Emissions
and Control Technologies in the Graphic Arts Industry, Phase I Final
Technical Report prepared under NAPCA-HEW Contract CPA 22-69-72,
Graphic Arts Technical Foundation, Pittsburgh, Pa., 1970.
7. D. 0. von Lehmden, "Basic Combustion Concepts," EPA Visible Emissions
Evaluation Manual. U.S. Environmental Protection Agency, Research
Triangle Park, N.C., 1973.
8. R. R. Gadomski, A. V. Glmbrone, M. P. David, and W. 0. Green, Evalua-
tion of Emissions and Control Technologies in the Graphic Arts Industry,
Phase II Final Technical Report prepared under EPA Contract 68-02-0001,
Graphic Arts Technical Foundation, Pittsburgh, Pa., 1973, p. 194.
9. A. Morosinl, Peoples Natural Gas Co., personal communication, August
27, 1974.
10. A. E. Blumenthal, and J. R. Plugge, The Short Term Shortage and Long
Term Availability of Resources Vital to the Printing Industry, Envi-
ronmental Conservation Board of the Graphic Communications Industries,
Inc., Pittsburgh, Pa., 1974, Appendix A, p. 2.
11. J. F. Eckelaert, TEC Systems, Inc., personal communication, May 21,
1975.
12. TEC Systems, Inc., "Natural Gas - Maintaining Production with Reduced
Supply Or: How to Get More production Out of Less Gas," TEC Engineer-
ing Concepts Report No. 7205, DePere, Wis., p. 3.
281
-------
13. Ref. 8, p. 195.
14. J. Bender, R. R. Donnelley & Sons, personal communication, June 11,
1975.
15. L. J. Bollyky, Ref. 4, p. 36-47.
16. Ref. 10, p. 11.
17. Ref. 10, p. 12.
NOTE. - A joint discussion with Zborovsky and Fremgen follows Fremgen's
paper.
282
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MONITORING AND TESTING OF EFFLUENTS
FROM LETTERPRESS AND OFFSET PRINTING OPERATIONS
Robert D. Fremgen*
Abstract
The methods of investigation and quantitative results obtained in
monitoring and testing emission control equipment are described. Introduc-
tory background includes the mechanisms and methods of drying as well as
the materials employed that give rise to hydrocarbon emissions. A number
of isokinetic source tests were made in conjunction with the evaluation
of electrostatic precipitators and fiber bed collectors. Evaluations in
both letterpress and web offset operations are reported. Simultaneous
source testing of input and output streams is covered along with the
particulars of the modified EPA impingement train used for source testing.
The results include the correlation of analytical testing with the actual
recovery of hydrocarbon oils from control devices as well as the performance
of emission control equipment.
INTRODUCTION
In determining hydrocarbon emissions from web printing operations there
are three principal interrelated systems elements that affect the result.
These are: the printing operation, the source sampling and analytical tech-
niques, and the emission control equipment if such exists.
With regard to the printing system, this investigation encompasses web
printing both by the letterpress and offset methods. Heatset inks are
employed extensively with both of these processes. Compositions will vary
considerably to accommodate either method as well as multitudinous product
possibilities. Briefly, heatset inks derive their name from the inherent
physical characteristics of the resinous binders used in these compositions.
Apparent dryness is achieved by two mechanisms in successive stages of the
Drying process. In the initial phase of drying, temperature and air
velocity are used to partially evaporate the solvent. In the second stage
*Chemical Process Engineer, Research and Development Department,
Dayton Press, Inc. (formerly the McCall Printing Co.), Dayton, Ohio.
283
-------
of the process, the ink film is chilled to congeal and harden the high-melt-
ing-point resinous components. These two operations convert the ink film
to a quasi nontacky and unsmearable condition.
The high-boiling oils employed in heatset inks serve both as a solvent
for the resinous binders and as a carrier of color matter to the imprinted
image. These ink oils are the primary source of hydrocarbons which occur
as emissions from web printing operations.
While ink oil is seemingly a common denominator, these oils are a
broad and complex category of hydrocarbon materials. In general, the indi-
vidual oils are selected petroleum fractions in the higher boiling range of
derivatives akin to kerosene and the fuel oils. There are in use a series
of a dozen or more narrow- to broad-cut fractions having their boiling point
range anywhere from 400° to 700° F- One or more of these oils are used in
proportions suited to meet specific product and process requirements; these
include, for example, the nature of the substrate to be printed, the method
of printing, drying conditions, and the like.
Being mixed species, the ink oils are compositionally identified only
in a very general sense. For the most part, the ink oils are composed of
mixed paraffins of the normal and isoparaffinic variety together with the
presence of cycloparaffins in some instances as well. They usually also
contain some aromatic and olefinic hydrocarbons, thus being within but
generally not too far removed from the usual regulatory definition for photo-
chemically reactive material. Consequently, deodorized grades of some ink
oils are now available which are outside this photochemical definition.
More recently, further refined grades of some ink oils have been commercial-
ized; these are comprised of fully saturated hydrocarbons. These two newer
varieties of the ink oils have achieved some degree of popularity. Yet,
their photochemical activity is only generally classified by virtue of
extrapolation from that which is known of their chemical characteristics;
substantially less is known of the emission products therefrom.
The drying operation is quite pertinent, since this is where emissions
are generated. In web printing heat is transposed to the moving sheet in
a variety of ways. These include conduction, convection, and radiation;
284
-------
in more than a few instances drying systems include combinations of these.
Such heating is accomplished by hot air streams, steam drums, direct flame
impingement or various combinations thereof.
Most dryers make use of moderate- to high-velocity hot air, as depicted
schematically in figure 1. Invariably, heatset printing will include the
chill roll stand where the web is cooled to harden the ink film thereon.
While the temperature of the drying air may reach as high as 550° F or more,
web temperatures of 275° to 350° F are quite common. Since web speeds
range from 800 to 1,800 feet per minute, this heating is usually accom-
plished in a time span of one-half to one second. Within this short inter-
val, a portion of the ink oil is vaporized, partially recirculated within
the hot air plenum, and partially exhausted.
Conceptually web printing is regarded as a continuous process. This
generalization, however, is somewhat deceiving. More accurately, web
printing is a random series of time-spaced continuous cycles. For example,
a typical time-temperature chart from a dryer recorder (figure 2) shows
running increments of various durations. Moreover, the idle cycles here
shown exclude the "make ready" period when a particular job is set up on
the press.
This random sequence condition shows that more than casual care is
required to assure that source tests are run at equilibrium conditions of
the systems at hand. Beyond the test operation, however, emission rates are
quite another question Process and job variations preclude an absolute
rate. Emissions are best expressed in terms of their concentration and
the rate per hour. The expression of emissions for web printing as a
daily rate has little meaning.
METHODS OF SOURCE TESTING AND ANALYSIS
A modification (ref. 1) of the EPA Method 5 impingement train was em-
ployed for source testing. The equipment configuration (figure 3) is some-
what different than that used for particulate sampling.
In brief, with this modification the sample probe is not heated. The
285
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ROOF LINE
Natural Gas Fuel
ro
oo
WET PRINTED WEB
Combustion
Air Intake
Exhaust
!D~D~D«D»D"D--D»D"D~
RECIRCULATING GAS FIRED
CONVECTION DRYER
CHILL ROLLS
Figure 1. Schematic of web drying process.
-------
Figure 2. Typical press dryer temperature chart.
287
-------
Thermometer
Check
Valve
Umbilical
Vacuum
Line
Air-Tight
Pump
Dry Gas
Meter
Reverse-type
Pitot Tube
Nozzle
Figure 3. Schematic of modified EPA Method 5 sampling train,
-------
purpose is to avoid interference with the physical state of the effluent
mixture in which translational kinetics may have already commenced. Then
too, the filter is located between the third and fourth impingers. Thus
this modified approach enables the gas stream to continue cooling; this
is intended to enhance aerosol formation and its subsequent impingement.
Nonimpingable aerosol particles, which most generally are present, are
trapped beyond the impingers where the filter has little chance of becoming
clogged. The probe of course is washed to recover any contaminents that may
have remained therein. The emission samples are then analyzed by convention-
al gravimetric techniques.
Initially this modification of EPA Method 5 was employed to survey a
variety of press and dryer systems to assess the magnitude of emission
problems. A typical analysis (table 1) showed hydrocarbon emissions in the
range of 20 pounds per hour. Emissions from other press sources were found
to be considerably lower and some were also higher. Since the initial sur-
vey, the modified impingement train has been used 42 times in the analysis
of effluent gases from 15 stacks on 8 printing presses.
The question occasionally arises, why use a test method which is de-
signed for particulates to determine hydrocarbon emissions? To date, while
various instrumental methods have been promulgated (refs. 2,3), regulatory
channels in general have been conspicuously silent in regard to methods for
hydrocarbon sampling and analysis. In retrospect, however, the modified
EPA Method 5 has certain advantages. Being isokinetic, this test is confi-
dently applicable to effluent streams over a broad range of temperatures,
including the comparatively cool exhausts from nonthermal abatement devices.
Additionally, as will be shown, emission measurements correlate quantitative-
ly with the actual collections of contaminents from control equipment. In
a statistical sense, a further advantage is the comparatively large pro-
portion of stack gases that are actually sampled in the 2-hour test period.
Then too, the actual weight of contaminants is determined as opposed to
the application of correction factors and comparative values in relation
to reference materials.
There are of course disadvantages as well. The entrapment of
289
-------
Table 1. Typical midrange level of emissions
from letterpress printing
Average press operating conditions
Printing rate
Dryer temperature
Web temperature
Average stack sampling conditions
Stack temperature
Velocity
Flow rate
Effluent summary
22,550 iph
540° F
295° F
414° F
2,150 fpm
11,457 ACFM
Volume
Concentration rate
(Ib/SCF) (SCFM)
Condensable hydrocarbons 55.82 x 10"6 approx. 0.72
Water
Dry gases
TOTAL
11.91 x 10"" 173.9
7.26 x 10"2 6,620.5
6,795
Weight
rate
(Ib/hr)
22.76
485.6
29,597
30,105
contaminants is limited to materials and the concentrations thereof which
are condensable at impingement temperatures. Unfortunately, the signifi-
cance of noncondensables is to date unknown, since a direct comparison with
other methods has not been made. A further limitation is that the time to
conduct the test severely limits the amount of testing that can be accom-
plished in a given period of time.
MONITORING OF CONTROL SYSTEMS
This search for a systematic means of abating hydrocarbon emissions
from heatset printing has been extensive. Investigations at our plant have
included the compositional aspects of inks as well as a variety of control
devices.
290
-------
Half of the source tests made using the modified Method 5 train were
concerned with efficiency studies on pilot abatement equipment. In these
instances multiple tests on the input and exhaust streams of these control
devices were conducted simultaneously with the use of two trains. Results
of analyses with the modified train were subsequently compared with the
actual collections of materials abated from the gas stream.
Various pilot systems were erected with rigid ducting to utilize a
sample stream from a particular press-oven exhaust stack. After their ini-
tial startup and adjustment, these pilot systems were monitored over an
extended period of continuous running. Such investigations covered from
130 to nearly 500 actual press-run hours.
Some of the more pertinent types of data which were recorded are depict-
ed graphically in the Systems Monitoring Log (figure 4). This diagram shows
several parameters of the abatement process and the press operation as well,
plotted on a time base. These particular data were obtained with a pilot
electrostatic precipitator system on a web offset press. The precipitators
examined were of the two-stage type; that is, ionization with subsequent
collection. Also, these systems were multiple effect configurations.
Throughout the time period here shown, the printed form—that is, the prod-
uct being produced by the press—remained the same. With the exception
of dryer temperature, each data point represents the accumulated average
quantity over the time period between readings or successive points. In
this way the trends and relationships between various processing parameters
were followed.
For example, the amount of hydrocarbon oils removed from each unit in
the abatement system were measured. Here these are shown as the ratio of
condensate in the heat exchanger and that of the aggregate of the oil col-
lections from the electrostatic precipitator units. The total quantity
of hydrocarbons abated from the sample exhaust stream is shown in pounds
per hour of actual press operation.
Press conditions are similarily depicted in the upper three line
plots, which include: the press-running time ratio, oven temperature, and
the average press speed in impressions per hour-
291
-------
Process
Time
Ratio
Oven
Temp.
F.
.80-
.40.
380-
350-
Average 26.000.
Press Speed 24,000-
iph 22.000-
Average
Hydrocarbon
Ibs/imp. - 104
2.5-
2.0-
1.5-
ro
10
no
Hydrocarbon 6-
Recovery 5.
Ib/hr 4.
Hydrocarbon .60.
Collection -SO-
Ratio
.40'
(Basis: 1,000 ACFM sample stream)
16:20
8:50 16:15
8:55 17:45
9:20 16:08
:vn
3/12
3/13
Time
3/14
Figure 4. Systems monitoring log for web offset press and electrostatic precipitators.
(Basis: 1,000 ACFM sample stream)
-------
The center-most line in figure 4 shows the relationship of the rate of
oil collection to the running rate of the press in pounds of hydrocarbons
per impression. To the uninitiated it might seem that this value should be
relatively constant, within some narrow range of experimental error. Not
true; printing is a craft wherein numerous parameters are continually ad-
justed to produce a uniform product. Such adjustments are necessary to
correct for the variances in raw materials as well as the drift or wear in
the replacement elements (plates, blankets, packing, etc.) of the printing
makeup. Thus hydrocarbon emissions deviate from the mean level, particular-
ly over rather broad time periods.
RESULTS OF SOURCE TESTS
Monitoring operations such as these were conducted over hundreds of
hours of operations with both electrostatic precipitator systems and fiber
bed collectors. Data plots such as these were utilized to track their per-
formance. With precipitator systems as well as with fiber bed collectors,
equipment from more than one manufacturer was examined. Consequently, it
is felt that the results can be discussed objectively in terms of the merit
of contemporary technologies while the specific manufacturers remain anony-
mous.
Insofar as possible source tests were made in the course of a printing
run so that monitoring data could be obtained before, during and after the
emission determinations. For example, the two-stage electrostatic precipi-
tator system in figure 4 was source tested in the period between 8:55 and
17:45 on 3/13. The hydrocarbon collection data for this same period were
used for comparison with the emission rates determined with the modified
Method 5 impingement train.
The results of source tests with four electrostatic precipitator sys-
tems are shown in table 2. The data were normalized to 1,000 ACFM input
for ease of comparison. The arithmetic difference between the source tests
for the input and exhaust streams is reflected in the column under Weight
removed, by analyses. For comparison, the hydrocarbon removal determined
from the actual material collected in the control system are labeled Weight
293
-------
Table 2. Performance tests for two-stage electrostatic precipitation systems*
(Basis: 1,000 ACFM sample stream)
Process
loading
System
System
System
System
Heat
E.P.
Comb.
"A"
"B"
"C"
IIQII
exchanger
Total
Super-
ficial
velocity
(fpm)
418
514
393
396
Percent
of
rated
capacity
83.9
100.4
76.8
79.5
Measure of
condensable hydrocarbons
Concentrations
(gr/SCF)
Input
1.046
1.094
0.941
1.463
0.593
Output
0.122
0.222
0.155
0.593
0.072
Weight removed
(Ib/hr)
By
analyses
5.40
5.27
4.96
2.44
4.84
7.28
Di rect
measure
5.61
5.64
5.67
2.38
4.65
7.03
Corre-
lation
(percent)
+ 3.9
+ 7.0
+14.3
- 2.2
- 3.9
- 3.3
Efficiencies
(percent)
Heat Total
exchanger E.P. system
41.4 69.2 82.0
33.6 65.5 77.1
32.2 74.5 82.7
30.5
87.3
91.1
*Systems A, B, and C were evaluated on web offset presses; system D was evaluated on letterpress
equipment.
-------
removed, by direct measure. The correlation between these two values is
rather striking. While better in some cases than in others, the two inde-
pendent data sources are in very good agreement. System "D" is particular-
ly significant; in this instance three source tests were run simultaneously.
These included the system inlet and exhaust streams as well as the gas
stream between the heat exchanger and the precipitator units. These test
results show excellent correlation, both for the individual processes and the
overall system as well.
Although different equipment is represented, the performances of these
systems are rather closely grouped. Even at less than rated capacity,
however, they failed to consistently achieve 85 percent reduction in con-
densable hydrocarbon emissions. Moreover, while not apparent from these
data, it was also conclusively demonstrated that two-stage electrostatic
precipitation is quite unfeasible at the moisture level of the press exhausts
from our plant.
In a further phase of these investigations, fiber bed collector systems
were similarly monitored and source-tested (table 3). In these performance
tests, however, comparative collection data could only be developed with
two of the four systems listed. Also, a broader range of condensable
contaminants was examined. As might be expected, lower concentrations di-
minish the possibility of hydrocarbon entrapment. At first glance the cor-
relation between the rates of hydrocarbon collection are not quite as
excellent as some of the examples covered earlier. Consider though that a
fiber bed is a wetted pad; at equilibrium conditions it will drain at a
constant rate. But, web printing is a random condition of running. Starts
and stops are prone to produce changes, both in the rate of drainage from
the pad as well as the proportion of oil and water in the drainage mixture.
Under these circumstances, and with no prescribed time or condition for
making the monitoring collections, correlation with the results of the
source tests are reasonably good.
Even at moderate-to-heavy loadings these fiber bed systems show a con-
siderable departure from 85-percent reduction requirements. Neither does
there seem to be any improvement with reduced flow rate.
295
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ro
Table 3. Performance tests for fiber-bed collection systems*
(Basis: 1,000 ACFM sample stream)
Process
loading
System "E"
System "F"
System "G"
System "H"
Super-
ficial
velocity
(fpm)
8,0
8.1
31.2
24.6
Percent
of
rated
capacity
88.8
90.6
102.0
80.0
Measure of Efficiencies
condensable hydrocarbons (percent)
Concentrations
(gr/SCF)
Input
0.176
0.372
0.952
0.820
Output
0.132
0.123
0.252
0.231
Weight removed
(ib/hr) Corre- Heat Fiber
By
analyses
0.22
1.35
3.73
3.21
Direct 1 at ion exchanger bed
measure (percent)
Not separately
identifiable
Not separately
identifiable
4.14 +11.1 17.5 55.5
2.95 - 7.9 18.4 56.3
Total
system
22.5
64.7
63.3
64.4
*A11 systems evaluated on web offset presses.
-------
In conclusion, the validity of source tests herein presented has been
substantiated by independent data from actual measurements of total abate-
ment. The value of systematic monitoring of process variables in achieving
definitive results has been demonstrated. Additionally, simultaneous mea-
surement of input and exhaust rates is a most meaningful measure of effi-
ciency.
From a business operational standpoint these studies were expected to
identify a practical method of hydrocarbon abatement; in this respect the
investigation failed. These process investigations have, however, demon-
strated that substantial capital investments in the technologies investi-
gated would be futile and unjustifiable. Moreover, short of thermal abate-
ment methods, which appear somewhat impractical for numerous reasons, an
effective method of control for heatset web printing remains to be developed.
ACKNOWLEDGMENT
The efforts of Mr. George Lock of Dayton Press, Inc., in assisting in
obtaining much of the data herein presented as well as in the preparation
of graphic exhibits is greatfully appreciated.
REFERENCES
1. R. C. Neal, P. L. Hayden, D. R. Grove, and E. A. Brackbill, "Test
Methods for the Evaluation of Hydrocarbon Emissions," Paper presented
at the 32nd Annual Meeting of the East Central Section, Air Pollution
Control Association, Dayton, Ohio, September 18-19, 1975.
2. J. Donald Carruthers, "Stack Sampling and Analysis," paper presented
at the 19th Technical Conference of the National Printing Ink Research
Institute, Lehigh University, Bethlehem, Pa., October 1972, American
Ink Maker, March 1963, pp. 31-40, 58-60.
3. R. R. Gadomski, M. P. David, and G. A. Blahut, "Evaluations of Emis-
sions and Control Technologies in the Graphic Arts Industries," Phase
I, Final Technical Report prepared under (NAPCA-HEW) Contract CPA
22-69-72, Sections 4.0 and 5.0, Graphic Arts Technical Foundation,
Pittsburgh, Pa., August 1970.
297
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DISCUSSION
CHAIRMAN SCHAEFFER: As I promised earlier, I think it only fair at this
point to entertain questions for both Mr. Fremgen and Mr. Zborovsky.
MR. RON LIPINSKI (State of Maryland, Bureau of Air Quality Control, Balti-
more, Maryland): I really have two questions and a comment to make.
The first is for Mr. Zborovsky. You mentioned the use of ultraviolet
inks and low-temperature-drying inks as an alternative control pro-
cedure. In discussing a compliance schedule with several printing com-
panies in Maryland, these were considered as an alternative. Both the
companies indicated they were not desirable because of problems in
color and sheen of the final printed product. Could you or someone
else comment on whether these problems have been eliminated and whether
that option is still a consideration?
MR. FREMGEN: Let me throw something in on that, if I may.
MR. ZBOROVSKY: Sure.
MR. FREMGEN: When you consider drying by the UV process, at the same time
you had better consider which segment of the industry it is in. I
think it was brought out in discussions, perhaps yesterday, that the
industry is broadly segmented, and what may be reality in one segment
of the industry can be a gross color problem in another segment.
MR. LIPINSKI: So there are individual problems then?
MR. FREMGEN: There are individual problems; I think that the ink companies
can respond better to that, but there are individual problems, yes.
MR. LIPINSKI: One quick comment if I could. In the State of Maryland,
where the air solvent control devices (e.g., CVM devices) were tested,
regulations do call for no visible emission. And in all fairness, Joe,
you mentioned that there was really no promise of the CVM device meet-
ing air pollution regulations.
It is our opinion that the device does have potential. We evalu-
ated the units under various conditions, as well as we could. It was
not specifically tested using this technique or some other technique,
but it is our opinion that with some modificiations it could be an
economically viable control device, depending, of course, upon the type
298
-------
of regulations you have to meet. It had difficulty meeting no visible
emissions, this is true. But it is our opinion that with some modifi-
cations it could even meet that.
My final question is to Mr. Fremgen. You mentioned in your
evaluations of the two-stage ESP that they were not viable control
devices because of the moisture content present in the exhaust stream.
Could you comment on that? Were these your letterpress ovens or your
web offset ovens.
MR. FREMGEN: Certainly, offset more than letterpress, but actually, both.
You will actually find the performance will change with the season
of the year- The season of the year determines the moisture content
in the ambient air.
If you look at a press, it has several important sources of
moisture. The first of these comes from the web that goes into the
press oven itself. The second important source of moisture is the
combustion with methane for the heating and drying. And the third
source, in the case of all presses, would be the ambient air that goes
into that oven simultaneously with the web. Specifically, in the
case of lithography, a fourth source is the dampening solution. It
tends to be a little heavier in moisture than the letterpress stream.
But we found and conclusively demonstrated that with the moisture con-
tent of the exhausts at our plant, the equipment will not take it.
MR. LIPINSKI: It will not operate efficiently then.
MR. FREMGEN: It will not operate reliably. There is no point in having
that dude on the roof if it will not run, it will not do the job you
guys want it to do.
MR. LIPINSKI: Joe, in your evaluation of this UAS ESP, have you received
similar comments that it is not a reliable control device from the
other people who have utilized it?
MR. ZBOROVSKY: I have heard some information, but some people have con-
ducted tests on the UAS system. And I think they obtained some of the
results that are very much the same as what Bob has obtained in his
studies. I have not seen any document evidence at this time.
CHAIRMAN SCHAEFFER: We have not done a study on that unit.
299
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MR. FREMGEN: The real key in any of this equipment, in putting it up there
and flipping a switch and looking at the plume, is that you really have
to concentrate on that equipment if you want to find out how it is going
to operate, what it is going to do for you. It takes intense study,
and I am afraid people who act on intuition are going to spend a heck
of a lot of money.
MR. LIPINSKj; Thank you.
CHAIRMAN SCHAEFFER: A question?
MR. JERRY NASS (United States Printing Company, E. Rutherford, New Jersey):
This question is for Mr. Zborovsky. In your data on low-solvent, low-
energy inks, your figures state as low as 25-roughly below what is
normally used in conventional inks. I would like to know the speed of
the press where this was taken, the nature of the job, the amount of
coverage, and whether it was with substrates such as coated paper.
Also, if possible, I would like to know whether it went to a sheeter
or folder, and finally, if this was a field trial or commercial run?
MR. ZBOROVSKY: That is a very interesting question. I do not have that kind
of information. Most of this information was supplied to me by Inmont
Corporation. And I think if you are interested in this, you could
possibly contact a gentleman from Inmont; his name is Joseph F. Ackerman
I think he might be able to supply you with that information.
CHAIRMAN SCHAEFFER: Joe, we were involved with a test with a low-tempera-
ture, low-solvent-drying ink on a field test, not a commercial produc-
tion run, which was a four-color production job. If I remember cor-
rectly, we attempted to run in the neighborhood of 800 to 1,000 fpm.
But it was not a very successful run as a field test.
MR. FREMGEN: Incidentally, preprints of my paper will be available in the
lobby.
MR. BRUCE LAMM (Fawcett Printing Corporation, Rockville, Maryland): This
is directed to Mr. Fremgen. You stated that the system will not handle
moisture. Yet in the two-stage electrostatic precipitator, you are
actually adding moisture to reduce the temperature, because the unit
will not accept temperatures higher than 200°.
300
-------
MR. FREMGEN: I am not using moisture as a cooling device. I am using in-
direct cooling. I did not add moisture to the stream. This particular
system, as a substitute, was cooled with a water tube heat exchanger.
This was only a substitute because pilot air-to-air heat exchangers
are rather difficult to come by.
MR. LAMM: We are in the process of adding the electrostatic precipitator
to two of our presses. And we are getting what we call the sonic heat
exchanger, which is nothing but a controlled water spray.
MR. FREMGEN: Right.
CHAIRMAN SCHAEFFER: Any other questions?
GENERAL CHAIRMAN FISHER: Mr. Zborovsky, you mentioned among the systems an
activated charcoal system. One of the things that bothers me about
these activated charcoal systems is their need for regeneration. If
you use a hot air regeneration technique, really all you do is collect
the material and let it out; you are not running other operations.
Do you have any information on exactly what process they are
using to regenerate the charcoal, and what controls they are placing
on the effluent from the regeneration?
MR. ZBOROVSKY: The activated charcoal system that Los Angeles Lithograph
Company is utilizing is a patented process where they have electrical
heating elements in each bed. They are using a vacuum system on this,
where they pull the vacuum down to about two torrs, or about two
millimeters of mercury. By lowering the pressure or pulling the vacuum
down on each bed and increasing the temperature of the bed, they are
able to flash-off these hydrocarbons. They have a condensation system
which is a series of condensers—first watercooled condensers and then
a refrigeration system—which brings the temperature down to maybe -40° F.
The hydrocarbons that are recovered then in the collection tanks
are trapped. And just by the different temperatures of these conden-
sers, they are able to get an effective separation between the high
boilers and the low boilers rolls that are entrapped on the activated
charcoal.
I do not think that there are any problems that I can recall in
301
-------
regenerating these particular systems other than some of the operation-
al problems they have in the actual design of the equipment. They
are plagued with a series of leaks, temperature drops, and temperature
control. That is the major problem with this particular type of
system. Other than that, it seems to be a very reliable system, pro-
viding these problems can be eliminated.
MR. FREMGEN: Consider also the fact that the vacuum installation is unique.
It is not like the systems used for gravure operations at all. The
carbon bed can get clogged up with a lot of resinous material. Replace-
ment of carbon is neither inexpensive nor easy.
MR. ZBOROVSKY: If there has not been adequate temperature control in that
particular bed, there will be some condensation of some of the resinous
material. You get some plugging or channeling in the bed.
CHAIRMAN SCHAEFFER: I think we have had two very interesting sessions in
looking at the Environmental Impact of Chemicals Used in the Printing
Industries. I want to thank the speakers for their very effective
presentations and you, the audience, for your active participation in
the program.
302
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23 September 1975
Session III:
IMPACT OF WASTE RECOVERY
AND RECYCLING ON THE ENVIRONMENT
Robert L. King*
Chairman
'General Engineer, Office of Enforcement, National Field Investigations Center, Environmental Protection
Agency, Denver, Colorado
303
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SESSION INTRODUCTION
Robert L. King
Session Chairman
In this session, the first two speakers talk in terms of two areas.
One is monitoring of wastewater effluents; the second looks at the new dirty
word in EPA, PCB's. The meaning is fairly well hidden, but behind the title
are sources of toxic chemicals.
304
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MONITORING OF LIQUID EFFLUENTS FROM
THE GOVERNMENT PRINTING PLANT
A. R. Materazzi, Ph.D., and J. U. Gouin*
Abstract
The program of monitoring our effluent water has given us a firm pic-
ture of the quality of our effluent, as well as an opportunity to work with
test procedures stipulated by the Environmental Protection Agency. We
found that in our laboratories tuo of these procedures had to be modified
slightly in order to avoid ambiguous results. Nearly all of our effluents
were within ranges acceptable to Government standards. The monitoring
program continues but at a reduced rate. We think that we can improve the
one or two problem areas indicated by our tests and that we should be able
to comply with the proposed EPA regulations. Despite our heavy consumption
of water, which will tend to dilute any contaminants entering the effluent,
we feel that the results we have obtained are indicative of what can be
expected by the printing industry in general.
The United States Government Printing Office was established in 1861
in order to provide printing services required by the Congress. The first
Government Printing Office was housed in a four-story wooden structure con-
taining 60,000 square feet of floor space; it housed 26 printing presses and
4 pieces of bindery equipment. Three hundred and fifty employees produced
Congressional printing valued at approximately $500,000.
Today the Government Printing Office occupies three eight-story build-
ings and one four-story building, which have a combined floor space of more
than 32 acres. It employs 8,500 people and produces or procures printing
and binding for the Federal Government valued at nearly $500 million in
fiscal year 1975. Even though almost 70 percent of the printed products
are procured from commercial printing sources, the remaining 30 percent is
considerable. To accomplish the in-house work, it utilizes 340 composing
and casting machines, 2 high-speed photocomposing systems known as the
*Albert R. Materazzi, Manager, Quality Control and Technical Department;
and J. U. Gouin; U.S. Government Printing Office, Washington, D.C.
305
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Linotron 1010's, 240 pieces of bindery equipment ranging from wire stitch-
ing to automated binding lines; 42 offset presses, and 83 letterpresses.
The most modern piece of equipment is the optical character reader and test
editing system, which greatly augments the output of the Linotrons.
Several types of relief plates are made, including photopolymer and
stereos in addition to copper, zinc, and magnesium engravings. Over 85,000
aluminum offset plates are used in 1 year and 1 million square feet of
photographic film. The paper required to produce this work requires nearly
7 freight cars and more than 11 truckloads each day. We manufacture 200,000
pounds of ink in a normal year and buy another 300,000 pounds. We make most
of our own adhesives and have our own carpenter, electrical, sheet metal,
and machine shops.
With the exception of flexography and gravure, the Government Printing
Office can be considered a microcosm of the entire printing industry of the
United States. Thus it can be argued that our experiences with problems
associated with the environment reflect those of the industry. The results
we obtained in monitoring our water effluents should be of interest and,
if typical, they would indicate that the printing industry is not a signifi-
cant contributor to the pollution of our water resources. The threefold
purpose of this paper is to document our experiences describing the test
methods utilized, to list the results obtained, and to compare them with
proposed EPA effluent limitation guidelines for discharge to surface water
of process waste pollutants of the paint, ink formulation, and printing
industry.
During the fiscal years 1972 through 1974 the water consumption of
the Government Printing Office averaged 240 million gallons per year.
Eventually all of this finds its way into the District of Columbia sewage
treatment plants. It is not possible to break out the specific amount of
water used by the manufacturing processes at the Government Printing Office.
In a general sense we know that a considerable portion of the water is
used for cooling purposes in linotype and monotype composing machines, in
the making of stereotype plates, and in the chill rollers of web offset
presses. A great deal of water is used in the production of negatives and
306
-------
offset plates. Also, significant users are in photoengraving, electrotyping,
the type metal foundry, and the inkmaking section. When we consider the
needs of over 8,000 employees and the industrial cleaning required for 32
acres of floor space, it is no wonder that on an average 24-hour working
day approximately 33,000 gallons of water per hour are used by the Govern-
ment Printing Office.
There are no regulatory limits on the quality of water being discharged
by large industrial users in the District of Columbia, Section 307B of the
Water Pollution Control Act of 1972 (Public Law 92-500) requires the Fed-
eral Government to establish regulations concerning the discharge of process
wastewater by industry. EPA has published proposed effluent limitation
guidelines for the paint, ink formulation, and printing industries which
are presently being reviewed and are targeted for adoption some time in
1976. The District of Columbia is waiting for limitations to be published
regarding discharge into sewage systems before issuing its own regulations.
It may adopt Federal regulations or modify them as the local situation
requires.
Consequently the Government Printing Office began to analyze its
effluent water early in 1975 in order to establish what problems might be
encountered in meeting the proposed standards. In addition, the informa-
tion was required for the environmental impact study currently in prepara-
tion looking forward to a new Government Printing Office early in the 1980's.
What follows is a report of the procedures and methods used and the results
we have obtained thus far, followed by a discussion of what we have learned
from this preliminary work.
Six discharge points in the Government Printing Office complex were
selected based on ease of availability and because they were the identical
points used for a special sampling conducted by the District of Columbia
Government during the summer of 1974. These points are shown in figure 1
and are assigned Roman numerals I through VI on table 5. Two men were used
to procure samples, which were taken by dangling a collapsible 1-quart
plastic container at the end of the strong twine into the effluent water.
Some 1-1/2 to 2 hours were required to procure samples at all six locations.
307
-------
I
I
I
1
1
1
H STREET.
•4
••
• ^
G STREET
•
BLDG. 3
BLDG. 1
•5
3
(_
• o
g
a.
u
• i
Z
i i
I
/
| BLDG. 4 )'
7
Figure 1. Combined sewer effluent sampling location,
U.S.G.P.O., Washington, D.C.
The containers were delivered to the laboratory and analysis usually began
the same day. Initially we used methods and procedures taken from Stand-
ard Methods for the Examination of Water and Wastewater," 13th edition,
(ref. 1), and "Methods for Chemical Analysis of Water and Wastes," 1971,
published by EPA (ref. 2). Some changes in these procedures became neces-
sary; these will be pointed out later on. The results were compared
against the proposed EPA limitations. The intent was that if we had found
significant variations from these standards, corrective action would be
taken. None was necessary.
Table 1 shows the metal concentrations obtained in these tests. Ini-
tially the analyses were made using an atomic absorption spectrophotometer,
model 403, built by the Perkin-Elmer Corporation. Suspended solids were
removed prior to analysis. All of the samples to the left of the bold
line are those that we determined to be below the concentration of the pro-
posed limitations and those to the right are over the limitations. It
should be pointed out that all of the lead determinations of the 60 samples
whose concentrations are listed in the 0.05 to 0.10 mg/1 category were
placed in that column because the detection limit of the spectrophotometer
308
-------
Table 1. Heavy metals analysis
Element
Lead
Chrome
Copper
Zinc
Iron
Manganese
Magnesium
Proposed
limita-,
tions
.05
.5
.5
.5
1.0
1.0
100.0
Cone.
in tap,,
water
<.l
<.05
<.05
<.05
<.10
<.05
5.5
<.05 mg/1
43
33
43
53
.05-. 10 mg/1
60
7
13
6
32
3
.11-. 5 mg/1
5
3
15
11
17
6
.51-1-0 mg/1
2
1
2
4
1.1-5.0 ng/1
1
2
1
1
1
1
13
>5.0 mg/1
2
'.7
^Proposed EPA effluent limitations for discharge of process wastewater pollutants expressed in
milligrams per liter.
P
Numbers 1n columns refer to number of samples analyzed which had that concentration.
Table 2. Lead determination by A. A. using furnace (flameless metnod)
Date
8/25/75
8/26/75
8/28/75
Proposed
limitation*
.05
I
.008
.019
.022
II
.004
.009
.005
III
.003
.002
.001
IV
.006
.008
.016
V
.003
.004
.002
VI
.002
.014
.004
Tap water
<.001
<.001
< 001
*Proposed EPA effluent limitations for discharge of process wastewater
pollutant-
NOTE.-Numbers in columns are mg/liter.
using the air-acetylene flame was only 0.10 mg/1. Subsequently we obtained
a furnace which extends the lower limit capability well below the 0.05
mg/1 limit. Table 2 shows the results obtained using this instrument modi-
fication and shows that we are well below the proposed standard. Since the
Government Printing Office manufactures or recycles over 12 million p^'nds
of type metal that is approximately 83 percent lead, we were pleasantly
surpri sed.
The next item of concern was the chromium content; 10 percent of the
309
-------
samples were over the recommended standard. Very little chromium enters
the effluent from the manufacturing process, a very minor amount from off-
set press fountain solutions, and a smaller quantity from the rinsing opera-
tions in electroplating. We now feel that the chromium found comes from
rust inhibitors incorporated in the water in our air-conditioning towers.
The air-conditioning system is being replaced and this situation should
correct itself.
The only other element we expected to be a problem was zinc coming
into the system from offset press fountain solutions, the diazo salts used
in offset plate sensitizers and zinc etchings. Only 2 out of 62 samples
were above the proposed minimums. Surprisingly, considering the occasional
hard water encountered in the District of Columbia and the number of mag-
nesium plates made, all of the samples were below minimum in magnesium
content.
Results for organic substances, suspended solids, and pH are shown in
table 3. Seven different samples were taken at seven different times at
each of the six sampling points. Once the determinations were made the
results were averaged. However, only three samples taken at three different
times were used for the oils and greases because of a problem with the test
method.
Even though the proposed standards have no limits for chemical oxygen
demand (COD), we made these determinations and they are listed in table 3.
It is not possible to assign to the manufacturing process an established
percentage of this value since the water from the manufacturing process
and that used for the elimination of human waste are discharged together
into the effluent.
It is readily apparent that we have no problem with pH despite the
use of caustic cleaning agents in our ink section and the use of acids in
photographic and etching operations.
Nor is any problem indicated with phenols. We did fail to comply with
the proposed standards for suspended solids in five of the six sampling
points. We are currently trying to determine the source of these solids.
One possibility is the lacquer developer used in offset platemaking, which
310
-------
Table 3. Miscellaneous water analyses
Analysis
PH
Suspended
solids1
Phenols2
Oils &
greases'
Chemical
oxygen
demand
Proposed ,
limitations
6-9
30
100
10
None
given
I
6.94
26.0
<2.5
23.6
124
II
7.43
121
<2.5
67.0
301
III
7.56
70.0
<2.5
19.7
48
IV
6.40
229
<2.5
142.9
512
V
7.44
51.0
<2.5
25.5
317
VI
7.58
76.0
<2.5
53.0
240
Hi
8.1
494
2.5
3.2
875
Lo
3.7
.1
252.8
24
Numbers are milligrams per liter.
o
Numbers are micrograms per liter.
Proposed EPA effluent limitations for discharge of process wastewater pollutants.
Table 4. Suspended solids (all samples are from Sample Point IV only)
Date
8/18/75
8/20/75
Proposed ,
limitations
30
•i
10:00'
63*
45
10:10
199
214
10:20
28
104
11:00
102
-
11:10
63
456
11:20
246
258
Average
117
215
^Column headings are the actual times samples were taken in the A.M.
lumbers are milligrams per liter.
^Heading is proposed EPA effluent limitation.
contains considerable quantities of insolubles. However, we had a large
variation in results, so on two occasions we sampled at ID-minute intervals
Table 4 shows the results with still a large variation. We suspect that
the variations are probably not due to the manufacturing process but to an
inadequacy of the sampling method which could include large undispersed
agglomerates. In any case, the sampling techniques employed are going to
311
-------
have to insure that the sample is dispersed and representative of the manu-
facturing waste only. If the waste can agglomerate, it would not be repre-
sentative. In that instance, sampling at consecutive brief intervals may
give more meaningful results. We intend to pursue this line of investiga-
tion further.
Oils and greases were above proposed limitations but since cafeteria
waste and human waste are included, no firm conclusion can be reached.
Table 5 lists the results of lead determinations compared with lead
content in tapwater and is included to show the degree of sophistication
required for analysis. Only the six circled points exceeded the amount con-
tained in tapwater. These determinations were made with the acetylene
flame before we acquired our furnace for the atomic absorption spectro-
photometer and we have not had time to repeat the work with the electric
furnace. However, this pinpoints a problem in sampling, since it is obvious
Table 5. Lead analysis
Date I II III IV V VI Tap
2/11/75 <.l <.l <.
2/20/75 .29 <.l <.
2/28/75 <.l
-------
had we not sampled the week of February 20, 1975, we would have been in com-
pliance at all but two points. From this, one should conclude that some
consideration will have to be given to the time lapse between samplings.
As was pointed out earlier, once we increased the sensitivity of our instru-
ment we were well below the proposed limits.
Discussion of test methods
Two of the test methods recommended by the literature gave us a prob-
lem. The first was the colorimetric method utilized for the determination
of phenol. This method is based on the use of 4-aminoantipyrine, which
reacts with phenol to produce a characteristic color that can be extracted
with chloroform. The absorption of the extraction at a selected wavelength
is measured in a colorimeter. The instructions in the literature indicate
that the 4-aminoantipyrine is added first, followed immediately with the
addition of potassium ferricyanide to avoid the color coupler being oxi-
dized by agents present in solution. When this happens, the color reagent
becomes darker in color and even unreacted dark color reagent would be
extracted, resulting in high readings. Both the reacted material and the
original color coupler are extracted by chloroform. We found higher values
when running blanks with distilled water and tapwater than those of the
samples being analyzed. By reversing the addition of the reagents, i.e.,
by adding the potassium ferricyanide first, the results obtained with the
distilled water and tapwater blanks were sensibly lower than the samples.
We now use this procedure in analyzing for phenol.
We theorize that dissolved oxygen in water was causing our problem
and it was prevented from reacting with the color reagent by adding the
anti-oxident first. We plan at some future time to prove this hypothesis
by using distilled water saturated with an inert gas—for example, argon.
The EPA "Methods for Chemical Analysis of Water and Wastes" specifies
the procedure for analyzing for oils and greases and requires that the
acidified sewer sample be filtered through muslin cloth and diatomaceous
earth. The filter pad is transferred to an extraction thimble and placed
313
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in a Soxhlet extraction apparatus and extracted by refluxing for 4 hours
with hexane. The solvent is driven off the extracted material and the
amount of oils and greases determined gravimetrically.
A problem was encountered using this method. Extraction performed
using distilled water and tapwater in place of the sewer sample also gave
high results. The I.R. curves of the water extractions were compared with
a hexane extraction of the muslin and filter aid; they were identical. We
were forced to assume that they contained hexane soluble materials.
We then tried an alternate procedure from "Standard Methods for "Exam-
ination of Water and Wastewater." This involved extracting the acidified
sample with hexane in a separatory funnel. The supernatant liquid was
filtered through No. 40 filter paper into a beaker, evaporated, and the
amount of oil and greases was then determined gravimetrically.
When this method is used with tap or distilled water, a negligible
amount of residual material remains in the beaker. More important, the I.R.
curves of sewer sample extractions are different than those obtained with
the muslin-filter aid extraction method. We consider this method to be
much more reliable.
Summary
The program of monitoring our effluent water has given us a firm pic-
ture of the quality of our effluent, which we could only estimate previously.
It also gave us an opportunity to work with the test procedures stipulated
by the Environmental Protection Agency. We found that in our laboratories
two of these procedures had to be modified slightly in order to avoid ambig-
uous results. The monitoring program continues but at a reduced rate. We
think that we can improve the one or two problem areas indicated by our
tests and that we should be able to comply with the proposed EPA regulations.
We also feel that despite our heavy consumption of water, which will tend
to dilute any contaminants entering the effluent, the results we have ob-
tained are indicative of what can be expected by the printing industry in
general.
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REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 13th
Edition, American Public Health Association, New York.
2. Methods for Chemical Analysis of Water and Wastes, Environmental Pro-
tection Agency, 1971.
COMMENT GIVEN AFTER PRESENTATION OF THE PAPER
Albert R. Materazzi
After listening to the papers presented thus far, I would like to make
a few observations and present for your consideration a few caveats in
light of Dr. Fisher's comments yesterday.
A casual count of the speakers during this conference breaks down to
9 from the governmental sector and 24 from the industry or its suppliers.
I include Bob Praskievicz and myself in the industry sector for obvious
reasons.
Industry speakers have uniformly presented what I consider to be well-
researched and documented papers, with little or no attempt to disguise
the warts. They have shown a keen awareness of the need to protect the
environment, their employees, and their customers—the consumer. They have
done their homework well and demonstrated excellent knowledge of existing,
proposed, and rapidly changing guidelines. The speakers from the govern-
mental sector have not (and I admit to some lack of objectivity) shown a
similar knowledge of the printing industry or a sensitivity to its problems.
Admittedly it is not as easy to understand the "fragmented" printing in-
dustry as it is to understand a well-written proposed standard in the Feder-
al Register; but we have heard a 25- to 30-year-old monograph on inks cited
as an authority; we have heard our unions cited as authority for the number
of employees in the industry; and overall it seems that the industry was
researched in the Encyclopedia Brittannica. If I exaggerate, I apologize.
While I realize that since Macy does not tell Gimbels, one should not
expect to get good information on Macy from Gimbels, I still submit that
the sometimes conflicting Environmental Protection/Employee and Consumer
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Safety regulatory bodies and the printing industry should not have the same
competitive relationship that Macy and Gimbels have--nor should it be an
adversary relationship.
You have heard the industry characterized as a $22 billion industry
and I assure you that the figure is on the low side. According to the
Federal Reserve Board index of Industrial Production, the industry accounted
for close to 8 percent of the total industrial production in the 1967 index
year and it was growing at a faster rate than the index. In August
of 1975, the index for all industrial production stood at 112.9, while that
for SIC Code 26 and 27, the Paper and Printing Industry, stood at 108.9.
The industry is in trouble and is still in an economic slump. Several
speakers have pointed out the fragmented nature of the industry, and the
number of "mom and pop shops." Their dependence on suppliers and trade
associations is almost complete in the area of ecology, employee protection,
and consumerism. As has been demonstrated, the industry research groups
are doing an excellent job and an inordinate amount of their time is con-
sumed in these problems. And I am sure I speak for all of them. Do not
hesitate to go to them for real information or to check data. I think I
speak for the Public Printer and GPO when I say we will be pleased to co-
operate in any reasonable, well-defined experiments designed to improve our
environment.
If you will permit a personal note, I came into lithography 35 years
ago. At the time we were extensively using wet plate photography, which
used a collodion binder on glass (gun cotton in ether and alcohol) sensi-
tized with silver nitrate. After exposure, it was developed with ferrous
sulfate and fixed with sodium cyanide. It was intensified by bleaching in
a mercury or lead salt and redarkened with a solution of sodium sulfide.
Pressmen were routinely using carbon disulfide to regenerate rubber blankets
and rollers; strippers were routinely using carbon tetrachloride to clean
film. All of these were gone long before the regulatory bodies came into
existence in 1970. The point is that the graphic arts industry was working
to improve itself long before EPA, and was doing a pretty good job.
It was Montaigne who pointed out, "There were never in the world two
opinions alike, no more than two hairs or two grains; the most universal
quality is diversity." And with that I heartily agree, but let me quote
to you from an address by the late President John F. Kennedy: "Let us not
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be blind to our differences—but let us also divert attention to our com-
mon interests and the means by which those differences can be resolved.
And if we cannot end our differences, at least we can help make the world
safe for diversity."
I trust that everyone attending this conference was listening and that
he does not leave here without a broader view of the problems which face
us in protecting this narrow, fragile biosphere in which we live without
crippling an important industry whose products are still the most important
means of communication ever devised by man.
DISCUSSION -
GENERAL CHAIRMAN FISHER: As General Chairman of this conference, I suppose
I really cannot let a malignment of the program go without comment. Dr.
Materazzi is, of course, entitled to his opinion, but I must say I
find it very discouraging that he seems to take the attitude that "If
you do not know as much about printing as I do, you have nothing to tell
me."
It is true that some of the speakers on this program are not
experts in the printing industry, but they are all here because they
are experts in something. And they have information which we feel
should be of interest and importance to you. People like Dr. Kay and
Dr. Herbert are not printers. Nobody ever said they were, nobody pre-
tended that they are. They are experts in their own field of investi-
gation. And they have been working in areas which happen to impact
on the printing operation. We feel it is perfectly proper and that
you should be aware of what they have found. They have found things
which, with all your expertise in the printing industry, you probably
never would have found because you are not an expert in epidemiology,
toxicology, and so on.
I find it a little surprising that I hear the attitude, "These
people are not qualified to talk to me." I realize that not all of us
think that all of the papers are of equal quality, but I think that
on the whole the papers have been good; I think they have been per-
tinent and I think all the speakers have contributed to our knowledge.
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DR. MATERAZZI: I have no further comments beyond to say that I did not
intend to be critical of the papers that you mentioned. But I was
critical of the application to the printing industry based on what
appears to me to be insufficient knowledge of the industry as such.
I think that they could have gotten far better inputs had they
gone to Dr. Schaeffer, to Harvey George, to Paul Borth, to any number
of people that are here from the industry, or to our suppliers.
Al Jasser back there has been looking out after the environment
and the safety of the industry long before OSHA was dreamed of.
Jackie Fetsko's work, I think, speaks for itself. This is the type
of thing that I am talking about. And while I have no objection to
people telling me what the carcinogens are in the industry, I submit
we knew they were there. Somebody had to tell us, and they are still
trying to tell us wf\at the limits are.
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DISCUSSION OF POLYCHLORINATED BIPHENYLS
IN WASTE STREAMS FROM PAPER RECYCLING
Karl E. Bremer*
Abstract
Current data on poly chlorinated biphenyls (PCB's), a family of chlorine-
containing organic chemicals, indicate that effluents of waste paper recy-
cling mills contain variable concentrations of PCB's. Surveillance of the
industry demonstrated that 7 of 14 waste papers destined for recycling con-
tained .1 to 3.6 ppm PCS. These waste papers represented SO percent of the
waste papers recycled at a particular mill. Current documentation suggests
that mill waste treatment systems, which effectively remove particulate mat-
ter 3 may remove PCB's.
INTRODUCTION
Polychlorinated biphenyls (PCB's) were first manufactured commercially
in 1929. In the United States, PCB's have been manufactured by a single
producer, the Monsanto Industrial Chemicals Company. In addition, PCB's
are manufactured in Great Britain, France, Germany, the U.S.S.R., Japan,
Spain, Italy, and Czechoslovakia (ref. 1).
PCB's have been used in the following broad types of applications during
the past 40 years (ref. 2):
1. "Open-ended" applications; for example, in paints, specialty inks,
paper coatings, plastics, etc.
2. "Nominally closed" applications; for example, as the working fluid
in hydraulic or heat transfer systems.
3. "Closed electrical system" applications, specifically as the
insulating fluid in certain kinds of transformers and capacitors.
The Monsanto Industrial Chemicals Company has marketed chlorinated
biphenyls under the trademarks Aroclor 1221, 1232, 1242, 1248, 1254, 1260,
*Chairman, Lake Michigan Cooling Water Studies Panel, U.S. Environmental
Protection Agency, Chicago, Illinois.
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1262, and 1268. The latter two digits designate the percent chlorine of
each formulation (ref. 3). During the period 1963-1971, U.S. domestic
sales of Aroclor 1242 and 1254 were higher than other Aroclors. Aroclor
1016 is currently replacing Aroclor 1242 as a capacitor impregnant (ref. 2).
Current data for 1974-1975 indicate that PCB residuals have been found
in fish from the marine coastal areas of the East and West, from the riverine
environment, including the Mississippi, Ohio, and Hudson Rivers, and from
the Great Lakes Basin, including Lake Superior, Lake Michigan, and Lake
Ontario.
Current data for 1974-1975 further indicate that PCB concentrations 1n
Lake Michigan coho salmon, lake trout, and chubs exceed the Food and Drug
Administration's temporary tolerance level of 5 ppm. These concentrations
have not decreased since 1972, although Monsanto has indicated limiting sale
of PCB's to manufacturers of sealed electrical equipment such as transformers
and capacitors. Past and more recent data demonstrate that loss of PCB's to
the environment constitutes an environmental and human health hazard and is
a direct cause of economic loss to the commercial fishery.
HEALTH EFFECTS
In 1968, a reported 1,000 Japanese were adversely affected after con-
suming rice oil containing an estimated 2,000 ppm of PCB's. During food
processing of the rice oil, leaking hydrolic fluid had contaminated the oil,
Japanese consuming the oil exhibited symptoms including eye discharges,
acne-form lesions, and skin pigmentation problems. Pregnant women suffered
miscarriages, and in childbirths, transplacental transfer of PCB's to
infants was observed.
Recently, the effects of PCB's have been demonstrated in subhuman pri-
mates (rhesus monkeys) (ref. 4). In studies at the University of Wisconsin
Medical School, six adult female rhesus monkeys were fed Aroclor 1248 at the
level of 25 ppm for 2 months. Facial edema, alopecia, and acne were devel-
oped within 1 month, and one animal died as a result of PCB intoxication 2
months after removal from the experimental diet. These observations and
others during the 1974 study attest to the toxicity of short-term, low-level
exposure to PCB's in subhuman primates. More recent data have been obtained
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at the 2.5- and 5-ppm level (ref. 5). General observations of subhuman pri-
mates subjected to prolonged consumption of Aroclor 1248 at these levels were
the following: alopecia, acne lesions, loss of weight, Increased secretion
of total urnlnary ketosterlods, Irregularities 1n menstrual cycles. Impaired
ability to maintain pregnancy, and undersized Infants.
Detailed presentations of biological effects on man (metabolism, toxi-
cology, and results of human exposures) and biological effects on animals
other than man have been developed by the Interdepartmental Task Force on
PCB's (ref. 1). It is of Interest that these and other studies demonstrate
that rats tolerate PCB consumption at the 100-ppm level; subhuman primate
studies show that the 100-ppm level 1s lethal and that the effect level 1s
2.5 to 5 ppm.
PCB'S IN WATER AND BIOLOGICAL ACCUMULATION
As Indicated by data on residual PCB's 1n fish, water 1s a principal
sink and transport mechanism for PCB's. Studies during 1971-1975 indicate
that, 1n Industrialized areas, wastewater-treatment-plant effluents are
major point sources of PCB discharge to surface waters. Because biological
accumulation of PCB's by fish and other aquatic organisms has been documented
as greater than 40,000 and 75,000 times the exposure level, respectively
(ref. 6), 1t 1s recommended that PCB's do not enter the receiving waters at
detectable concentrations. (Currently detection limits range from .02 to
.05 ppb.)
During the Spring of 1975, the Wisconsin Department of Natural Resources
analyzed, as a part of their ongoing surveillance program, a number of dis-
charges to Green Bay and Lake Michigan (ref. 7). Concentrations during this
survey ranged from <.l to 18.5 ppb. Because PCB concentrations were high 1n
effluents of paper recycling mills, Inplant investigations were requested of
the Industries. Analysis of 14 wastepaper samples Indicated that 7 wastepaper
grades contained PCB's ranging from .1 ppm Aroclor 1254 and .5 ppm Aroclor
1242 In heavy printed bleached Kraft to .4 ppm Aroclor 1254 and 3.6 ppm
Aroclor 1242 1n sorted office wastepaper. The seven wastepapers containing
PCB's represented 50 percent of the wastepapers recycled at a particular
mill. In addition, it was speculated that the majority of these wastepapers
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represented office waste forms, NCR carbonless paper, and ledgers from
old files, which would date back to the period when PCB's were used in the
manufacture of carbonless papers.
The Wisconsin Department of Natural Resources, in a continuing monitor-
ing program, tested the effluents of 16 pulp and paper mills. Analysis
demonstrated that nine mills had discharges of PCB's ranging from .1 to more
than 18 ppb. The higher concentrations of PCB's were found in effluents of
two mills which deink and recycle wastepapers.
The Central Regional Laboratory of the U.S. Environmental Protection
Agency in Chicago has, and is currently assisting Wisconsin and other States
in the Great Lakes Basin. The laboratory is currently involved in analyses
of common forms and inks, and in analysis of PCB's in air.
CONTROL
As a suggested means of reducing PCB concentrations in waste streams
I would like to present an excerpt from the recent Wisconsin Hearings on
PCB's. This short presentation (ref. 8) was developed by Francis Early, a
physical scientist of the Environmental Protection Agency.
Mr. Early states: "A problem of real concern at this time must be the
relatively high discharge concentrations from certain Pulp and Paper mills
which deink paper.
"For the record, let me briefly sketch in words the general processes
used for deinking paper. The deinking pulp producer buys waste paper, which
is carefully selected for the end product paper which he intends to make
from the deinked pulp. These waste papers are slurried in hot water with
wetting agents or dispersants and an alkaline or acidic agent to adjust the
pH. Other chemicals are used as required. Once slurried, the paper, now
undeinked pulp, is screened and cleaned to remove undispersed material,
pieces of metal, and grit. The actual deinking takes place in a series of
washers which are usually operated with countercurrent process streams. The
undeinked pulp enters the system of washers at one end while clean water is
introduced at the opposite end. The deinked pulp and dirty water are dis-
charged at opposite ends. A primary objective of this process is to recover
a quality fiber free from all inks, chemicals and pigments. As required by
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the needs of the end product paper, one or more stages of bleaching may be
used.
"Where do PCB's enter this process? In the waste paper which is the
raw material for the process. They are discharged with the dirty water
because they are essentially associated with and attached to the pigments and
inks removed during the deinking process.
"Having removed the undesired material with water the processor now
has to remove them from the water before discharge to the public waters or
recycling to the process.
"These waters can be given primary and secondary treatment in order to
meet the requirements of N.P.D.E.S. permits, which require close control of
Biologic Oxygen Demand and Suspended Solids, along with other requirements.
"There is extensive literature on the presence of PCB's in water and
their introduction into the food chain. However, few of these address how
it is present. However, Dr. W. Peter Schoor of Gulf Breeze Environmental
Research Laboratory, in an article to be published in 1975, in England in
the scholarly international journal Water Research, has demonstrated that
Aroclor 1254 is soluble in water at a concentration of less than 0.1 part
per billion. What this means is that any amount of this material present
in water greater than this miniscule amount must be either in the suspended
solids portion or in the form of an emulsion stabilized by a surface active
agent. Since only a very small portion of the total amount of PCB material
can be in the true solution state, limiting the discharge of these materials
in paper deinking plants can be greatly enhanced by improved suspended
solids removal and effective secondary treatment for removal of the oxygen
consumptive material.
"The effect of improved suspended material removal on PCB discharge is
intuitively evident, since a significant portion of the PCB is undoubtedly
attached to the suspended particles because all PCB's are extremely lyophobic
in water, and therefore have a strong tendency to coalesce with other
lyophobic materials and to adhere to lyophic sites on suspended particles.
In conclusion, I think we can say that, although PCB discharges from
these deinking paper mills now tend to be rather high, we can look forward
to significant reduction in discharge concentrations as the programmed and
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projected treatment systems required by the N.P.D.E.S. program become
effectively operational.
REFERENCES
1. Poly chlorinated Biphenyls and the Environment, Interdepartmental Task
Force on PCBs, Washington, D.C., May 1972.
2. American National Standard Guidelines for Handling and Disposal of
Capacitor- and Transformer-Grade Askarels Containing Polychlorinated
Biphenyls, American National Standards Institute, Inc., January 9, 1974.
3. Martin G. Broadhurst, "Use and Replaceability of Polychlorinated Biphenyls,"
Environmental Health Perspectives, October 1972.
4. J. R. Allen, et al., "Residual Effects of Short-Term, Low-Level Exposure
of Nonhuman Primates to Polychlorinated Biphenyls," Toxicology and Applied
Pharmacology, 1974.
5. D. A. Barsotti and J. R. Allen, "Effects of Polychlorinated Biphenyls
on Reproduction in the Primate," presented at the meeting of the Federa-
tion of American Societies for Experimental Biology, Atlantic City,
New Jersey, April 18, 1975.
6. David L. Stalling and Foster Lee Mayer, Jr., "Toxicities of PCBs to
Fish and Environmental Residues," Environmental Health Perspectives,
April 1972.
7. Stanton Kleinert, Wisconsin Department of Natural Resources, personal
communication, June 30, 1975.
8. Public hearing to review and receive comment upon proposed administra-
tive rules relating to the discharge of polychlorinated biphenyls (PCB's)
into the waters of the State, Docket No. PCB proposed rules, Madison,
Wisconsin, August 28 and 29, 1975.
DISCUSSION
MR. WILLIAM S. BEGGS (New Jersey Department of Environmental Protection,
Trenton, New Jersey): I have several questions. Number one, can you
give some idea what kind of test methods are used to detect these PCB's?
MR. BREMER: Generally mass spectrophotometry and gas chromotography are
used. There have been some updates on the methods, (and maybe I am
going a little bit to far here) but there is an open debate right now
on detection levels. The detection levels that I presented in this
report are those detection levels from the Duluth National Water Quality
Laboratory and from the Central Regional Laboratory of the EPA.
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MR. BEGGS: Was there some sort of concentration requirement necessary before
you went to Mass Spec (sic), perhaps a GC discharge to the Mass Spec or
something like that? In other words, there is a technique I know that
has used capillary GC equipment to go right into the ionizing region
of the mass spectrometer. Well, you tell me.
MR. BREMER: Actually, to be honest with you, I do not perform the analysis.
I know that the scanning is done by Mass Spec. Samples are extracted
and subjected to gas chromotography. I do not actually perform these
analyses. Possibly I could take your question back to one of the
laboratory people.
MR. BEGGS: I have one other question. I think you indicated that PCB's were
associated with the pigments. That is how they got into the chain in
the first place; is that correct?
MR. BREMER; Historically, we know there were high concentrations of PCB's
in the NCR carbonless carbon paper forms. And if you take the carbon-
less carbon paper forms, that I am sure you fill out every day, you will
pick up PCB's in analysis of those forms. We have run a scan on some of
those at the laboratory. They are still pretty high. Some of them are
older forms and quite often it is hard to date them. Some forms were
produced before 1972 and are still around. This is one good source.
The other concern is that in some of the pigmented inks, back-
documentation indicates the PCB's were used in formulation. This was
documented in the departmental task force presentation on PCB's. I be-
lieve there are patent numbers associated with this documentation.
We are still working on inks, taking a cross section. I would like
to know that PCB's are not there, because if they are used in inks, we
have a real problem, and the paper recycling industry has a real problem.
MR. BEGGS: Thank you.
MR. FRANK DICK (Converters Ink Company, Linden, New Jersey): The gentleman
from New Jersey, my contact, Doctor Seymour Gilbert in the Food Science
Department at Rutgers University, probably has a bigger file on PCB's
than anybody in the country.
MR. BREMER: Fine. Thank you.
MR. THEOPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
There are certain things that I cannot say. But I can say that our
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chemists have been working on the methods of determining PCB's. And if
I can get your name, I might be able to get you some information that
could help you.
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RECOVERY OF MATERIALS USED IN LETTERPRESS
AND ROTOGRAVURE PLATE PREPARATION
William A. Rocap, Jr.*
Abatract
The materials used in the construction of letterpress and rotogravure
printing plates are identified, and the handling of them is discussed, with
particular attention to their recovery and recycling. The chemicals used in
plate preparation as well as in the preparation of the materials used in the
"prep" areas are also discussed, with like emphasis on the ability to recover
recycle, or reuse. The overall theme is to discuss the above with respect
to the impact of platemaking operations upon the environment. Slides will
be shown to illustrate the presentation.
Before proceeding to the identification of specific materials and
processes in the letterpress and rotogravure segments of the graphic repro-
duction industry and looking at their impact on the environment, I would
like to make a few observations concerning the approach which is being taken
to these matters from several viewpoints.
First of all, I would like to commend the people who have put this
program together on their choice of a title "Conference on Environmental
Aspects of Chemical Use in Printing Operations." During the past several
years, it has been the practice to brand many of the people who have been
involved in the printing and related industries as polluters of every part
of the environment whether or not this has been, in fact, true. Much of the
finger pointing and damaging adverse publicity has been spawned by people
who care very little about either our business or our government and would,
in fact, like to bring both down. Unfortunately, at times, the press in an
effort to capture sensational headlines and some do-gooders who really do
not know the first thing about the problems being discussed, join in. This
may be news to some of you but let me please tell one brief story to illus-
trate my point. A series of announcements were run about a year ago on
*Director of Research and Development, Meredith Printing, Division of
Meredith Corporation, Des Moines, Iowa.
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radio and T.V. telling their listeners of the evils of pollution. They
appealed for action on the part of the citizen: "If you see smoke coming
from a stack, report it," etc. This was followed up by many articles in
local papers along the same line.
About a week after this general attack on industry, a class of junior
high students toured one of the local plants. One little boy firmly told
his tour guide, "We are going to shut this plant down." You see, the propa-
ganda had hit the mark. My question is, is this the way to solve our
environmental problems?
A second observation involves semantics again. Many plants have what
.they call a quality control department. Some plants prefer to call this a
quality measurement or quality assurance department; why? It is felt that
the people who are directly responsible to the management, owners, and stock-
holders for the quality of the product are the ones who should be controlling
the process. I read in a trade publication recently, "So the question is,
does the government want to control pollution or control industry? If the
objective is to lessen pollution quickly and dramatically, requiring less
would accomplish more." Again, I like the title Environmental Protection
Agency better than Environmental Control Agency, and it would behoove all of
us to strive to keep EPA protecting rather than controlling.
My third point is one of procedure and it involves the way many of our
larger companies have already set up within the framework of their staffs
one person or more responsible for environmental impact.
There is much to concern the printer today other than producing graphic
reproduction on time, with acceptable quality and hopefully at a profit. He
must now face the problems posed by a myriad of Federal, State and local laws,
regulations, and programs. He has to deal not only with environmental prob-
lems concerning air, water and solid waste, but with OSHA, fair employment
practices, equal rights, and a myriad of other regulations, the existence of
which he has not the slightest knowledge.
The printing industry is a very large one and it employs a vast army
of people; however, many of the graphic reproduction establishments are quite
small, with 20 employees or less. One large printing plant with which I am
acquainted has three people who work full time on problems related to the
environment. Much of this time is spent in reading the new regulations
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that come out in a seemingly endless stream, week after week, and in trying
to interpret them to their own situation. In a small plant, the plant mana-
ger must add this function to an already busy schedule. Is it any wonder
why in many cases he simply does not know of the regulations or how they
apply to his situation? Recently a technical representative of a fairly
large supplier of graphic reproduction material tossed a copy of a technical
bulletin on standards for photographic effluents on my desk, with the ques-
tion, "What is this all about? I can't make heads nor tails of it?" This
from a graduate chemist who has been in the trade a number of years. My
third suggestion then is to "keep it simple." Because of the nature of our
graphic reproduction industry, new laws and regulations should be widely
disseminated in understandable language. Trade associations and trade publi
cations should be in the vanguard to accomplish this.
I. I would like to first mention the materials used in the preparation of
letterpress plates and rotogravure plates and cylinders. In the
preparation of letterpress plates, it is necessary to produce relief
type and halftone images on some sort of image carrier or plate from
which this image is transferred to a substrate such as paper, plastic,
etc.
1. In order to produce the halftone images or illustrations, it
is generally necessary to produce continuous tone and line
film from which a sensitized plate in imaged. The production
of this film involves photographic processing that generates
photographic wastes. Here I would like to quote PERI Information
Bulletin No. 14 (ref. 1) on this item. "Manufacturers of photo-
graphic materials have generally given a great deal of attention
to the problems of waste disposal and their technical personnel
can generally aid the platemakers in such matters."
2. The Eastman Kodak Company has an excellent publication called
"Disposal of Photographic Processing Wastes" (ref. 2), which
should be in every platemaker's library. One metallic element
found in wastes of all common photographic operations is
silver, which is present in used processing baths as a silver-
thiosulphate complex. Both from the economic standpoint as well
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as for environmental control, it is important that this metal
be removed and recovered. Excellent silver recovery systems
are available through graphic arts suppliers. They remove silver
from solution either by electroplating the metal onto a metal
cathode, or by a chemical reaction that causes it to deposit on
metallic fibres. All platemakers should consider such treatment,
both because silver recovery helps to insure a continuing supply
of a metal vital to the platemaking industry and because it
is a means of environmental protection.
One recent development in the area of film is the Scott S.G.
film which is silverless and does not require a development
solution for processing. It is processed by ammonia, which of
course requires a somewhat different environmental treatment.
Another recent development in film is the 3M QA Mark IV
graphic film, which is advertised for the "elimination of all
high polluting substances from coatings on both sides of the
film."
Insofar as reclaiming of used and scrap film is concerned, it
is collected in drums and sold for approximately 30
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neutralization takes place, a heavy brown precipitate of iron
compounds will form. When formation of the precipitate ceases,
neutralization is complete. After the precipitate has settled,
the clear solution is drained off and is further treated with
limestone and sent to the sewer. The precipitate is dried, made
into cakes and is hauled off, usually by a paid disposal service.
The used plates are sold as scrap as are the trimmings and shavings,
the copper being kept separate from other metals during processing.
7. Zinc and magnesium are used in addition to copper engravings,
as original etched plates in the letterpress process. Like copper,
the sheet magnesium and zinc etching baths must be treated in
order to dispose of them properly. Also like copper, the zinc
and magnesium metal is carefully separated and returned to a
metals dealer for recycling. A number of firms assemble and sell
packaged units for the treatment of etching wastes. Among these
is the Ball Metal and Chemical Company, Greenville, Tennessee,
which handles a unit that can be modified to handle products of
zinc, magnesium, and copper etching.
8. Type metal consisting of 82 percent lead, 11.5 percent antimony,
and 6.5 percent tin is used in linotype, monotype, and foundry
type setting for the manufacture of letterpress plates. Most
of this material can be very readily recycled and is exchanged
pound for pound with the payment of a very small refining fee.
9. Rotogravure prepress operations use film in the same manner
as letterpress preparation, with one additional step—the
preparation of carbon tissue used to control the delicate
etching of the tiny cells into the gravure copper. There is also
the plating of the rotogravure cylinder with copper and its washing
and polishing, which necessitates treatments of these rinses to
remove the copper. After use, the gravure cylinders are stripped
of their Ballard shells of the plated copper. The shells are
dechromed with HC1 and are sold as an almost pure copper; however,
they do contain a trace of nickel from the "parting layer" of the
gravure cylinder.
331
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A recent development in rotogravure called mechanical engraving,
which is done with a machine called a Helio-Klischograph, elimi-
nates the need for an etching step in producing the ink-carrying cells
on the cylinder. However, much liquid etching with ferric chloride
is still done, and this etching bath, must be treated and disposed
of in the same manner as the letterpress copper engraving bath.
Unfortunately, an economically feasible method of reclaiming the
copper from this bath has not been found. In the case of the roto-
gravure cylinder, after etching, proofing, and correcting, it is
chrome plated and used directly on the rotogravure press.
II. In the letterpress process, original engravings and set-type are
rarely used in the actual printing processes. Rotary printing presses
require curved plates and one such duplicate plate is the electrotype.
In electroforming an electrotype, a plastic mold is made of the original
engraving and type by pressing a sheet of pure plastic against the form
under carefully controlled heat and pressure. (It should be possible
to find a use for this molding plastic, which is thermoplastic, but
unfortunately it is presently scrapped.) After molding, the plastic
is sprayed with silver to make it conductive, the excess silver spray
being carefully collected and recycled. The silvered plastic is elec-
troplated with nickel, copper, tin, and finally chrome to give it a
long-wear characteristic. The shell thus produced is an exact replica
of the original engraving and type and it is curve cast in a rotating
cylinder, forming a curved press plate by a process called centrifugal
casting. After shaving and correcting, this curved segment is finished
and is delivered to the pressroom. After its run in the pressroom, the
discarded plate is separated mechanically and the elements are returned
to a metals refiner where they are exchanged pound for pound. A small
price is paid for the refining. Time does not permit going into detail
to describe the care necessary in handling the plating baths. Great
care, though, is exercised in employing as much of the used materials
as possible. Copper, for example, is recovered from the copper bath
electrolytically, as is the chrome. The used copper anodes, nuggets,
etc., are returned to the metal supplier and are recycled.
-------
Stereotypes are also duplicate plates that-are made from originals
by "rolling up a matte" and casting molten type metal into the matte 1n
a curved casting mold. Stereotypes are largely used to produce news-
papers and since they are made entirely of type metal, they can be very
readily recycled and reused, usually onsite.
III. In the past several years, a number of plastic letterpress plates have
found widespread use, particularly in newspaper printing. Typical
brand names are NAPP, Dycril, Kodak KPR, Brace, Merigraph, etc. These
plates are made of various plastics, usually polymers--polyamindes,
polyurethane, etc.—and they consist of the imaged plastic usually
attached to a thin sheet of aluminum. The aluminum bases can be
recycled, but the plastic polymers cannot. The plates are made by
several means, from both solid and liquid materials, but generally an
exposure to light through a negative and a washout to produce the relief
is necessary. Some of the washed out plastics are biodegradable and are
washed out with warm water and run down the sewer; others are insoluble
and are collected, treated, and disposed of in sanitary landfills, etc.
IV. One important development similar in some respects to the mechanical
engraving of the rotogravure cylinder—which eliminates many steps,
including liquid etching and its associated disposal problems—is the
laser-etched letterpress plate. This is produced by engraving a letter-
press plate through scanning a black and white line copy with a laser
and producing an engraved plate by removal of plastic with two other
lasers. Control of the vaporized plastics is of course necessary but
liquid echants are eliminated.
In conclusion, it might be said that much has been done to reclaim and
recycle the materials used to make letterpress plates and rotogravure cylin-
ders, but there is still much to be accomplished. The future looks exciting
though challenging.
(The following 9 figures are illustrations of the processes described
in this paper.)
333
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Figure 1. Conservation of water by use of recirculators such as
this one used in color film processing, resulting in savings
of water and heat.
334
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Figure 2. Silver reclaim unit on each photographic film
processor to recover silver.
335
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Figure 3. Collection of film in drums to be sent to a reprocessor
for recovery of silver and other materials.
336
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Figure 4. Copper recovery unit to remove copper from concentrated
plating solution; it recycles both the copper and the bath.
337
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Figure 5. Fume separator over the copper recovery unit to filter
out and recover any carried-over materials.
-------
Figure 6. Copper anodes sent out to be recycled are made into new
anodes—replaced pound-for-pound with a small recycling charge.
339
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Figure 7. Machine used to separate the various metals of the
letterpress plates for more advantageous recycling.
340
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Figure 8. Used monotype and linotype metal ready for return to
the foundry to be recycled.
341
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Mgure 9. View of plate materials that have been separated and
are ready to b
-------
REFERENCES
!• Pollution and the Platemaker. PERI Information Bulletin No. 14,
PnotoplatemaKers Educational and Research Institute, Park Forest, Illinois,
January 1971.
2- Disposal of Photographic Processing Wastes. Publication No. J-28, The
Eastman Kodak Company, Department 412-L, Rochester, New York.
343
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SOLVENT RECOVERY IN A MODERN
ROTOGRAVURE PRINTING PLANT
B. Gordon Watkins, Jr., and Paul Marnell, Eng. D.*
Abstract
Toluol, the principal solvent in rotogravure inks, is the common name for
the aromatic hydrocarbon methylbenzene (CJ1CEJ. Toluol is a photochemically
reactive organic compound which reacts with oxidizing chemicals in the atmosphere
under the influence of sunlight to form what is commonly called "smog." Progres-
sive management stipulated that the new Meredith/Burda rotogravure printing plant
to be built in Lynchburg, Virginia, should be as pollution-free as modern tech-
nology could provide. A fully automatic solvent recovery system captures toluol
vapors at their sources on the printing presses and recovers liquid toluol, which
is reused in making gravure ink at the nearby ink plant. This paper illustrates
the basic components of the solvent recovery system and describes their operation.
Design objectives and operating performance of the system are presented.
In late 1969, Meredith Corporation of Des Moines, Iowa, joined forces with
Burda Druck GmbH, headquartered in Offenburg, West Germany, to form Meredith/
Burda, Inc. The goal of this venture was the construction and operation of a
modern and highly efficient rotogravure printing plant, which would utilize the
best technology of both parent companies. A site was selected in Lynchburg,
Virginia, and construction of the 120,000-square-foot first stage of the plant
began in 1970. An additional 115,000 square feet were placed in operation in
mid-1974.
Progressive management dictated that the new plant would not only produce
the highest quality product, but would be as pollution free as could be designed.
It was imperative that Meredith/Burda be a good neighbor in its beautiful setting
on a hill in suburban Lynchburg. This policy meant in practical terms designing
a plant with extremely low levels of air and water pollution and odor emission.
This paper presents the system used to control the emissions of the vapor of the
principal solvent in rotogravure ink, toluol.
Toluol is the common name for the aromatic hydrocarbon methylbenzene
(CeHj-CH,). It is a highly flammable, moderately volatile, moderately toxic
*B. Gordon Watkins, Jr., Vice President and Manager of Project Administra-
tion, Wiley & Wilson, Inc., Lynchburg, Virginia; Paul Marnell, Manager, Environ-
mental Business Development, American Lurgi, Inc., Hasbrouck, New Jersey.
344
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liquid. In vapor form toluol is considered an air pollutant. As a photochemi-
cal ly reactive organic compound, it reacts with oxidizing chemicals in the
atmosphere under the influence of sunlight to produce what is commonly known as
"smog."
The Regulations for the Control and Abatement of Air Pollution of the Common-
wealth of Virginia (ref. 1) provide specific limitations on the amount of organic
solvents that may be lawfully emitted to the atmosphere. Paragraph 4.05.03 (g)
of these regulations, entitled "Organic Solvents," states: "A person shall not
discharge more than 40 pounds of organic material into the atmosphere in any one
day from any article, machine, equipment, or other contrivance used . . . for
employing, applying, evaporating, or drying any photochemically reactive organic
compound or material containing such solvent unless all organic materials dis-
charged from such article, machine, equipment or other contrivance have been
reduced by at least 85$ overall .... Emissions of organic materials into the
atmosphere . . . shall be reduced by:
(a) Incineration
(b) Adsorption, or
(c) Processing in a manner determined by the Board to be not less effective
than (a) or (b) above .... The word person shall be synonymous with and have
the same meaning as the word owner . . .."
In order to comply with these regulations as a minimum requirement, a sol-
vent recovery system having two basic objectives was designed for the plant:
1. Solvent removal from the exhaust-air from the printing press dryers,
which would meet and exceed any existing air pollution, health, or
safety ordinances regulating emissions of toluol vapor into the
atmosphere;
2. Recovery of liquid toluol of sufficient quality and in sufficient
quantity to be economically worthwhile to use in the manufacture
of gravure inks in the nearby ink plant.
The solvent recovery system selected for use at the Meredith/Burda plant in
Lynchburg was designed by Lurgi GmbH of Frankfurt, West Germany, and installed
under the direction of American Lurgi, Inc. Installation was designed by the
firm of Wiley & Wilson, Inc., Engineers-Architects-Planners, headquartered in
Lynchburg, Virginia. This presentation will describe the specific Lurgi system
installed in the Meredith/Burda plant, although certain principles are common to
other solvent recovery systems.
345
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The basic system consists of four principal elements: collection of vapors,
transp6rting vapors to the solvent recovery plant, adsorbing the vapors, and
finally condensing and separating the liquid toluol. Although oversimplified,
figure 1 illustrates the concept of the complete system.
Toluol begins to evaporate from the web immediately after being in contact
with the impression cylinder. Most of the vapor is captured and drawn into the
dryer at point (T) (figure 1). Other escaping toluol vapors from the web and ink
fountain settle to the floor, since toluol has a vapor density relative to air
of 3.1, and are collected by the floor sweep (point (2)).
The presses installed at Meredith/Burda utilize a steam-heated, recircu-
lating forced air dryer on each unit to vaporize the solvent from the web. A
portion of the recirculated air, approximately 2,000 cubic feet of air per minute
per unit, is continuously drawn off for transport to the solvent recovery plant
(point (3), figure 1).
The uptake duct from the dryer on each unit of the press (figure 2) includes
a paper filter, motor-operated shutoff valve, which is connected to the dryer
blower motor, and a flow indicator with an alarm.
A uniform flow of air and vapor from each press to the solvent recovery plant
is kept uniform by a motor-operated valve, which maintains a constant 150 mm hLO
negative pressure in the press header duct (item (4), figure 1).
The solvent recovery plant serves four 10-unit rotogravure presses and one
four-unit proof press. The common transport duct is run above the roof (item (5),
figure 1). It is protected from fire internally by an automatic carbon dioxide
deluge-type system. The duct is equipped with lightning rods to reduce the chance
of damage from this source. The duct contains a solvent concentration meter,
which will sound an alarm in the pressrooms if the toluol vapor in the duct
reaches 25 percent of the lower explosion limit and will shut down the presses
automatically if the concentration should reach 40 percent of the lower explosion
limit.
The recovery plant itself consists of filter house, blowers, adsorbers,
condenser-aftercooler, and separator.
The filter house (item (6), figure 1) contains a traveling curtain, self-
cleaning air filter. Five direct-drive high pressure blowers (item (7)) operat-
ing in parallel provide the total motive force to move the air-vapor mixture
from printing-press dryer systems to the discharge side of the adsorbers. Six
identical adsorber tanks (item (I?)) cleanse the air stream of solvents. The
346
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CO
•£»
-4
BACK PRESSURE
REOULATINO VALVE
UPTAKE DUCTS FROM OTMBU UNITS Of PRESS PROM FLOOR
SWEEP
1BO mrn H
NEO PRESS
^PURIFIED AIR
SUPPLY*! *¥ T
/ADSORBER TANK
I (TYPICAL OF SIX)
CO g OELUQg
x £
ROOF
it i> f*
"HEADER OUCT-CONNECTS TO
FOUR TEN-UNIT PRESSES
IEAOER DUCT
FIVE BLOWERS
IN PARALLEL
3OO mm
ttS
CONOENStR
AFTERCOOLER
^ . WATER OUT ^1O f
J* WATER IN 7» F
WATER-TOLUOL
SEPARATOR TANK
jWATER TO DRAIN
Y
RANSPORT
OLICT
-AUTOMATIC
AIR FILTER
Figure 1. Schematic of the solvent recovery system.
-------
HEADER DUCT
FLOW ORIFICE
FLOW METER
AND ALARM
MOTOR-OPERATED
SHUTOFF VALVE
CONNECTION TO PRESS DRYER
CIRCULATING AIR SYSTEM
Figure 2. Solvent recovery uptake duct for each press unit dryer.
348
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fully automatic control system maintains five adsorbers on the line at any one
time with the sixth unit being regenerated. Each adsorber tank contains a bed of
activated carbon held in place by ceramic grilles.
During normal operation of the adsorber tank, inlet valve (9) (figure 1) 1s
open and the air-vapor mixture is circulated through carbon beds. Cleansed air
is discharged to the atmosphere through valve ® . During regeneration, valves
(9) and ® close, and steam is admitted through valve (fj) , steaming the ad-
sorbed vapor from the carbon. The toluol-steam mixture passes through valve ©
and is condensed and cooled in the condenser-aftercooler © . Finally the water
and solvent are separated by specific gravity in tank @ . The liquid toluol is
piped to an underground storage tank © and water is discharged to drain ® .
The method utilized to provide cooling water for the condenser-aftercooler
is worthy of special mention. The criteria for cooling water dictated by design
of the condenser-aftercooler required that the water entering the aftercooler be
a constant 75° F all year. A normal full-load water temperature leaving the after-
cooler would be 120° F. The required entering water temperature was too low to
utilize a cooling tower in summer, and city water would be expensive. To cool the
water entirely by mechanical refrigeration would also be expensive. A further
consideration was the desire of the engineers to use a closed-circuit water loop
for the condenser-aftercooler to eliminate regular shutdowns for cleaning the
tubes of these heat exchangers.
The equipment and piping system selected by the engineers to provide the
cooling water is illustrated graphically in figure 3.
Primary and secondary pumping circuits are utilized, with most cooling of
the water being done by a Fluid Cooler (item (T), figure 3). Water leaves the
condenser-aftercooler (item (J)) at 120° F and enters the coils of the fluid
cooler. A fluid cooler is similar to a cooling tower except that the water to be
cooled flows through closed coils while recirculated water is sprayed over the
coils, cooling the water in the coils by evaporation.
At normal maximum summer-design conditions water will be cooled by the fluid
cooler from 120° F to 85° F. A portion of this 85° F water is returned to the
plant chilled-water-system return main (point (3), figure 3). The plant chilled-
water supply (5), which is 42° F, is blended with the 85° F return water to pro-
duce 75° F water to the condenser-aftercooler unit (point (6)). As outdoor tem-
perature and humidity drop, the temperature of water leaving the fluid cooler
drops. When the temperature drops to 75° F, no plant chilled water is required,
and the water is cooled exclusively by the fluid cooler. Water temperature 1n
349
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TOLUOL-STEAM VAPOR
PROM ADSORBERS
CONDENSER
cn
o
AFTERCOOLCR
TOLUOL-WATER
TO SEPARATOR
as r
39 C
WATER RETURN
Figure 3. Schematic of pipe solvent condensing.
-------
cold weather is maintained at 75° F by sequential control of fans and damper
control on the fluid cooler. This sytem has demonstrated a significant saving
in energy while maintaining the reliability of the system.
The process aspects and the economics of the solvent recovery plant are
presented in the following paragraphs.
The Lurgi Supersorbon* process is employed universally for the recovery of
various organic solvent vapors and contributes, therefore, to increasing the
profitability of many industrial operations. At the same time, it prevents the
discharge of noxious vapors into the environment, and its use brings about com-
pliance with the air pollution acts brought into force in recent years. At
present, there are over 3,000 Lurgi Supersorbon plants in operation worldwide.
The Supersorbon process, which is based on the affinity of certain activated
carbons for organic vapors, can be applied in most industries employing solvent,
e.g., surface coating, impregnating, extracting, rotogravure, viscose fibres,
acetate silk, films, rubber goods, imitation leather, etc. In this paper, we
describe its utilization in a modern rotogravure plant. However, the principles
are quite general and are employed in most applications of the process.
The Supersorbon process comprises two key steps:
1. The purification of the solvent-laden exhaust-air (SLA) by exposure
to Supersorbon activated carbon, which results in a selective and
highly efficient adsorption of organic vapours, even at low concen-
trations. The removal efficiency generally exceeds 99 percent.
2. The regeneration of the carbon, with steam permitting the recovery
of the adsorbed solvents and the further solvent recovery by the
carbon.
Properties of the Adsorbent
Before, describing the sequence of process steps, it is worth while to men-
tion the characteristics of the activated carbon used to remove, by adsorptiont,
the printing ink solvents from the SLA (solvent-laden exhaust air).
Activated carbon is a product of organic matter (e.g., peat, wood, brown
*Supersorbon is a registered trademark of Lurgi.
tConsult any standard physical chemistry text for a discussion of the ad-
sorption mechanism. For our purposes here, we may describe it as a purely physi
cal process whereby the surface forces of the carbon are such that the solvent
vapor molecules are bound to the carbon surface. As the temperature is in-
creased, the bound vapor molecules are further energized and can overcome the
binding forces and thereby escape (desorb).
351
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coal, coconut shells), which is produced in numerous special grades. For
exhaust air purification and solvent recovery, cylindrical shapes with a grain
o
size of 3 to 4 mm and a bulk weight of approximately 380 kg/m are used.
Depending on the application, a grade is selected having suitable capillary
structure, surface area, adsorptive capacity, and mechanical strength. The
2
inner surface area of the various grades is in the range of 1,000 to 1,500 m /g
of activated carbon.
The key point is that the carbon used should be tailored to the applica-
tion. This will insure maximum recovery at a minimum cost.
We will now describe the two key process steps, i.e., adsorption and
desorption (regeneration).
Adsorption (Charging Cycle)
The solvent-laden air (SLA) produced at the rotogravure machines is drawn
off by means of the blowers and, after dust removal, flows upward through a por-
tion of the adsorbers. The other adsorbers are simultaneously being regenerated,
i.e., the solvent is being removed for them. The adsorbers are filled with the
highly activated Supersorbon carbon, which is supported on perforated ceramic
trays, which in turn are supported on grates. The activated carbon adsorbs the
solvent, and the solvent-free air leaves through the top of the adsorbers to the
atmosphere.
The adsorber-charging step is continued until the solvent is no longer com-
pletely adsorbed in the uppermost activated carbon layers. This so-called
"breakthrough" (end of charging cycle) is monitored by a concentration-measuring
instrument called a Solvomat* installed in the switch panel, which serves to
initiate automatic control of the Supersorbon plant.
Desorption (Regeneration)
When breakthrough occurs, the gas inlet and outlet valves (?) and @
(figure 1) to the adsorbers are automatically (by means of the Solvomat signal)
closed and the steam inlet and distillate valves (H) and © are opened. The
object of the steaming process is to raise the temperature of the carbon bed in
order to free the bound solvent molecules from the surface of the Supersorbon
activated carbon. The slightly superheated steam passes down through the bed,
*Solvomat is a registered trademark of Lurgi.
352
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and the resulting steam-vapor mixture leaves the bottom of the adsorber and is
condensed In a condensor-aftercooler unit © .
Since toluene and water are immiscible, the toluene is easily recovered in
the separator and then sent to .tank storage.
After desorption, the hot and moist Supersorbon carbon in the adsorber is
dried and cooled down to normal charging temperature as quickly as possible.
This drying and cooling of the activated carbon is achieved by recharging with
SLA. For this mode of operation, it is essential that the activated Supersorbon
carbon has a sufficiently high adsorptive capacity even at elevated temperatures.
The Meredith/Burda plant is fully automatic, so that the timed sequencing
of the charging and regeneration of each adsorber is controlled by instrumenta-
tion. The Solvomat concentration analyzer developed by Lurgi monitors the exhaust
vapor solvent concentration. When the concentration rises, the Solvomat transmits
a control signal whereby the inlet and outlet air valves (?) and © are closed,
and immediately thereafter (2 to 3 seconds) the steam and distillate values @
and © open to initiate the regeneration step. In general, an adequate number
of adsorbers must be available to handle the solvent removal while the other
adsorbers are regenerated. At Meredith/Burda, five adsorbers are in various
stages of charging while one adsorber is discharging (being regenerated).
Maintenance of the Supersorbon plant is routine and is carried out during
the period set aside for press maintenance. Hence, the Supersorbon solvent re-
covery plant does not reduce or curtail production time in any way.
The original carbon charged in 1971 is still performing satisfactorily
with no apparent need for recharging imminent.
The general economic operating parameters of a Supersorbon plant are stated
below:
Operators per Shift 1
Utilities
Steam (25 50 psi), Ib steam/lb recovered solvent 2-3.5
Electricity, kWh/lb recovered solvent 0.1
Cooling Water, gal/lb recovered solvent 4 6
Carbon Loss, Ib carbon/lb recovered solvent 0.0005 0.001
The basic operating data for the Lurgi Supersorbon facility at Meredith/
Burda are as follows:
OPERATING DATA
Operating days per year 250
Shifts per day 3
353
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Throughput of solvent-laden air
Toluol recovery per 24-hour day
Electricity
Water (closed system cooling)
Steam (60 psig)
Labor, man/shift
The annual operating costs for the plant are:
ANNUAL OPERATING COSTS
Labor (@ $10/hr total)
Utilities
Electricity (@ 2.2 cents/kWh)
Steam
Gas Fuel, 80% $ 16,400
Oil Fuel, 20% $ 12,200
Refrigeration of condenser water
Water
Fluid cooler makeup
Steam makeup
$
1,360
2,090
Taxes and insurance (@ 3% of capital investment)
Maintenance (@ 1% of capital investment)
Total annual operating costs
The capital investment costs for the plant are:
CAPITAL INVESTMENT COSTS
Solvent recovery equipment (including instruments
and Lurgi engineering)
Erection of solvent recovery equipment
Water system piping (installed)
Steam piping (installed)
Process building
Foundations and pipe supports
Chilled water system (incremental cost charged
to solvent recovery plant)
Nonprocess engineering fee
354
88,000 cfm
6,720 gal
13,000 kWh/day
20,000 gal/day
168,000 Ib/day
0.2 man/shift
$ 12,000
$ 71,500
$ 28,600
$ 2,000
$ 3,450
$ 36,000
$ 12,000
$165,660
$800,000
$ 40,000
$ 71,000
$ 8,000
$174,000
$ 12,000
$ 72,000
$ 17,000
$ 1,194,000
-------
The annual recovery of purchased toluol is 97,200 gallons per month x 12
months = 1,166,400 gallons. At a current price of $0.59 per gallon, this repre-
sents a saving of $688,176. In addition, there is a recovery of the toluol in
the purchased printing ink. This toluol is sold to the ink manufacturer. The
credit is 42,800 gallons per month x 12 months x $0.20 = $102,720. (Note that
the total monthly recovery rate of toluol is 97,200 + 42,800 = 140,000 gallons.)
The total annual credit for recovered toluol is $790,896.
The overall plant economics can now be summarized as follows:
Capital Investment $ 1,194,000
Annual Toluol Credit 790,896
Annual Operating Costs - 165,550
Annual Profit $ 625,346
Hence, the payout period (neglecting interest) is
$1,194,000 = 1 9, Y
$625,346/Year Kyi Years
In summary, the solvent collection and recovery system serves the important
functions of safely removing solvent vapors from the printing presses and trans-
porting them to a plant which through adsorption cleanses the solvent from the
air stream. It recovers liquid toluol in sufficient quantity and purity to make
the system an attractive investment for the modern rotogravure printing plant.
REFERENCE
1. "Regulations for the Control and Abatement of Air Pollution," State Air
Pollution Control Board, Commonwealth of Virginia, February 3, 1974.
DISCUSSION
MR. W. N. FINGLAND (International Paper Company, Clinton, Iowa): I have some
questions. In recovering toluene by adsorption, are you not also picking
up other solvents? And then subsequently, how do you separate them?
Finally, do you have a constant mixture of toluene that you are using?
DR. MARNELL: To answer the latter, we do have a constant mixture of toluene.
In the first instance, again, this particular plant was a simple plant
in that it had a constant mixture. Toluene was the basic component. And
most important, the toluene was immiscible with the water.
In the more general cases that we have handled, you have a mixture
355
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of hydrocarbons and then you have added distillation steps. So you have
a little more in the way of capital equipment. But there is no. problem
as far as effecting the separation.
MR. FINGLAND; In the event you have a mixture, then you can distill out?
DR. MARNELL: Yes, absolutely. We have done this also.
MR. FINGLAND: Thank you.
MR. WILLIAM S. BEGGS (New Jersey Department of Environmental Protection, Tren-
ton, New Jersey): You say that toluene is insoluble, and yet it is
soluble to a certain extent. What is the concentration of toluene in
the effluent?
DR. MARNELL: As it stands now, I do not know what the concentration was. I
know it has not been a problem in the State of Virginia. If it did be-
come a problem, then we would introduce either a distillation step or
steaming out step to take care of any residual.
You are absolutely correct; it is not 100% insoluble. If there were
trace amounts that could become objectionable, we could handle it with
a simple steaming process. I do not have the exact figure.
MR. BEGGS: Thank you.
MS. EMILY A WEBBER (Oxy-Catalyst, West Chester, Pennsylvania): Are those capital
costs 1n 1970 dollars?
DR. MARNELL: No, 1975.
MS. JACQUELINE M. FETSKO: I think you ought to mention that your border plant
In Germany for many years ran medical examinations on the staff and workers
that were exposed to toluene. And they found no cumulative effects after
20 years.
DR. MARNELL: Thank you for mentioning it.
MR. WATKINS: Let me make one additional comment at this point. The design
requirements on this plant were that at no time during normal operations
could the toluol level in the pressroom exceed 200 ppm. It is checked
regularly and is operating under 100 ppm.
356
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24 September 1975
Session III: (con.)
IMPACT OF WASTE RECOVERY
AND RECYCLING ON THE ENVIRONMENT
Robert L. King
Chairman
357
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AN ECONOMIC APPROACH TO TREATMENT OF LIQUID WASTES
IN
ROTOGRAVURE CYLINDER PREPARATION
Donald P. Manning*
Abstract
In the preparation and maintenance of rotogravure cylinders, printing
plants are concerned about the need to comply with ever-tightening environ-
mental standards. Long-term solutions to the problems of liquid waste handl-
ing are being sought. As State and Federal agencies more vigorously enforce
regulations on discharge of heavy metals and other toxic materials, innova-
tions' in techniques must be forthcoming. This paper discusses the extent of
a conceptual system required to suit, economically, the sundry problems pecu-
liar to a given plant operation.
INTRODUCTION
Rotogravure printing requires a cylindrical printing plate where an
image is etched into the surface of the plating. After being rotated in an
ink bath to fill all etched depressions and after excess ink is wiped away
by a doctor blade, the ink left in the depressions is absorbed by the paper,
thus producing a high-quality reproduction of color work.
The preparation of the cylindrical plate for this highly sophisticated
printing method requires many steps. Liquid wastes are associated with
several of these steps—copper plating, chrome plating, and image etching.
The aim of this paper is to suggest options available today for the
handling of these liquid wastes, with a special emphasis on economy. What is
required for a given plant depends on a number of variables typical of that
plant's operation. For an environmental specialist who has understood his
plant's operation, the extent of a conceptual system needed to solve waste
problems can be discerned.
*Manager, Plant and Process Engineering Department, Wiley & Wilson,
Inc., Lynchburg, Virginia.
358
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PLATING AREA
LIQUID WASTE
i L
I—
r i j
RECOVERY h—J
I I
I
SPILL
PROTECTION
CUSTOM DISPOSAL
RECOVERY
LANDFILL
TREATMENT
SANITARY SEWER
PLATING AREA
SCRUBBING LIQUID
IN-PLANT FACILITY
CHEMICAL
TREATMENT
LANDFILL
SANITARY SEWER
Figure 1. Liquid waste handling concept.
LIQUID WASTE HANDLING
A proposed concept of liquid waste handling would follow a step-by-step
course suited economically to the pollution abatement required to meet exist-
ing State and Federal regulations. This concept, illustrated in figure 1,
shows the flow of liquid waste from the copper plating, chrome plating, or
image etching processes. The liquid waste is either totally or partially
recovered for recycling or, in the event of spillage or dumping, passes on
to a holding tank where it can be pumped to a custom disposal truck or to a
chemical treatment facility before disposal to a sanitary sewer. Even though
wastes from the separate processes of copper plating, chrome plating, and
359
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image etching cannot be mixed, it is possible to join the three separate
treatment processes in a multiple batch series, in order to utilize the same
treatment facility. The separation of the three different categories of
wastes is necessary since intermixing would be hazardous and would make
recovery/treatment expensive.
PLATING CHEMICALS RECOVERY
Significant cost savings can be realized in the recovery of plating
chemicals, especially chrome. As other packaged units become economically
feasible, recovery of other chemicals may be justified. Savings have been
proved to result from recovery in the following ways (ref. 1):
1. The purchase of plating chemicals is reduced by 50 percent.
2. The purchase of chemicals to neutralize or destroy unrecovered
chrome is no longer required.
3. Less water and less sewage require treatment.
4. There is no sludge to haul to landfills.
For large printing plants consuming at least 10,000 Ib/yr of chrome-
plating chemicals, a recovery system could be justified fully. In a cylinder-
plating operation, the fume scrubber liquid will be a more valuable recover-
able source than the plating tank "drag out." A recently marketed evaporator
unit which costs in the range of $20,000 could be employed effectively on
the scrubber liquid, if it is recirculated and allowed to become as concen-
trated as 2 to 3 oz/gal (ref. 2).
SPILL PROTECTION
Spills and dumped plating bath solution are not readily recovered, and
thus there is need of additional provisions such as a holding tank. Spillage
can result from overflowing tanks, leaks, and careless handling of chemicals.
Overflowing tanks are avoided by the installation of either level alarms or
predetermined flow counters. Leaks can occur in steam heating coils in
plating tanks, resulting in the plating chemicals being siphoned out due to
the vacuum created by condensing steam. Through the use of a conductivity
meter, contaminated condensate can be detected and then diverted into a
360
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holding tank. From the plating operation, all waste liquid is collected
in a holding tank, as shown in figure 2. Waste liquid from this holding
tank is circulated through the scrubber, which condenses fumes from the
hot plating baths, thereby limiting the amount of waste and conserving
the use of plant water for the scrubbing liquid.
The options available to handle the contents of the spill-protect!on
holding tank are several:
1. Plating chemicals may be recovered and recycled to the plating
tank.
2. The contents of the tank can be analyzed and discharged to the
sanitary sewer, if within ppm limits and pH tolerance.
3. The contents can be picked up and trucked to a custom disposal
plant.
4. The contents can be chemically treated before discharge to the
sanitary sewer.
In one specific plant with existing plating operations, it was found
that an interim solution to disposal problems consisted of separate holding
tanks, one for each category of waste (ref. 3).
CUSTOM DISPOSAL
Since recovery may not be economically justified for some of the cylin-
der preparation waste liquids, and since spills and dumped plating baths
usually are destroyed, printing plants need provisions to handle these
remaining liquid wastes. One method to accomplish the necessary disposal is
to provide adequate holding tank capacity for pickup by a custom disposal
tank truck. In an engineering study to compare the merits of custom disposal
versus in-plant treatment, it was shown that the cost of trucking and custom
disposal was half that of the cost of owning and operating a small in-plant
treatment facility. This study was made in a plant that chrome plated 5 to
10 cylinders per month (ref. 4).
Since the only usual requirement of custom disposal service companies
is that the waste liquid be basic rather than acidic, the stored waste
liquid may be adjusted to a relatively high pH by adding caustic soda.
361
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IN-PLANT CHEMICAL TREATMENT FACILITY
Good economics require that in-plant chemical treatment equipment be
functional for all three categories of wastes—copper plating, chrome
plating, and image etching.
One economic approach was developed whereby the three different waste
liquids are handled consecutively by multiple series of batch operations.
The operations below are shown in figure 3 (ref. 5):
1. The treatment of chrome plating waste in treatment tank A is the
first-step reaction obtained by initially adding sulfuric or
hydrochloric acid and then adding sulfur dioxide gas. This first
step insures the reduction of hexavalent chromium, which is highly
toxic, to the trivalent or chromic state.
2. The treatment of trivalent chrome is the second-step reaction and
occurs in treatment tank B or C, where lime slurry or caustic soda
solution is added to precipitate chromic salts.
3. The separate treatment of copper plating waste occurs in treatment
tank B or C, where lime slurry or caustic soda solution is added to
precipitate copper hydroxide. (Note the system flexibility pro-
vided by a distributor box above tanks B and C).
4. The separate treatment of iron chloride etching waste also occurs
in treatment tank B or C. The metallic iron is then precipitated
with a lime slurry or caustic soda solution, with the result that
all metallic ions are converted into hydroxides as solids.
5. Treated batches in tanks B and C are discharged one at a time to
the filter press where the sludge is collected as a solid for dis-
posal and where the effluent is passed through to treatment tank E.
6. In treatment tank E, the effluent is treated by adding sulfuric
acid to adjust the pH to the required level before releasing it to
the sanitary sewer.
The design criteria for the in-plant treatment facility described above
were based on a maximum production rate of 10 cylinders in an 8-hour opera-
ting shift.
363
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UQUIO
LIQUID MUtl
PMMHU.VZCH
CO
cr>
TO SANITARY SCWCR
Figure 3. In-plant treatment scheme.
-------
SUMMARY
Many printing plants using the rotogravure method have already mounted
continuing environmental programs. These programs include consideration for:
1) the recovery of chemicals from rinse water, 2) improved practices for
handling chemicals, 3) spill protection, 4) fume scrubbing, 5) segregation
of the various categories of liquid wastes, 6) water conservation, and 7)
custom disposal or in-plant treatment.
Careful scrutiny of the needs of one's own operation is the all-impor-
tant first step in attaining long-range solutions to problems of waste handl-
ing. Customer engineering is required to solve individual problems that each
printing plant presents. Through innovations on the part of the designer
toward the greatest practical use of the facilities required, the safe dis-
posal of liquid wastes in rotogravure cylinder preparation can be economically
handled.
REFERENCES
1. "Recovering Plating Chemicals," Process Design, March-April, 1975.
2. Telephone Communication with Mr. R. G. Jump, Manager, Distributor
Sales, Chemical Recovery Systems, at Corning Glass Works, Corning,
New York, August 8, 1975.
3. Clarence T. Sloan, Jr., "How to Handle Spent Plating Solutions,"
Industrial Waste, November-December 1974.
4. Unpublished engineering report, J. L. Montague, chemical engineer, Wiley
& Wilson, Inc., June 1975.
5. Unpublished engineering report, R. E. Lipscomb, design engineer, and
R. W. Nash, retired chemical engineer, Wiley & Wilson, Inc., December
1970.
DISCUSSION
MR. W. N. FIN6LAND (International Paper Company, Clinton, Iowa): Are there
any problems with the disposal of the resulting solids?
Second question: A filter press is pretty darned expensive for
a medium-sized operation. Have you seen, or do you know now of the
use of centrifuges?
365
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MR. MANNING: Yes. To answer the first question, with a filter aid, the
filter press does a very good job. If there is any carry-over, and
you are allowed to dump into the municipal sewer, dumping will handle
that satisfactorily.
The cost of the particular type filter press that was used was in
the neighborhood of $30,000.00 to $40,000.00, I believe. It is a leaf-
type filter press. I might say here that the total cost for this in-
plant treatment facility was about $130,000.00. So that was a major
cost item in the design of this facility. Does that answer your
question?
MR. FINGLAND: Except as to the disposal of the sludge.
MR. MANNING; The sludge is handled by putting it into Dempster-Dumpsters
and hauling it away to landfills.
MR. FINGLAND: No problem with that?
MR. MANNING: No real problem. Any other questions?
MR. ALVIN SALTZMAN (New Jersey Bureau of Solid Waste Management,
' Trenton, New Jersey): I have a response to that statement. Actually,
we are having problems with landfills, particularly with leachate. I
can anticipate that in the future, if not now, at least in New Jersey
landfills, you will have some problems with disposal of the materials
containing heavy metals that were shown coming from the precipitators.
366
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RECOVERY AND REUSE OF ORGANIC INK SOLVENTS
R. L. Harvin, Ph.D.*
Abstract
Environmental and OSHA requirements are coupled with solvent supply
and economic factors to make examination of solvent recovery and reuse
important for the solvent-using industries. Solvent recovery process
choices are discussed. For most solvent drying applications, with rela-
tively low concentrations in the solvent-laden air, activated carbon ad-
sorption is shown to be most suitable. Some theory and details of the
adsorption process are presented. Applications of the carbon adsorption
and solvent separation processes are discussed for several cases involving
either single solvents or mixtures of solvents. A case history is pre-
sented of a gravure plant solvent recovery system that has been in oper-
ation since 1971. The recovery system treats all the plant exhaust and
recovers 38,500 gal/wk, of which 12,900 gal/wk are exported for reuse in
ink manufacture and the balance is reused for ink dilution. The overall
efficiency of the solvent recovery and recycle system is about 90 per-
cent. The consumption of solvent has been reduced from 2,215,000 gal/yr
to about 215,000 gal/yr. The solvent cost savings and the independence
from solvent supply problems are cited as valuable justifications for this
system.
INTRODUCTION
This paper was prepared for a conference focusing on the environ-
mental aspects of chemical use in printing operations. Thus, in the con-
text of this conference, solvents are those used in inks as a medium to
carry pigment to the surface of a web. However, in the broader sense,
we are discussing any process wherein organic solvents are used in the
application of a dissolved material to a moving web or film. The major
*Engineering Specialist, C&I/Girdler Inc., Louisville, Kentucky.
367
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examples of such processes and the ones to be referred to in this paper
are: (a) gravure or similar printing, and (b) continuous coating on paper,
metal, or plastic films. In addition, many other processes could be men-
tioned, all of which have the same essential elements: namely, a) appli-
cation of a high-solvent-content material to the surface of a moving web
or film; b) rapid evaporation of solvent to enable further processing
or handling; c) evaporation accomplished by movement of heated air across
wet surface; and d) solvent-laden air exhausted from system.
On examination of modern industry, one finds the concept of recovery
and reuse of chemicals and solvents is not a uniformly accepted practice.
Certain highly sophisticated industries have always recovered every BTU
or pound of material and have indeed gained an edge in the competitive
race by a fractional improvement in such schemes. Other industries have
been quite content to use materials on a once-through basis and have
concentrated their competitive efforts in other areas. The uniformity
that is found is that, within a particular industry, all members treat the
concept similarly. One must conclude that through experience and with
mutual assurance, each industry has moved in the direction of maximum
profits. In a perfectly free society, abundant in raw materials and
energy, this is the conclusion that economic theoreticians would predict.
However, we are no longer in a free society, abundant in raw materials
and energy. Out of necessity, we are giving up the free society in favor
of limitations that are intended to preserve our resources, restore the
environment, and improve the quality of life. Industry now has the prob-
lem of reexamining its previous conclusions in light of these new re-
straints.
Emission Restraints
The most compelling of the new factors influencing consideration of
solvent recovery are the emission control regulations that are now in
effect in most States. Although there are differences in these regu-
lations, it is safe to predict that the ultimate effect will be that users
of solvents will gradually reduce emissions to the environment from 100
percent of the solvents used in their processes to the 2- to 10-percent
range.
368
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OSHA Restraints
Under the influence of the OSHA health and safety regulations, the
management of solvent-using plants will have to give increased attention
to lowering the concentration of solvent vapors within their plants. The
preferred way is by improved plant design to prevent escape of the solvents
from the process equipment. Solvent vapors that connot be contained must
be recaptured by exhausting the solvent-laden air from the area and this
adds to the plant emission problem.
Solvent Supply Restraints
The current shortage of supply of all types of solvents is an
accepted fact and the long-term trend is certain to be of increased
scarcity. Conditions exist which can cause a tenuous situation to develop
into an absolute disappearance from the market of certain raw materials.
The quantities of solvents used by many industries are such that it is
impractical to inventory more than a few days or weeks supply. For
example, it is not uncommon for a gravure printer to consume 20,000 to
40,000 gallons of solvent per week and to depend on deliveries every few
days. With application of the solvent recovery and reuse principles
available today, it is possible to eliminate such dependence and remove
the spector of plant shutdown due to a solvent shortage.
Economic Restraints
The cost of solvents has increased dramatically and the occurance of
spot shortages can cost additional premiums in order to maintain plant
operations. Such economic pressures emphasize the importance of examining
solvent recovery and reuse. However, due to the increased cost of facili-
ties and their operation, solvent recovery projects do not always show an
attractive return on investment. If it were so, then everyone would prob-
ably be doing it—for the reason cited earlier. When considered as a
resolution to a problem involving the other factors mentioned above, sol-
vent recovery and reuse may be easily justified.
369
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PROCESS CHOICES
Industry has available a number of alternate commercial processes for
handling solvent emission control and occupational health and safety prob-
lems. First, consideration should be given to improvements to the design of
the basic equipment for utilizing the solvent efficiently and keeping it
physically contained within the system. Then through the use of inciner-
ation, adsorption, absorption, or condensation, the emissions to the
atmosphere can be controlled. When the objectives also include solvent
recovery and reuse, only adsorption with activated carbon has much appli-
cation. Under certain conditions, condensation and/or absorption could
be used in conjunction with one of the other processes to achieve both
solvent recovery and the desired degree of emission control.
The outstanding advantage that the activated carbon adsorption proc-
ess has over other solvent recovery processes is its ability to remove
all the organics (solvents) from the air regardless of variations in con-
centration and humidity conditions. Concentrations of 3,000 ppm and be-
low can be recovered at high efficiency leaving only a few ppm in the
effluent airstream. With due allowance for explosive mixtures, con-
centrations above 3,000 ppm can be handled at even higher efficiency.
The condensation process, by comparison, can recover only those
constituents above the saturation concentration at the condensing temper-
ature. Even with refrigeration, condensation as a means to recover most
commercial solvents would only be practical at vapor concentrations well
above 10,000 to 20,000 ppm. Then after condensing, the residual solvent
concentration would be several thousand ppm and probably well above
emission requirements. The usual 25- to 50-percent LEI safety require-
ment for solvent-laden air systems therefore precludes the use of con-
densation for solvent recovery in the usual printing and coating operations.
In the petroleum and petrochemical industries, where condensation has
application, the residual gas stream would either be recycled to the proc-
ess to pick up more solvent or would be treated by another control
scheme before release to the atmosphere. Closed-loop systems may be
operated safely using an inert carrier gas, such as nitrogen, or using
air if the solvent is nonexplosive, such as methylene chloride.
370
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The absorption process depends on a component's solubility in a
relatively nonvolatile absorbent liquid. Solubility is directly related
to vapor concentration, so absorption at low vapor concentration is highly
inefficient. For solvent recovery applications with concentrations in
the 0- to 3,000-ppm range, the absorption process requires excessively
large equipment. Thus, the process is not suitable for solvent recovery
for the printing and coating operations. There are special applications
for a direct contact absorber or scrubber on a solvent-laden air stream
as a pretreatment before going to another emission control scheme.
ADSORPTION PROCESS
The adsorption process is dependent on the property of a solid sur-
face to capture and accumulate molecules of a fluid with which it comes
in contact. All molecules, whether gas, liquids, or solids, are subject
to this phenomenon but the degree to which each material is affected is
a characteristic of that material. By this process, constituents of an
airstream may be selectively adsorbed or removed by materials known as
adsorbents.
The exact mechanism by which adsorption takes place is still un-
certain. Most theories attribute the phenomenon to the forces causing
cohesion in solids and liquids. These forces can be divided into two
groups: intermolecular or van der Waals forces causing physical adsorp-
tion, and chemical forces causing chemisorption. In the former, the
adsorbed molecules are preserved intact while in the latter the adsorbed
molecules break up into atoms or radicals which are bound separately to
the surface as in chemical combination. In physical adsorption the surface
of the adsorbent may be covered with multiple layers of molecules depending
on the intermolecular forces. In chemisorption the mechanism is limited
to a mono!ayer.
Most applications of the adsorption process to recovery of organic
vapors involve only the physical adsorption mechanism. The process
strongly resembles condensation and is accompanied by the liberation of
heat of the same order of magnitude as the heat of liquifaction. The proc-
ess can be reversed by supplying heat of this magnitude, whereby the
adsorbent surface is regenerated.
371
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It is apparent that the effectiveness of a solid to adsorb molecules
is strongly related to the amount of interfacial surface. Therefore, to
achieve a high degree of adsorption, it is expedient to create the maximum
obtainable surface area within the solid phase. Commercial adsorbents,
such as activated alumina, silica gel, and activated carbon, contain a
large number of micropores having hundreds or thousands of square meters
of surface within a gram of solid. Adsorption process equipment is de-
signed to contain a quantity of adsorbent in small pellet or granular form,
suitably arranged so that the adsorbate-containing air can flow through the
entire quantity. The dimensions of the bed of adsorbent and the flow of
air are selected so that adsorption can be substantially complete in the
time of contact. After some period of flow, the adsorbent will become
saturated with the adsorbate and will cease to function. When this occurs,
the adsorbent must be replaced or regenerated.
Vapor phase adsorption is essentially an exothermic gas-solid equili-
brium process, and conditions which shift the equilibrium toward satura-
tion usually improve the process. Consequently, adsorption will take
place more efficiently near the dew point and it is beneficial to operate
at the lowest practical temperature. Regeneration of the adsorbent can be
accomplished by raising the temperature of the system and supplying
sufficient heat to break the adsorption bonds. However, some molecules
are more difficult to remove from the microporic structure then others and
tend to remain as a residual or "heel."
If the vapors to be adsorbed consist of several components, the ad-
sorption of the various components will not be uniform. Generally, these
components are adsorbed in an approximate inverse relationship to their
volatilities. Hence, when air containing a mixture of organic vapors is
passed through a bed of adsorbent, the vapors are equally adsorbed at the
start; but as the amount of higher boiling constituent retained in the bed
increases, the more volatile component revaporizes and moves on through
the bed to a more favorable adsorption site. Eventually some of the
more volatile constituent will be forced out completely and can be detected
in the effluent. The higher boiling component has thus displaced the lower
boiler component, and this mechanism if continued would result in only
the highest boiling component being retained on the adsorbent.
372
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SOLVENT RECOVERY DESIGN
The detailed procedures for the design of activated carbon adsorption
processes are well documented in the literature. These lead to the
selection of such items as carbon bed dimensions, number of adsorber
vessels, cycle timing, regeneration conditions, precooling requirements,
and condensing duty. This paper will not consider these design principles
but will discuss questions of application to the overall solvent recovery
problem.
Basic Process Flow Diagram
In the typical solvent recovery application, illustrated in figure
1, activated carbon is used as the adsorbent, and multiple vessels (ad-
sorbers) containing the carbon are provided so that one can be off-line for
regeneration while the other(s) are actively treating the solvent-laden
airstream. Adsorbers may vary considerably in design and in orientation
of the carbon bed. However, with the usual design criteria, carbon beds
are 16 to 24 inches thick and composed of pelleted or granular material
in the 1/16- to 1/4-inch size range. Pretreatment of the solvent-laden
airstream frequently consists of dust removal and cooling. For regener-
ation, steam is used in the reverse direction through the carbon bed to
clean the outlet portion most thoroughly. The steam and solvent vapors
are condensed and either decanted for reuse or further processed by
distillation or other means.
The process, as illustrated, represents a sizeable number of actual
installations. The plants are simple, they work well, and the carbon gives
years of active service. However, conditions may exist which require
special attention.
Nonregenerable Constituents
Process generated particulates, airborne plant dust, and low-vapor-
pressure components from the ink, coating, or web may be present in minute
quantities but can accumulate on the carbon bed to substantial amounts
after a period of operation, since they are not removed from the carbon
during regeneration. Also, certain constituents from the ink or coating
373
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FILTER COOLER
DECANTER
SOLVENT
CONDENSATE
Figure 1. Adsorption process flow diagram.
may have a tendency to polymerize after adsorption or during regeneration
under the influence of the heat and possible catalytic effect of the
carbon or impurities.
The dependence of the process on available surface and on freedom
of molecular movement in the adsorbent pore structure make it evident that
any physical blockage will destroy the ability of the adsorbent to per-
form. High-efficiency particulate filters should be provided unless the
cleanliness of the airstream is assured by other means. Nonregenerable
vapor components can usually be removed from the airstream by providing
a carbon bed filter or sacrificial bed. Initially this bed will adsorb to
saturation all components of the vapor. Gradually, the lower boiling
material will displace all other components and the sacrificial bed will
be replaced. Prevention of polymerization products on the carbon re-
quires a knowledge of the chemistry involved in order to predict how to
avoid such damage.
Variation of Solvent Composition
Prolonged use of the carbon on sol vent-laden air of a particular
solvent composition results in the formation of a heel composed of each
374
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molecular species in "equilibrium" with the vapor composition. If the inlet
airstream composition is altered in any way, the carbon will shift toward
a new heel composition and the recovered solvent composition will show the
effects of this shift until a new heel composition has been established.
If air containing a new species of solvent is passed through the adsorber,
the new species will compete for adsorption sites with those forming the
heel from previous use and the recovered solvent will be contaminated by
each species of solvent on the carbon. Such contamination may persist
through several cycles.
SOLVENT REUSE FLOW DIAGRAMS
Single Solvent
If a single solvent (1 species) is used, its recovery for reuse can
be very simple, as illustrated in figure 2. The solvent vapor and re-
generation steam will be condensed. If two phases are formed, separation
is effected and frequently the solvent can be reused without further treat-
ment. In case of partial or complete solubility in water, distillation
may be required to produce a reusable solvent as well as a reusable or
disposable condensate. Dehydration schemes for many solvents are de-
scribed in the literature.
Mixed Solvent
If a solvent composed of two or more species is used, then the air
from the drier will contain a mixture of the solvents and these will be
adsorbed and recovered together, as illustrated in figure 3. If, upon
condensation, two phases are formed, separation by decantation may produce
a mixture suitable for reuse. However, due to variations of volatilities
in the drier, variations of recovery efficiency in the adsorption, and
variation of solubility in water, the recovered solvent mixture will differ
slightly from the original composition. Based on a laboratory analysis,
the composition can be restored by "doctoring", using fresh solvents.
If the solvents are partially or completely soluble in water, then
the condensed mixture must be distilled to dehydrate. In so doing, the
organic material will be separated into several fractions which, upon
375
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CONDENSER DECANTER
CARBON
ADSORPTION
A
INK
CONDENSATE
i
—-\
r—*—i
(DISTILLATION |
I I
U J
(RECOVERED \
SOLVENT J
Figure 2. Solvent reuse diagram—single solvent.
CONDENSER DECANTER
VENT
•
—I
IDISTILLATION|
i i
L _ 1
"
L .
MAKE-UP
SOLVENTS
RECOVERED
SOLVENT
ABC
^
Figure 3. Solvent reuse diagram—mixed solvents.
376
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analysis, can be recombined to yield the desired solvent formulation.
The distillation need not be designed to produce solvent fractions of
the same composition or degree of purity as the commercial solvents used
to prepare the original formulation. Solvent mixtures, whose components
coexist simply as the result of mixing dissolved pigments, resins, driers,
and vehicles to prepare an ink or coating, are unique mixtures and may
pose difficult problems of separation. The components are seldom members
of a single family or homologous series of solvents and they range over
the extremes of polarity. Such systems invariably contain potential
constant-boiling mixtures or azeotropes. Liquid-liquid extraction and
azeotropic and extractive distillation can be used to circumvent the for-
mation of some constant-boiling mixtures. However, as an alternative
to the expense of such a complex separation system, careful consideration
should be given to reformulation of the ink or coating to allow the use
of solvent fractions only partially separated or of azeotropic composition.
Success or failure of a recovery and reuse effort can hinge on a
company's willingness to face this problem. The marketing organization
insists that a product of a certain quality and uniformity be produced;
the product development group insists that the formulation used in their
product development program be adhered to; the production group wants to
produce the desired product efficiently; the environmental group interprets
the regulations and specifies the ambient and effluent requirements; and
the facilities group, which has the responsibility for providing a solvent
recovery plant to please everyone, must do so within a budget and schedule.
Multistage With Different Solvents
If the solvents used in successive stages of printing or coating
differ, either in percentage composition or species, then the air from the
driers will contain a blend of all solvents and these will be adsorbed
and recovered together, as illustrated in figure 4. The condensed solvent
mixture, whether soluble in water or not, will have to be separated into
fractions by distillation in order to reuse in the separate stages. If
the formulations for the stages differ only in percentage composition,
then the components need not be highly segregated in the distilled frac-
tions. On the other hand, if the formulations differ in the components,
377
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CONDENSER
DECANTER
VENT
1
CARBON
ADSORPT1
ABC , A
INK
DISTILLATION
RECOVERED
FRACTIONS
,-*-, JL ,-«
T^S H [ABC) [AI
4 *—^—^
RECOVERED
SOLVE,,!
RECOVERED
SOLVENT
Figure 4. Solvent reuse diagram—multistage with different solvents.
a much higher degree of segregation may be necessary in the distilled
fractions. This raises questions of compatability of the ink or coating
with solvents which are normally not used in the formulation. Here
again, cooperation of the various interests within a company is needed
to establish realistic design requirements.
In the extreme, if complete segregation of the solvents is necessary,
it may be preferred to prevent the initial mixing in the drying airstream,
by completely evaporating the solvent from one stage before going into
the next stage. Separate adsorption and recovery systems would be needed
for the different solvent-laden airstreams. This could result in an inter-
mi ttant-continuous process which is practical in the case of certain proc-
esses but highly impractical in a high-speed multipress gravure-type
operation.
Separate Products with Solvents of Different Percentage Composition
If solvent formulation, differing only in percentage of components,
are used in separate products run either simultaneously on parallel
378
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presses or intermittantly on a single press, the air from the driers may
be handled by a single adsorption system if distillation is required for
separation. This is illustrated in figure 5. In this scheme, the com-
position being recovered at any time is effected by the heel of solvent
from previous operation and thus does not exactly correspond to the com-
position of solvent being used in the product. Alternately, if the
solvents are insoluble in water, separate adsorption systems with decan-
tation for each formulation may be practical.
Separate Products with Solvents of Different Components
If solvents containing different species are used in separate products,
run either simultaneously on parallel presses or intermittantly on a
single press, the air from the driers should be handled by separate ad-
sorption systems for each formulation, as shown in figure 6. The separate
condensed phases would be either decanted or distilled as required. How-
ever, any distillation system needed would probably be less complex due
to the complete isolation of the different chemical species.
A CASE HISTORY
The Standard Gravure Corporation of Louisville, Kentucky, installed
solvent recovery facilities in 1971. At the time, public awareness of
the environment was in full bloom. Some communities had established
emission regulations while others, including Louisville, were just be-
ginning to analyze the problem. Only "pessimists" were forecasting an
energy shortage and the price of solvents had been relatively stable at
18 to 20 cents per gallon. Nevertheless, for reasons of good community
relations, the Standard Gravure management made a decision that airborne
solvent emissions were to be controlled and that recovery and reuse of
the solvent were prime objectives.
Standard Gravure has its plant facilities in a complex of multistory
buildings also housing the corporate offices and publishing facilities of
the jointly owned Courier Journal and Louisville Times newspapers. The
entire complex is air conditioned from a central utility area. The air
exhausted from the ovens and other operating units in the printing areas
379
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CONDENSER DECANTER
MOOUCT
Y -*
Figure 5. Solvent reuse diagram—multiple products with similar solvents.
CONDENSER
DECANTER
VENT
Figure 6. Solvent reuse diagram—multiple products with different solvents,
380
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1s replaced by fresh, conditioned air distributed to various locations in
the building complex. Solvents that escape from the presses or remain
temporarily in the printed product are kept at a tolerable level by room
exhausts in the printing areas. Thus, within the plant buildings, air
flow is toward the printing areas and solvents are not distributed through-
out.
Plant emission tests were set up to study oven and room exhaust sol-
vent concentrations on a 24-hour basis. Inventory records of the quantity
of solvent consumed indicated that the plant should be designed to recover
approximately 2 MM gal/yr. On the basis of a straight average, this is
a usage of 1,800 Ib/hr at a concentration level of 400-500 ppm at pro-
jected exhaust volumes. However, the study of the actual concentration
in the exhaust streams from individual oven discharge blowers showed
variations ranging up to five times the average. The room exhausts were
found to contain 100-300 Ib/hr, thus indicating that they should be in-
cluded in the solvent recovery system. Also, using the records of the
preceding year, the actual operating times and exact quantities of sol-
vents used were analyzed. A design basis then was selected which would
handle the exhausts under all extremes of operation.
The gravure printing operations followed the time honored procedure
of maintaining several bulk solvents with different drying speeds and
solvency. Depending upon the job specifications, different amounts of
solvents such as VM&P naphtha, toluol, xylol, etc., were used as diluents
of the inks to obtain certain printing characteristics. These solvents
are relatively insoluble in water so that an organic solvent phase could
be separated from the regeneration steam condensate. Distillation would
be required to separate the organic phase into fractions with properties
similar to the solvents used. However, to avoid the expense and complex-
ity of a separation plant, investigations proceeded into the possibility
of using a single formulation of a "base solvent" that would handle all
but proof press operations and specialty jobs. This study had to take
into account the solvent used by the ink manufacturer since it would
also be recovered. With favorable indications that such could be done,
Patent pending on "base solvent" formulation by J. K. Anderson.
381
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a solvent recovery plant was installed based on decantation and reuse of
the solvent mixture.
Process Description
A simplified process flow diagram is shown in figure 7. There are
two gravure printing rooms, each designed for oven and room exhaust air
volumes of 120,000 acfm. The exhaust plenum from each area has an auto-
matic relief to the atmosphere in the event of an interruption in the
solvent recovery plant. Solvent-laden air from each area flows through
.separate two-stage high-efficiency filters to remove paper and ink par-
ticles. The air to the gravure ovens is drawn from the pressroom, which
is supplied with filtered air so that atmospheric dust does not represent
additional load to these filters. The pressroom is held at approximately
75° F and 50 percent relative humidity and the combined oven and room
exhausts range between 100° and 110° F. With these conditions, no further
cooling or humidity control is required for efficient adsorption or plant
safety.
From the filters the airstreams flow into two booster fans with
automatic control to adjust to the capacity variations of the gravure
presses.
Six activated carbon adsorbers are provided and each has inlet valves
on the air ducts so that it can be switched in and out of service in-
dependently. Four adsorbers are active, each handling 25 percent of the
total flow, and the two adsorbers not in service undergo a two-stage re-
generation made up of back-flow steaming followed by forward-flow cooling
with air. The four active adsorbers are always sequenced so that they are
equally distributed on the loading cycle; that is, they are 25 percent
of the loading cycle apart. When one adsorber becomes loaded to capacity
with solvent and begins to break through, the others are 75, 50, and 25
percent loaded. In order to maintain this relationship, it is necessary
to have balanced flow to the four adsorbers.
By automatic selection, samples of each of the purified air exhausts
are withdrawn and a composite analysis of the total hydrocarbon content
is continuously recorded. When a carbon bed becomes saturated with sol-
vent, its breakthrough is detected by its effect on the composite sample.
382
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ee
1
CO
oo
CO
FILTERS
P
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a:
STEAM
A t*
r-r-t*
r(
£_.=-_
* ^ I
I
r
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i
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- T" "~ " ' 00 *
H^
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ADSORBERS
i—i r^
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COOLING
WATER
SOLVENT RECOVERY
Figure 7. Simplified process flow diagram—Standard Gravure Corp.
-------
At this point, the air flow is diverted from the saturated adsorber to the
one having been steamed and cooled.
Regeneration is accomplished by the use of low-pressure steam flowing
equally through all portions of the carbon bed. The mixed steam and solvent
vapors from the adsorber are condensed and the two liquid phases are
separated by decantation. The solvent flows directly to the 20,000-gal-capac-
ity underground storage system, ready for reuse. The separated solvent
contains approximately 200 ppm of dissolved water and with proper decanta-
tion there should be no separation of water from the solvent as it is re-
used. However, the underground tankage allows additional time for minute
water droplets to settle out.
The Solvent Recycle System
In this plant, all solvent-laden exhausts are treated and the entire
plant is operated under conditions to minimize loss of solvents. Since
the gravure ink, which is purchased outside, contains an appreciable
quantity of solvent, the recovery system always generates a net surplus
which must be exported from the plant. The quantity exported is approxi-
mately equal to the solvent in the purchased ink, less any losses in the
system. The exported solvent is used by the ink manufacturer in formu-
lation of new ink supplies for the gravure plant. This recycle system
for the "base solvent" is illustrated in figure 8. The plant also main-
tains a supply of xylol for operation of proof presses and Lactol for
Spectacolor work. These solvents are the only ones still purchased and
they are recovered with the base solvent.
During 1973 and 1974, the average quantity of solvent recovered was
38,500 gal/wk. Of this amount, an average of 12,900 gal/wk were exported
to the ink manufacturer and 25,600 gal/wk were reused for dilution and
minor purposes such as washup, cylinder cleaning, etc. The use of xylol
and Lactol during this period was about 1,500-2,100 gal/wk. The quantity
of base solvent in inventory throughout this period averaged 12,000 gal
or about a 2-day supply. In the manufacture of ink, 1,800-2,000 gal/wk
of additional solvents were used. If the base solvent composition required
some adjustment, appropriate additions of the needed solvent could be made
by the ink manufacture.
384
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800 GAl/WK
LOSS
\
IOSS •• I=T=^M-!^I
fc**** — — ^- —'-^H -i —
CO
00
in
r- .SOLVENT LADEN AIR.
ACTIVATED CARBON
SYSTEM
LKTOL D
1500-2100 GUI WK
Figure 8. Solvent recycle system.
-------
The overall solvent cycle efficiency is about 90 percent based on
total solvent imports of 42,600 gal/wk. This total is derived from plant
records which take into account all solvents brought into the plant in
the form of production ink, proof ink, and the xylol-Lactol solvents.
Of the 4,100 gal/wk apparent loss, approximately 800 gal/wk can be
accounted for as leakage through the carbon adsorbers. The charts re-
cording plant effluent concentration trace variations from a low of
about 5 ppm immediately after a fresh adsorber is online, up to about
15 ppm at the end of a cycle. An approximate mean value of 8 or 9 ppm
amounts to a 2-percent breakthrough loss, based on average inlet air
concentrations of 400-500 ppm. Other solvent losses include; solubility
in the decanter condensate, washup uses, solvent remaining in the product
and handling losses.
Regular chromatographic analyses of the base solvent are run to make
sure that the major components are within the established tolerable limits.
Over several years of operation, compositions have stayed within these
limits remarkably well. The use of xylol for proofing and Lactol for
Spectacolor have offsetting effects and the additions made by the ink
manufacturer have been sufficient to maintain the base solvent within
specifications.
The Standard Gravure Corporation considers the solvent recovery
system a great success story. Not only has the project met all of the
technical objectives, but it has been given credit for keeping the plant
running by making it independent of solvent supplies. Since the solvent
recovery system is the major source of solvent for the ink manufacturer,
the assurance of this supply is an additional benefit of equal importance.
During the petroleum shortage of 1973 and the resulting energy crunch,
crude oil was diverted from production of naphtha to other more profitable
petrochemicals. Suddenly, naphtha was in short supply and its price soared
to 56 cents per gallon, with some offered for as high as 80 cents per
gallon. This was not a serious problem for Standard Gravure and its ink
manufacturer, since it had reduced its solvent consumption form 2,215,000
gal/yr to 215,000 gal/yr.
The price of solvents has fluctuated considerably and is currently
about 36 cents per gallon. It is obvious that the rate of return on
386
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investment has Improved considerably as compared with 1971.
ACKNOWLEDGMENTS
The author wishes to acknowledge the gracious consent on the part
of Standard Gravure Corporation in allowing publication of information
concerning its plant and operations. Also acknowledged is Mr. Jack Uhl,
Production Engineer, whose helpful cooperation during the preparation
of this paper was greatly appreciated.
DISCUSSION
MR. ALVIN R. SALTZMAN (New Jersey Bureau of Solid Waste Management,
Trenton, New Jersey): It is a very interesting paper. And I think
it really gets down to the nitty-gritty of some of our recycling
problems.
You have shown a closed loop system having variable inputs,
composition, and other factors. For this type of system, feeding
back directly into the printing system, the matter of stability and
control becomes a very important factor. Is that correct?
DR. HARVIN: That's correct.
MR. SALTZMAN: In that case, I wonder if you can provide us any informa-
tion on how you go about the setting up of the stability and control
system; particularly, how you decide whether you are going to use
offset rate or proportional control?
DR. HARVIN: Are you referring to the control of the solvent composition
limits?
MR. SALTZMAN: I am talking about all the subsystems, for instance on the
distillation apparatus—
DR. HARVIN: I can go through the control theories on the solvent recovery
system. However, I am not from the Standard Gravure Corporation, so
I cannot speak of their control of the composition or concerning how
they use their ink, except for the fact that we know they do reuse it.
There is a representative here from Standard Gravure who may wish to
comment.
387
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Regarding the control of the solvent recovery system, I men-
tioned the fact that the inlet air system has variable capacity
control on the blowers. Therefore, regardless of the number of
presses operating or the amount of effluent air, the system can
accommodate that particular air volume through automatic duct
pressure control. Thus, the system can always handle all the air
that is being sent out or being used by the plant. In the event
of an emergency shutdown of the solvent recovery plant, the solvent-
laden air will automatically vent to the atmosphere.
The inlet air composition is measured and recorded by total
hydrocarbon analyzers on the incoming airstreams. The outgoing com-
position is also measured and recorded. A composite sample of the
effluent from the four active adsorbers is used. Just after the
plant switches to a new drum, there is about a 5-ppm breakthrough.
Then the breakthrough gradually rises to a predetermined set point,
which is currently set at 14 ppm. When 14 ppm is detected by the
analyzer, the system cycles. It usually slips on by about 15 ppm
before it finally completes switching. When it switches over, a new
drum comes on and the breakthrough goes back to about 5 ppm. So
the effluent composition follows a sawtooth pattern.
As I mentioned, we avoided the use of distillation because
Standard Gravure went to the use of a base solvent composition.
Because of the way they operate with proofing operations, Specta-
color, and their regular gravure work, the solvent composition
meanders but nevertheless stays within certain prescribed limits
set up by Standard Gravure.
The laboratory people analyze the solvent on a regular basis.
If they find that for some reason or other, due to the products they
are producing, the xylol content is getting down a little bit, all
they have to do is call up the ink manufacturer and tell him to go
heavy on xylol in the small amount of solvent he must add. That
will build up the xylol content of the inventory. Does that answer
your question?
MR. SALTZMAN: Yes, I understand what you said. Thank you.
388
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MR. WILLIAM H. BROWN (FMC Corporation, Marcus Hook, Pennsylvania): What
steam to solvent ratios do you find typical in the adsorption cycle?
DR. MARVIN: This particular adsorption cycle is not the most efficient
1n the world because of the fact that the Standard Gravure people
elect to operate a very low ppm value—400 to 500 ppm. So the
loading of solvent on the carbon is relatively low, and the steam-
solvent ratio is not the most optimum. Its range is between five
and seven.
MR. BROWN: Thank you.
DR. MARVIN: That, incidentally, is something that is less subject to
the design of your plant and more subject to the way you operate
your plant. There are some solvents that can be recovered with
ratios down in range of three, and other solvents that require much
higher steam ratios. The steam/solvent ratio is more a function of
the particular solvent system and the way a plant is operated than
of the design equipment being used.
MR. KING; Thank you.
389
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24 September 1975
Session IV:
IMPACT OF NEW DEVELOPMENTS AND
CHEMICAL FORMULATIONS
Robert H. Downie*
Chairman
'Vice President and General Manager, Research Division, Moore Business Forms, Inc., Niagara Falls,
New York.
390
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OPENING COMMENTS
Farley Fisher, Ph.D.
General Chairman
Our final session is on the Impact of New Developments and Chemical
Formulations. It was with considerable pessimism that I originally accepted
the idea that we should try to hold a session on new developments. My first
reaction was, "Who is going to want to talk about something that they are
trying to keep under their hats until they are ready to sell?"
I must say that I have been very gratified by the response from the
industry. We do have a number of people here who are going to talk about
some relatively new techniques and methods, which may offer real advantages
from the point of view of environmental control.
391
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SESSION INTRODUCTION
Robert H. Downie
Session Chairman
In looking at the speakers for this session, their themes, and their
topics, I was impressed that this was only one of a group of people that we
could have invited. These were not the sole four papers that we were able
to garner from our industry, which showed new developments. When I looked
at the papers, I tried to find some coherence in them. It struck me immedi-
ately that we are not looking at new developments here; we are looking at
second- and third-generation solutions to problems that the industry recog-
nized years and years ago. There is no new revelation being cast upon us in
the graphic arts industry. There are some things wrong, and there are some
things that could be better. What is typical of the papers and the develop-
ments that you're going to hear? These are not first-stab answers at cor-
recting these problems. These are third- and fourth-generation answers to
correcting them.
The unfortunate part from a profit point of view is that some of the
first- and second-generation solutions that we came up with never did pay
for themselves, other than by laying the foundation for the particular de-
velopments that we have now. In addition, there is absolutely no guarantee,
as you well know, that the money that we are investing in current develop-
ments will be spent with successful results.
You are going to find that many of the developments were dictated by
that wonderful disciplinarian, the marketplace. The American marketplace is
a unique broth of ideas that is constantly burbling. I am always impressed
at the way the weak and the unseemly and the nonmarketable get turfed out
and at the correctness of things that persist, all without regulation and
all with simply a discipline of what people want and are willing to buy.
Every one of the developments that you are going to hear about today falls
into this particular category. You will find strong evidence of creative
and positive thinking on the part of the companies that are represented here
392
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and are willing to take you into their confidence, willing to show you what
some of their advance thinking is.
I hope one of the benefits all of us will get out of this meeting is
that we recognize the same problem, when we are through and identify them.
EPA and industry must find a common theme and a common purpose. It is less
than constructive if we do not get in the boat together, find out how we can
exploit new solutions and developments, and bring them to their optimal, not
their idealistic, marketing value.
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UV AND OTHER METAL-DECORATING PROCESSES
Elgin D. Sallee*
Abstract
Inks used in metal-decoration are not significant sources of emissions
since they contain essentially no volatiles. The conventional organic
solvent-borne surface coatings used in conjunction with metal-decoration,
however3 are important potential sources of hydrocarbon emissions. The pre-
ferred control measure for such emissions is reformulation of the surface
coating to eliminate, reduce, or alter the volatiles content. Where this
is not feasible., emissions are incinerated, using natural gas or LPG as
auxiliary fuel. Incineration is relegated to last resort action in view of
the extremely critical fuel supply situation. This paper describes fuel-
savings features of solvent vapor incineration systems, as well as the environ-
mental concerns in selection of chemicals used in formulation of UV-curable
and other solvent-free or low-solvent materials for metal coating and
decorating.
In discussions of the environmental concerns involved in any manufac-
turing process, the first item of significance is the quantity of materials
used. In attempting to total metal-decorating materials, confusion is
encountered from the outset because of varying definitions of metal decorat-
ing. Many of those who are experienced in the business call metal decorat-
ing any process in which •a colorant is applied to the metal surface. This
would include paint, enamels, inks, and even those varnishes, lacquers, or
shellacs that impart color to the metal surface.
Others regard metal decorating as only those processes in which ink is
printed on the metal by means of an offset or lithograph press. Yet in some
instances such equipment is used to apply ink uniformly over the entire metal
surface. Some people call this application surface coating rather than
metal decorating. Ordinarily only a specialist in the business would be
able to tell whether the dried, uniformly colored surface had been printed
*Director of Environmental Sciences, Corporate Environmental Affairs,
American Can Company, Greenwich, Connecticut.
394
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with an ink or whether an enamel of the same color had been applied by a
roller coater machine.
Many of the ingredients of inks and surface coatings are similar. Th«re
are also close similarities in the environmental concerns and control meas-
ures involved. Metal surface coating is frequently considered ancillary to
metal printing; both done in the same manufacturing room, and sometimes on
the same manufacturing line with both materials dried simultaneously in the
same oven.
Accordingly, my comments include metal-decorating inks and coatings
as separate items for those processes and materials now in large-volume use,
as well as some of those involved in new technology.
The can-manufacturing industry is by far the major user of inks printed
on metal. To my knowledge usage in industries other than can manufacture
amounts to less than 1 million pounds annually, whereas ink for metal cans
made in this country amounts to about 15 million pounds per year. Currently,
about 90 percent of this ink is printed on metal sheets before the sheets
are cut to size and formed into cans; the remainder is printed on formed
can parts. Inks are for the outside surfaces only.
Currently about 85 percent of the metal-sheet-printing ink is the con-
ventional thermally cured type applied in about equal proportions by the
dry offset printing process and the wet lithographic process. These inks irt
of the same general type, and environmental aspects are the same for both
printing processes.
Figure 1 is a schematic of the typical conventional ink application and
drying process. It depicts the printing press with the printed sheets
moving into the drying oven where they are picked up by supports (called
wickets) on a continuously moving chain, which carries them through the
oven with exposure to uniform temperature of 330° to 350° F for about 6
minutes. The lower part of the oven (empty wicket chain return section) is
sealed off, except at entrance and exit, from the upper part through which
the printed sheets move. Uniform temperature is maintained in the oven
zones by the circulation of large volumes of air heated by gas burners. A
comparatively minor proportion of the circulated air is drawn from each oven
zone, so there is general air movement toward the oven exhaust stack. Fuel
combustion products as well as any materials volatilized in the oven are
395
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exhausted at this point. The returning empty wickets must be heated just
before they pick up the printed sheets; otherwise the quality of the printing
is affected. Ink usage rates vary, of course, with the area of surface
printed and thickness of the ink film applied. Typically, it may be as
little as 0.1 Ib/hr per color, or, in the case of a heavy white ink covering
the entire sheet, as much as 35 Ib/hr.
Table 1 gives general information on the composition of conventional,
heat-cured metal-printing inks. Note that the extent of vehicle or resin
in individual formulations may vary widely dependent on the extent of color-
ant and extender (the extender is primarily for dilution of the colorant).
Some inks require no extender, dryer, or solvent. All inks printed on metal
are commonly termed as free of volatiles. This is not absolutely true, since
any free solvent is driven off in the oven along with any volatiles released
in the resin polymerization. At most, however, the extent of volatiles from
the latter amounts to 3 percent of the resin. Typical volatiles content of
the ink is less than 1 percent, with a maximum of 3 percent.
Accordingly, emission problems involved in application of conventional
thermally cured ink for metal are practically nonexistent. Ordinarily no
emission-control devices are required for the oven exhaust if the process
involves use of ink only.
However, in the major proportion of printing on metal (in my company
about 70 percent) the printing is followed by a tandem roller coating of
solvent-borne varnish. In most instances this overprint varnish is applied
over the wet ink, as shown in figure 2. Both the ink and the varnish are
oven-dried simultaneously. Were it not for the varnish, emission control
problems in the use of metal-printing ink would be essentially nil.
I mentioned previously that currently about 85 percent of metal-printing
ink is the conventional heat-cured type. Essentially all of the remainder
is the ultraviolet-cured type. Use of UV ink has no marked advantage (or
disadvantage) over conventional inks with respect to emission control, since
neither contains a significant extent of volatiles. Use of UV ink with con-
ventional tandem roller coating of overprint varnish, as shown in figure 3,
still requires use of an oven for the varnish. This process is ordinarily
the first phase in the development of technology for use of UV curable
materials. This ar ngement does have a distinct advantage in savings of
fuel gas in those situations where the ink must be dry before varnish is
396
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applied. With inks that must be dry before varnishing, the figure-3
arrangement eliminates one pass of the metal sheets through the gas-
heated oven. BTU's required for UV curing are about one-tenth of those
for gas-heated oven operation.
Application of varnish or of any organic solvent-borne roller coating
on metal involves obvious emission control problems. Measures to counteract
these include reformulation of the coating to eliminate or reduce extent of
solvent content, or change to preferable solvents, such as less photochemi-
cally reactive types, or incineration of the oven exhaust. Other types of
emission control devices, based on adsorption, absorption, condensation,
scrubbing, chemical oxidation, electrostatic precipitation, or a combination
of these principles, have been evaluated thoroughly and found inadequate or
impractical except in rare instances. Where an emission control device is
necessary, incineration is almost invariably the only dependable control
technology. Particularly because of the fuel supply situation, use of incin-
eration is relegated to last resort action. Where there is no practical
alternative to incineration, it is essential to do it with minimum fuel
consumption.
Figure 4 is a schematic of a typical sheet-coating operation. Basic
equipment is similar to that for roller coating of varnish illustrated pre-
viously, except that the oven for drying enamels and lacquers is usually
larger to accommodate greater usage rates of material. Typical solvent
vapor emission rates from a print-varnish oven are 40-80 Ib/hr, whereas a
modern coater oven may emit as much as 200 Ib/hr.
Figure 5 depicts a roller coater unit with "straight-through" incinera-
tion of the oven exhaust air. This consumes vast quantities of fuel gas.
To reduce fuel consumption, various arrangements of catalyst systems,
heat exchangers, and heat-recovery systems, or a combination of these, are
used. Figure 6 is a schematic for a catalytic incineration system showing
typical temperature measurements.
Figure 7 traces the route of oven exhaust through a heat exchanger and
a thermal incinerator and typical temperatures involved. Figure 8 shows an
arrangement of heat exchanger, burner, and catalyst unit, and figure 9 the
same kind of arrangement but with the addition of heat recovery.
397
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In most instances, particularly in can-manufacturing plants, it is not
possible to make practical use of heat discharged from such systems for
other than the litho-coating process itself. This, of course, depends on
circumstances. Most solvent vapor incinerator systems are add-on installa-
tions made long after the plant was constructed. Possibly for a new plant,
beneficial use of heat discharged from such control devices can be designed
into the plant for space heating or for processes other than heating the
litho-print or coater oven itself.
Figure 10 depicts a system used extensively in my company. Incinerator
discharge air is ducted to the various heating zones of the oven, replacing
burners for the oven zones and wicket preheat section.
At best, all solvent vapor incineration systems consume some fuel gas.
Under present circumstances it is preferable to change to use of coating
materials that obviate need for emission control devices. This, however, is
much easier said than done. Successful reformulation of coating materials
used by can manufacturers is a tremendous task, particularly for those
coatings used for can linings.
Table 2 lists the most common ingredients of conventional solvent-borne
can coatings in decreasing order of volume usage for the respective types of
ingredients. Several others of each type ingredient are actually used, but
extent of such usage is comparatively small, their total combination amounting
to less than 10 percent of the respective total. Except for varnishes, most
such coatings contain no drying oils. The majority contain no additives.
Lubricants most commonly used are silicones or wax. Various combinations of
the resins listed may be used in an individual formulation. Some coatings
may contain only one solvent, such as mineral spirits; others may contain
as many as 10 different solvents.
The effort to reformulate to low-solvent or no-solvent coatings is com-
plicated by the wide variety of coating material end uses and resultant
physical requirements. Well over 600 different coating material formulations
are used in the can-manufacturing industry. My company routinely uses more
than 300 formulations of solvent-borne coatings. Some of our individual
plants use as many as 90 different formulations annually.
The important criteria for all coatings used in can manufacture are
summarized in table 3. This list is an oversimplification of the concerns
398
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involved. A formidable amount of investigative work goes into the successful
development of each new coating material. The formulating laboratory,
despite long experience and knowledge of the chemical and physical properties
of the various individual ingredients, ordinarily compounds and tests a
great many formulations before deciding on one considered sufficiently
promising to warrant submitting samples to the user. The user or can
manufacturer then subjects the new material to a gamut of testing with
emphasis on freedom from difficulties and hazards in application and use of
the material and assurance that the material will do the job intended with
respect to maintaining quality of end-use product. The latter includes
packing the customer's product in the cans and examining it after varying
storage and abuse conditions.
Toxicity of the coating material, of course, is of primary importance.
Where toxic properties of the ingredients and formulated coating are not
already known, this must be evaluated carefully. The materials must be
relatively nontoxic to can-plant employees, plant neighbors, can packers, and
to anyone involved in the product-distribution, product-consumer, and
container-disposal and -recycling system. Screening information (tests on
animals) must be made available for toxic effects through ingestion, inhala-
tion, and skin absorption, as well as tests for eye irritation and determina-
tion of whether the material is a primary skin irritant. Such information is
required on individual ingredients as well as the compounded formulation.
Where screening-test information indicates potential for adverse effects,
further detail is required, such as potential chronic tbxicity information
and hazard-control detail.
Closely allied to toxicity detail is knowledge of the volatility of the
ingredients and the formulated material, with respect to protection of our
plant employees and control of emissions. Fire hazard and any nuisance or
physical hazard to employees or facilities are also important considerations.
Stability of the material is important. It must not change during
transportation and storage at our plant. Otherwise, troubles might be
encountered in use of the material in can-manufacturing processes, or ad-
verse effects might be encountered by our customers or ultimate consumers.
Applicability of a new formulation is extremely important. It must be
free of significant problems in application to the metal surface, drying the
399
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coated film, and fabrication of the coated metal into containers at high
production rates. The dried film must not be affected during storage and
transportation and must cause no difficulties to the customer in filling,
sealing, and processing the filled containers.
The prime requisite of the container is its integrity; it must provide
required shelf life for the canned product and preserve its quality. No
detectable portion of the coating material can leach or migrate into the
canned product. Flavor, odor, and texture of the product must not be affected.
If a new resin system, one that does not have prior Food and Drug
Administration sanction, is used in a coating formulation for lining of cans
for edible products, then lengthy extraction and animal-feeding tests are
required. The usual time required for these is 2 to 4 years at costs now
exceeding $500,000 for each new resin system.
The standard procedure for evaluation of a new coating material sub-
mitted to the can manufacturer involves laboratory examination followed by
plant trial use, fabrication of about 1,000 cans, filling them with the
customer's product, and periodic examination after storage. If the material
passes all requirements, then larger quantities are fabricated, packed,
examined, etc. Usually, progression in three stages to the million-can
quantity is required before customer approval for use of the new coating
formulation in commercial quantity is obtained.
Obviously, availability of the new coating formulation at practical cost
is essential. Otherwise, it would be better to continue with conventional
time-proved materials with provision of the control devices for the emissions.
New formulations can be rejected for failure to measure up to standards
for any of the foregoing criteria. The track record for new formulations
attests to the difficulties involved. In my company's experience an average
of 3 of 100 candidate materials submitted by coating-material suppliers
eventually reach the commercial use stage.
Appreciable success is being attained in reformulating to water-borne
varnish and various other surface coatings for metals. A relative few of
these contain no organic solvent, but in most of those now in commerical use,
the volatile portion consists of 20 percent organic solvent and 80 percent
water. With some materials prohibitive troubles are encountered if the
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organic solvent portion of the volatiles is lower than 30 percent. The most
commonly used organic solvents in water-borne coatings are cellosolves and
butyl alcohol.
Comparatively amazing success has been realized in development of UV
curable inks. There is good promise that this will continue and that this
experience will enhance success in development of UV curable surface coatings
for metal.
Table 4 lists the kinds of ingredients in UV metal-decorating materials
(coatings and inks) now showing considerable promise. There are many
variations, of course, in choice of these components and concentrations
involved in individual formulations. At the moment, apparently most progress
is being made with acrylate systems (free radical cure systems), but signif-
icant progress is also being realized with cationic, two-package epoxy
formulations. Of prime importance in the development of UV materials is the
requirement that volatility of the material be closely limited. This must
be controlled by specification. It is essential for protection of can plant
employees as well as prevention of emissions to the extent that no emission
control devices are required.
Figure 11 illustrates UV ink application by tandem presses, each fol-
lowed by a UV drying system. In most such arrangements each press may apply
two colors of inks. These are followed by application of water-borne varnish
which requires no emission control device for the oven exhaust air.
The typical UV curing unit has two exhaust ducts handling a total of
about 3,000 CFM. This is for exhaust of air for cooling of the UV lamps,
the ozone they generate, and any monomers or oligomers volatilized during
the UV cure. As mentioned, extent of the latter is limited by specification.
My company rejects UV-curable material formulations if the volatiles result
in emissions greater than 0.5 Ib/hr. Ozone evolved and exhausted to the
atmosphere varies with power of the lamps, but never exceeds 1 ppm in the
exhaust air or 0.02 Ib/hr.
Even though hydrocarbon emission problems are resolved through use of
UV inks and water-borne coatings, fuel gas consumed by the drying oven for
the latter, or for high solids content solvent-borne coatings, remains as a
critical problem. Accordingly, progress is being made in development of UV
401
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ro.ller coatings. With these the figure-12 schematic of process equipment is
used, and the gas-heated oven is eliminated.
Although my comments have been on decoration of metal sheets before
fabrication into cans, technology developments in decoration and coating of
formed cans are keeping pace. We expect continued rapid growth of UV
materials in the metal-decorating industry, with major replacement of
thermally cured materials in only a few years. My company, for example,
currently has 17 metal-decorating lines equipped with UV units in commerical
use. Eight more will be using UV materials by mid-1976. By 1980 we antici-
pate that all of our metal printing and half of our metal coating will be with
UV materials.
(On the following pages are the 4 tables and 12 figures cited in the
text.)
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Table 1. Conventional (heat-cured) metal-decorating ink
Component
Percent
Low-viscosity resin 30 to 95
(e.g., oil-base alkyd, epoxy ester)
Pigment or colorant 5 to 60
(e.g., cobalt blue, iron oxide, earth colors,
organic dye coprecipitated with aluminum
hydroxide, titanium dioxide)
Extender 0 to 50
(e.g., aluminum hydroxide)
Dryer 0 to 0.2
(e.g., cobalt naphthenate, manganese
naphthenate)
Solvent 0 to 1.0
(e.g., high-boiling mineral spirits)
Table 2. Conventional solvent-borne
roller coatings for metal sheets
Resins
Vinyl
Epoxy
Alkyd
Phenolic
Polybutadiene
Oleoresinous
Polyester
Acrylic
Ami no
Additives
Titanium dioxide
Aluminum powder
Zinc oxide
Lubricant
Solvents
Aliphatic petroleum hydrocarbons
Methyl isobutyl ketone
Methyl ethyl ketone
Glycol ethers & ether esters
Xylene
Butyl acetate
Butyl alcohol
Drying oils
Linseed
Cottonseed
Soya
Coconut
Safflower
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Table 3. Criteria for metal-decorating material
Toxicity Stability Integrity
Volatility Applicability Availability and cost
Table 4. Ultraviolet-curable metal-decorating materials
Component Percent
Vehicle 40 to 90
(e.g., bisphenol-A epoxy diglycidyl ether,
trimethanolpropane triacrylate, urethane,
2-package epoxy systems)
Photoinitiator or photosensitizer
(e.g., bisphenol, Michler's ketone,
Lewis acid)
Accelerator 1 to 6
(e.g., methyl diethanolamine, other
tertiary amines)
Stabilizer 0 to 1
(e.g., benzoquinone)
Additives 0 to 5
(e.g., wax, silica gel)
NOTE.-The above materials are typical of those used in
UV varnish. They are also typical of those used in UV
inks containing up to 50 percent pigment.
404
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EXHAUST
STACK
PRINT
OVEN
Figure 1. Metal sheet decorating unit
conventional heat-cured ink.
EXHAUST
STACK
PRINT VARNISH
COATER
OVEN
Figure 2. Metal sheet decorating unit using
conventional ink and solvent-borne
varnish roller coated over the wet ink
405
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EXHAUST
STACK
PRINT
VARNISH
COATER
OVEN
Figure 3. Metal decorating unit using ultraviolet
curable ink and solvent-borne overprint
varnish.
8-
COATER
EXHAUST
STACK
OVEN
Figure 4. Metal sheet roller-coating with
solvent-borne enamel, lacquer,
sizing or varnish.
406
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INCINERATOR
1,250° - 1.400°F
EXHAUST
STACK
8-
COATER
Figure 5. Roller-water unit with thermal
incinerator for oven exhaust.
8-
BURNER
CHAMBER
EXHAUST
STACK
Figure 6. Coater unit with catalytic
incineration system.
407
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EXHAUST
OUT
800"
300°
EXHAUST IN
700°
BURNER
CHAMBER
HEAT
EXCHANGER
1,400°
Figure 7. Thermal incinerator with
heat exchanger.
EXHAUST
OUT
650°
300°
f
EXHAUST IN
HEAT
EXCHANGER
CATALYST
900°
550°
BURNER
CHAMBER
750°
Figure 8. Catalytic incinerator with
heat exchanger.
408
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EXHAUST
OUT
vo
CATALYST
EXHAUST
IN
HEAT RECOVERY
BURNER
CHAMBER
HEAT
EXCHANGER
Figure 9. Catalytic incinerator with heat
exchanger and heat recovery.
-------
8-
INCINERATOR
1150°-1300°F
PREHEATERl^
INTAKE
t
INCINERATOR DISCHARGE AIR DUCTED TO
OVEN ZONES, REPLACING ZONE BURNERS
-*-PREHEATER
EXHAUST
Figure 10. Thermal incinerator with
heat recovery.
-------
PRINT
PRINT
VARNISH
COATER
EXHAUST
STACK
OVEN
Figure 11. Tandem UV printing units followed
by solvent-borne varnish.
PRINT
PRINT
VARNISH
COATER
Figure 12. Tandem UV printing followed by
UV varnish.
411
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THE APPLICATION OF SOLVENTLESS INKS
IN WEB AND SHEETFED OFFSET SYSTEMS
W. E. Rusterholz*
Abstract
A brief history of solventless ink systems introduces this review. The
factors that have led to the current usage of ultraviolet curing systems in
web and sheetfed offset printing are presented. A survey of the advantages
and disadvantages of these ink systems is made with relation to this segment
of the printing industry. The roles of energy, pollution regulations, and
economics as motives for using solventless inks are discussed. Finally, the
estimated $4,000,000 market for 1975 is broken down by end-use applications.
No one can argue that the concept of a solventless ink system is not
timely; and it is certainly not new. In fact, it has its roots in the tradi-
tional mechanisms associated with the method by which a printed ink film is
immobilized. These methods are: 1) Oxidation (chemical), 2) Penetration,
3) Solvent evaporation, and 4) Moisture setting (precipitation). There
is no doubt then that a news ink is a solventless system since, it is a
dispersion in essentially nonvolatile liquid carriers that set by absorption
into the pulpy news stocks, which function like a blotter. In the same
sense, many traditional sheetfed inks are also solventless systems, being
dispersions in nonvolatile oleoresinous vehicles. These cure in time by
oxidation.
Today most people feel that solventless inks were developed to replace
conventional heat-drying offset inks. High-speed web offset has been one of
the largest growing segments of the converting industry since the 1960's.
At about this same time, concerns for the environment with regard to air
pollution were growing with equal vigor. It was already obvious in the mid
to late 1960's that this expanding market was on a collision course with the
environmental legislation.
*Manager, Technical Support Section, Sun Chemical Corp., Carlstadt,
New Jersey.
412
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The heart of the conventional offset heatset ink formulation is a low-
molecular-weight resinous binder dissolved in a proprietary hydrocarbon
solvent blend. Standard formulations utilize up to 35-40 percent by weight
of these hydrocarbon solvents to impart the flow properties necessary in the
printing process. The setting of the ink film is then accomplished by
removal of most of the hydrocarbon solvents by evaporation. The low-molecu-
lar-weight resin is regenerated and forms the binder of the dry, pigmented
ink film.
By the early 1970's the models for the current air pollution regulations
were hitting hard at these same hydrocarbons as a major source of organic
pollutants. In addition the concept of first dissolving and then regener-
ating heatset resins was recognized as an energy-expensive procedure. On one
hand there is use of energy to effect solution, and very high energies
(1,000,000 Btu/hr) associated with common gas-fired heatset ovens are used
to evaporate the solvent from the printed film.
One solution to heatset solvent emissions in the late 1960's and early
1970's was the afterburner. This energy-wasteful device became less feasi-
ble by 1973 as natural-gas shortages developed. By 1974 it was a hard fact
of life that severe gas shortages were threatening the gas previously
allocated to standard web, offset oven operations; to this must be added
the well-remembered chemical raw materials shortages of 1974. The stage was
set for the entrance of the sol vent!ess ink alternative.
Over the past 10 years, the major ink producers have committed
increasing percentages of their research dollars to solventless ink develop-
ment. This technology evolved through a series of steps paced by the con-
fining restraints of pollution, energy, and, finally, cost. As these
factors came into play, the solutions ranged from exempt solvent formulations
to high-resin solids and low solvent content and, finally, to no solvent.
All of these alternative systems are available today.
Solventless inks can be thought of as ones in which the high-molecular-
weight resinous binder is formed immediately after printing. These can be
roughly divided into systems initiated by heat or by higher forms of energy.
The thermally curing solventless system is based on the copolymeriza-
tion of a blend of liquid synthetic resins. The reaction is initiated by a
latent catalyst present in the one-pot system, which is triggered by the
413
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heat of a conventional heatset oven. The advantages of the system are good
gloss and excellent film properties, and, especially, rub and grease resist-
ance. The disadvantages are chiefly costs. Some effluent is also liberated
because this is a condensation polymerization that, depending on the raw
materials used, evolves water, lower alcohols, and trace organics such as
aldehydes. With inks of this type, it was possible to approach an 85 per-
cent reduction in emissions with no hydrocarbon effluents.
Considering the history of printing ink technology, heat-catalyzed
systems with these advantages should have been a major development. However,
the rapidly changing influences of the critical factors mentioned previously
virtually obsoleted these systems due to their poor economics and to their
reliance on gas-fired drying equipment.
At present, solventless ink technology has turned to more energetic
types of drying. The three areas that have been most intensively investi-
gated are microwave, electron beam, and ultraviolet radiation. The micro-
wave technology is restricted to ink systems with high loss factors which
limits its present use to water-base vehicles. Electron beam offers advan-
tages of curing thick films (greater than 1 mil), but this technology has
been applied only in the coatings area to date. Ultraviolet curing has
gained wide acceptance in printing because it offers an acceptable compromise
of an easily shielded, reasonably high energy radiation from available
sources at a reasonable cost.
The ink systems commercially used in both web and sheetfed offset
printing are composed of liquid nonvolatile monomers and prepolymers combined
with a photoinitiator. When the composition absorbs UV light, the photo-
initiator is activated and a rapid crosslinking reaction occurs. Since this
reaction is based on an addition polymerization, no effluent at all is
liberated from the ink during the drying (curing) period.
The main advantages of UV to web printers have been:
1. Lack of pollution,
2. Excellent stability on the press distribution system,
3. Independence from gas-fired equipment,
4. Less substrate degradation than in conventional heatset ovens.
The advantages to sheetfed printers are somewhat different. Since sheetfed
has essentially always been a solventless process, the lack of pollution is
414
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not the incentive. It is here that the enhanced film properties of UV-cured
inks most often account for its usage. The advantages are that:
1. The instantaneous film properties allow work and turn in produc-
tion,
2. Offset spray is eliminated,
3. Secondary in-line processing becomes possible (die cutting).
The disadvantages of UV curing are the same to both areas of usage. These
are:
1. The higher cost of inks due to replacement of solvent with high-
cost monomers,
2. The purchase of new "drying" equipment,
3. Difficulty of deinking fully cured prints by conventional methods,
4. More sophisticated safety requirements in handling the uncured inks,
The question of safe handling of UV systems is an important one. At
present most commercial UV inks are based on acrylate chemistry. In compari-
son to conventional ink vehicles, acrylates have a higher intrinsic toxicity
associated with them. They are irritants to the eye, and most are rated as
potential skin irritants by standard testing procedures.
As UV solvent!ess inks have moved into commercial usage, an effective
exposure reduction program for the pressroom is essential. Prescreening of
commercial ink vehicles for skin irritation potential provides a sound
approach to reduce hazards. In practice the exposure reduction program for
offset pressrooms is a fairly simple one and represents a second-line pre-
cautionary measure.
It has been found that the biggest single obstacle to lowest practical
exposure at the converting level is a worker's own past experience. This is
because conventional offset inks use raw materials of very low inherent
toxicity, even at very high dose rates. An effective safety program usually
stresses a reeducation to good commonsense work habits at both the worker
and supervisory levels.
To put the present picture in perspective, the printer has a series of
restrictions that are driving him away from his traditional technical and
business posture. The ink industry has sought alternatives that can offer
both immediate and, hopefully, longer term benefits. The degree of accep-
tance of sol vent!ess systems into the web or sheetfed markets results in a
415
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series of trade-offs by the individual converter to balance his particular
needs.
1. Utilities vs. Agencies: On one hand, there is pressure to
eliminate pollution by incineration, but on the other, many
converters can have no new gas allocations and even face cut-
backs on existing equipment.
2. Print Quality—Solventless Systems vs. Conventional: The indi-
vidual converter's product mix requirements affect his need to
choose between such things as improved printing sharpness and
improved film properties at nearly equivalent gloss of conven-
tional inks.
3. Benefits vs. Economics: On ink cost alone UV is certainly not
justified. The current pricing on web UV process colors averages
a 100 percent upcharge over conventional. For black a 200 percent
upcharge is usual because of the relatively low price of conven-
tional black inks.
4. Enforcement vs. Competitive Position: The equitable enforce-
ment of pollution regulations is necessary to prevent removal
of work from one plant to another or one competitor to another
because of the converting costs. The ultimate solution to
inequitable enforcement has been the relocation of plants and
its attendant dislocations in employment.
With this perspective it is worth noting that the estimated dollar
market for UV paper applications will approach $4,000,000 for 1975. At
mid-1975 this market was based on the following distribution of press
installations:
40 web presses printing envelopes, catalogs, magazines, books, etc.,
15 sheetfed presses printing cartons,
20 sheetfed presses printing labels, brochures, book jackets, etc.
In summation, it can be said that conferences such as these can provide
a forum for both the government and the printing community to exchange
viewpoints. It would seem that the greatest danger to all of us is to be
precipitous in our actions. It is necessary to have the time to develop
sound technology in response to what is reasonable to achieve, and all of
this must fit some reasonable economic framework.
416
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BIBLIOGRAPHY
R. W. Bassemir and A. J. Bean, "Parameters of UV Inks," TAGA Proceedings
1974, Technical Assn. of the Graphic Arts, Rochester, N. Y., 1974.
Robert W. Bassemir, "Solvent Free Inks for Litho and Letterpress--The State
of the Art," TAPPI, Vol. 55, No. 5 (1972), p. 729.
Robert W. Bassemir, "UV Ink Chemistry: Paper and Paperboard," American
Inkmaker, Vol. 52, No. 12 (1974), p. 33.
G. R. Berbeco and S. V. Nable, "Electron Beam Curing," Paint and Varnish
Production. August 1974, p. 39.
Daniel J. Carlick, "The Suncure System," Penrose Annual 64, Lund Humphries
Publishers Ltd., London, 1971, p. 68.
Daniel J. Carlick, "Ultraviolet Curing of Inks," Modern Packaging, Vol. 45,
No. 12 (1972), p. 64.
"Curing Ink With Electron Beams," Business Week, March 24, 1975, p. 44H.
A. deKerhor, "The UV Drying of Offset Inks at 'Sud-Ouest'," Newspaper
Techniques, August 1973, p. 10.
Paul W. Greubel, "The Impact of U.V. Inks on the Graphic Arts Processes,"
Printing Plates Magazine, Vol. 60, No. 5 (1974), p. 3.
"Inks That Dry With UV Light," Graphic Arts Monthly, May 1975, p. 40.
Leslie J. Jezuit, "U.V. Drying and Sheet Fed Offset Printing: Marriage or
Mirage," J. Radiation Curing, Vol. 1, No. 3 (1974), p. 19.
Vincent D. McGinniss, "Acrylate Systems for U.V. Curing. Part I: Light
Sources and Photoinitiators," J. Radiation Curing, Vol. 2, No. 1
(1975), p. 3.
V. D. McGinness, and V. W. Ting, "Acrylate Systems for U.V. Curing. Part II
Monomers and Crosslinking Resin Systems," J. Radiation Curing, Vol. 2,
No. 1 (1975), p. 14.
Henry Monti 11 on, "The Use of UV Inks and UV Curing System—A Case History,"
Proceedings (Part I) 1973 Conference Web Offset Section, Printing
Industries of America, May 15-17, 1973. p. 44.
"Popularity Grows for UV-Curing Systems," Electronic Packaging and Produc-
tion, Vol. 14, No. 6 (1974), p. 71.
I. K. Shahidi, J. C. Trabellas, and J. A. Vona, "Multifunctional Monomers
for UV Cure," Paint and Varnish Production, August 1974, p. 32.
I. K. Shahidi and T. M. Powanda, "Ultraviolet Curing: A Review of the
Technology," American Inkmaker, January 1975, p. 21.
Joel J. Shulman, "Prospects for Radiation Cured Inks Are Best in Paperboard
Packaging," Paperboard Packaging, May 1974, p. 20.
417
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Joel J. Shulman, "Ultraviolet Sensitive Inks: A Cure for Scuff, Scratch
and Rub?" Paperboard Packaging, November 1972, p. 22.
"Ultra-Violet Curing for Printing Inks," Pigment and Resin Technology,
Vol. 11, No. 12 (1972), p. 21.
"Ultra-violet Ink Drying," leaflet published by British Federation of
Master Printers, 11 Bedford Row, London WC1R 4DX, England.
"Ultra-Violet Radiation Curing," Pigment and Resin Technology, Vol. 2, No. 2
(1973), p. 14.
"UV Cure Cuts Pollution, Energy Use," Environmental Science and Technology,
Vol. 7, No. 6 (1973), p. 502.
J. W. Vanderhoff and J. Lavelle, "De-Inkability of Wastepaper," NPIRI
forum meeting, October 18, 1973.
John W. Vanderhoff, "De-Inking—The Ink Industry's Position," American
Inkmaker, April 1973, p. 38.
"Web Offset Printing and U.V. Curing Under Production Conditions," Modern
Lithography, June 1972, p. 14.
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ELECTRICURE* ENVIRONMENTAL IMPACT
Robert G. Muggli, Ph.D.t
Electricure electronic systems' effect on the environment inside and
outside a printing plant is total. The ultimate environmentalist objective
of zero pollution is now completely realizable. As are other electronic
devices, Electricure electronic systems, are compact, sophisticated, pre-
cisely controllable, quiet and instantaneous in operation, energy conserva-
tive, and a quantum leap ahead of conventional methods. Their use in the
printing industry becomes a question of "when," not "if," once Electricure
systems are understood completely. The scope of this presentation does not
permit their uses, however, so those concerned are encouraged to examine
references 1,2, and 3.
Briefly but systematically, I would like to describe Electricure elec-
tronic systems and their "impact" on the environment and on the printing
industry.
Electri Graphics
E6I is concerned with complete production systems designed to utilize
emerging electronic technology to the optimum. We abandon laboratory de-
vices to those with lesser objectives. Our reasoning is that the industry
problems of energy, pollution, cost, petroleum shortage, and OSHA standards
are here with us now, and need to be solved now. Research conducted to
prove that which is already known, as is depicted in the cartoon, "Research
is what we do to prove what we know," does not make progress now. Thus we
will leave this area to the nonpragmatist. In Chicago, we have entertained
many researchers, only to learn later that they have rediscovered what they
had already seen and heard at EGI!
Electron Accelerators
For over 20 years, electron microscopes, cathode ray tubes, electron
*Electricure is a trademark of Electri Graphics, Inc., Chicago,
Illinois.
•{Technical Director, Electri Graphics, Inc., Chicago, Illinois.
419
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beams, and electron curtains have been in use for various purposes: re-
search, entertainment, vulcanizing of rubber, curing of plastics, coatings,
etc. Electricure electronic systems employ electron acceleration, and our
recent developments impart the industrial reliability needed. A precisely
defined, uniform, continuous, high-energy electron discharge of any width
is maintained constantly and is automatically controlled. The principal of
operation is basically simple: electrons available from incoming power
lines are raised a thousandfold in potential by a transformer-rectifier net-
work encased inside power supply modules. Cable transmission is made to the
accelerator, where this energy is shaped and projected outwardly, lengthwise
of the tube, at the product (web, sheet, item, etc.). The quantity is regu-
lated or slaved to the press, thus eliminating the need for a Ph.D. to oper-
ate a system (my job security seems to be on a limb).
Process Environment
The atmosphere within the process zone is reduced by the energetic elec-
trons emitted from the accelerator, thus preventing the formation of ozone
and eliminating the need for nitrogen blanketing.
Chemistry
Electricure inks, coatings, and adhesives are real-time examples of
quantum concepts of chemistry: orbital states, energy transition, etc.
They are stable, nonvolatile, nonflammable, nontoxic, liquid, and semi liquid
compositions prone to instant solidification when energized by high-speed
electrons.
Air Pollution
Electricure electronic systems offer an alternative to afterburners,
smoke precipitators, solvent incinerators, solvent recovery plants, and air
contamination. Cold ovens without exhaust piping, drying without heat, and
ink without solvents are Electricure precepts. The elimination of pollution
is complete: no thermal pollution, no solvent pollution, no combustion
fumes, no noise pollution.
420
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Solvents
The amount of solvent in conventional inks varies from a small quantity
to over 75 percent. The process of ink drying by evaporation of these sol-
vents causes air contamination of press rooms and the surrounding environ-
ment. The storage of large quantities of solvent presents major fire haz-
ards, as both Chicago and Philadelphia have experienced. Electricure elec-
tronic systems make these problems characteristic of a bygone era. Petrole-
um usage is further reduced as less frequent washups are required. Elimina-
tion of premature ink drying on the press is axiomatic because Electricure
inks can only be dried by high-energy electrons. A further coorelative is
that the liquid inks with complete press stability can be printed with thin-
ner, more pigment-concentrated films, thus saving on chemical usage. Simi-
larly, the constant addition of solvent on a press in order to maintain
viscosity vanishes with this new technology.
Press Speeds
Electricure ink drying speed is measured in milliseconds. Unlike con-
ventional drying where press speeds are limited by the drying capacity of the
ovens, Electricure electronic systems are limited by the speed capability of
the press. This reverses the historic dependence on drying-time considera-
tions in printing.
Press Design
Because of their compactness, Electricure electronic systems permit the
design of smaller, but faster presses. With 100 percent stable inks, auto-
mation of press operations is possible, freeing people from mundane opera-
tions, such as removing dried ink from rollers, plates, and cylinders;
doctor blade adjustments; solvent additions; ink addition; and the numerous
other details a pressman must attend to in order to keep printing with inks
that dry everywhere, as well as in the oven.
Pressrooms
A pressroom with Electricure electronic systems can be ideal. It would
be air conditioned and brightly lighted with small compact presses without
exhaust systems, heat, smoke, fumes, or fire hazards—a modern illustration
421
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of an industrial plant designed with people in mind and for sharp contrast
to contemporary pressrooms.
Print Quality
Instantaneous, cold-energy ink drying produces copy that is sharper and
more vivid; has higher gloss, increased durability, and more skuff resis-
tance; and possesses higher consistent color fidelity than any prior method
of ink drying. A few researchers have contrasted Thermal, UV, and Electri-
cure quality of printing and have confirmed the fact that Electricure inks
are, in all aspects, unmatched.
Cost
The capital cost of Electricure electronic systems is greater than that
of conventional ovens; electronics are simply more expensive than sheet metal
tnd pipes. The economic benefits of all capital equipment come with use, not
ownership. EGI's leasing policy reduces capital expense and permits the ac-
quisition of an entire system while not having to be concerned with technical
obsolescence. The numerous other advantages to a printer can be learned from
any comptroller of any major corporation. More important than capital costs
•re the costs of consumables. In minimizing these costs, Electricure elec-
tronic systems are unequaled. Consider the following variable costs:
1. Energy--Lower utility costs because of reductions in usage of
electricity, gas, water, etc., required for drying, cooling, in-
cineration, and recovery of solvents. (Freedom from dependence
on natural gas is invaluable in itself.)
2. Productivity—Increased production from faster presses, quicker
make-ready, and less down time.
3. JjTk^-Less waste and greater mileage with somewhat higher ink cost
per pound, resulting in lower ink invoice costs.
4. Waste—Slaved drying response and instantaneous response produce
less scrap paper.
5. Paper—Thinner grade and lower coating-weight papers are permissi-
ble with compact cold ovens that use inks that dry before they
penetrate.
422
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6. Labor—More effective use of manpower, resulting from automatic
operation. Complete cost models have been prepared for various
printing processes, but even though figures don't lie, liars can
figure, so we prefer that these computations be prepared by you;
we offer our assistance only.
Safety
Electricure electronic systems eliminate heat, fumes, and fire hazards
from the pressroom. They meet OSHA requirements, national electrical codes,
and State regulations. Pressrooms can thus become safer as well as more
pleasant work areas.
I would like to pause after this expose" of all of the virtues of Elec-
tricure electronic systems and comment on the disadvantages.
Pride
Electri Graphics is not a major corporation but has hit the industry
with what has been referred to as "fantastique, the greatest invention since
Gutenberg, magic." The NIH (not invented here) effect on research directors
has been for some to fund their own research and rediscover electron drying
in their own laboratories. Their game plan is simple: prove what has been
demonstrated by EGI; assemble reports dating back 20 years to show that they
were not inactive these past years; piously ponder the engineering difficul-
ties of high-energy electronics, aerodynamics, and printability of this new
technology; recognize the inevitable by postulating that it is 5 to 10 years
away; then pride themselves with the rapid success of their own developments.
The realization that no one has a monopoly on talent is difficult to acknow-
ledge when you are responsible for large research budgets.
Hangup
The U.S. printing industry has a hangup: UV. The vast amount of dol-
lars spent on research, engineering, equipment, and promotion by a large
number of companies, including chemical companies; ink, lamp, and press
manufacturers; and printers can not be justified. The meager sales of UV
inks—less than 1 percent of the market—are a measure of the actual print-
ing after 10 years of commercial exposure. The effort to make this low-
423
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energy source do the impractical has been horrendous. As with all hangups,
preoccupation with UV is hard to identify, painful to acknowledge, and per-
sistent. Perhaps at one time the effort was worthwhile in order to prove
that that new technology could do new things, but that time has passed. The
abandonment of all further UV research by a number of industry leaders at a
time when there are more manufacturers of equipment than ever (11) is a good
omen.
Credibility
We live at a time when cynicism is a daily fact of life. Deceit in
business and private and public life is common and causes all to doubt most
statements. The newer, the more significant the development, the greater
the doubt. We are delighted to demonstrate the scientific validity of all
of our statements, but so often justification for doubts is what is sought.
Scientists also have lost credibility. Perhaps in 1985, after 10 years of
commercial installations, this doubt will disappear.
Money
When venture capital was needed by the manufacturer of our accelerator
to prove the concept on a commercial level, high interest rates dried up
venture capital more severely than it did research budgets. The problems of
tomorrow were forgotten for the problems of today. This injury caused delay
but shifted electron technology to EGI, and we now captively manufacture the
entire Electricure system. With the delay behind us, our technical strength
is greater.
Risk
The capital cost of large electronic systems is high. This makes the
gamble large, and doubting people become cautious. The thrill of being
first is lost to the necessity of being safe inside the fold. From that
position, one can complain about EPA regulations, OSHA inspections, energy
interruptions, and material shortages, and still do nothing and not be
noticed. To the real leaders, not necessarily the big printers, this is
nonsense, and explains why their profit margins are greater. With more ex-
pensive, yet more productive equipment, and consequently with lower cost,
424
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these firms grow at the expense of other larger, more ponderous ones.
I would like to apologize for straying from the environmental effects of
our Electricure system. It is difficult to find more to express after one
has demonstrated zero pollution, except that partial solutions become inade-
quate. Incinerators, afterburners, smoke precipitators, dust collectors,
and solvent recovery plants become inadequate and obsolete before they are
purchased.
REFERENCES
1. "Instant Ink Drying," Printing Impressions, May 1974.
3. "Electricure Images of the Future," Gravure Technical Association
2. "Cathode Ray Emission System," Paperboard Packaging, October 1974.
"Electricure Images <
Bulletin, Summer 1975.
COMMENT
CHAIRMAN DOWNIE; I am struggling hard to find what Bob's talk illustrates.
I think maybe it illustrates the ingenuity of American industry to
respond to a challenge. I think it might illustrate serendipity,
where you fall into something ghastly and come up covered in diamonds.
I think it illustrates that if I had seen his paper first, I think
I would have asked the first two speakers not to bother. I will tell
you what I am going to do. I am going to change my name from Bob to
Thomas because that is exactly what I am. I am sorry, Bob, I am a much
doubter. What a bloody awful talk.
425
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CARBONLESS COPYING PAPERS
George Baxter, Ph.D.*
Abstract
The application of microencapsulation technology to pressure-sensitive
copying systems in modern manifold business forms has grown, dramatically in
the past few years. It appears tht the higher cost and higher waste during
forms manufacture with such systems have become less significant factors in
curtailing their use than they were formerly. The improved quality and
cleanliness of the copy obtained with microcapsule systems as compared with
the older hot melt wax (carbon paper) systems is only a partial explanation
for their wider use. Short supply of raw materials, preservation of the
ecology, and waste disposal are now serious considerations Uniting the use
of the older pressure transfer copying systems. The technical and economic
feasibility of recycling carbonless copying papers after use has been demon-
strated and this is an additional attractive feature of such systems.
INTRODUCTION
The most widely used copying system in business forms today is still
carbon paper. This term covers a multitude of pressure transferable, mark-
producing coatings. The most common system utilizes wax-based coatings con-
taining carbon black or other pigments (figure 1). Such coatings are of
necessity relatively soft and of low tensile strength and they tend to be
dirty to handle. Also, they are prone to premature transfer in the business
form as the result of accidental scuffing, or the impressed image itself is
liable to smudge and offset onto hands or clothing. A few of these difficul-
ties have been avoided by the development of certain more coherent pigment-
containing coatings that will transfer only to specially treated adjacent
*Manager, Chemical Development, Moore Business Forms, Inc., Niagara
Falls, New York. •
426
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PAMft
WftlTINq
_.
Figure 1. Image formation by pressure transfer
of hot melt carbon coatings.
surfaces, but there still remain many problems associated with the use of
these continuous, pressure-transferable coatings.
In addition to the functional and aesthetic shortcomings of carbon
papers, certain other adverse pressures have been applied in recent years.
Emphasis on the preservation of the ecology has had a very significant effe<
In the great majority of these systems, carbon is coated on tissue and intei
leaved between the bond papers receiving the copy. When such forms are
decollated after use, the problem of carbon paper disposal remains. No
longer can these materials be incinerated in the downstairs furnace, buried
in the backyard, or discarded as carelessly as before. Frequently, a signi
ficant cost is involved in their satisfactory disposal after use. Also,
increasing pressure is being applied to manufacturers of carbon or other
427
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pigments to clean up their manufacturing operations. This has lead to the
shutdown of several such plants with resultant supply problems to carbon
paper manufacturers. Other raw materials used in this industry have also
been withdrawn for ecological or toxicity reasons. The strong dependence
on petroleum products has introduced additional difficulties; I will not
elaborate on these. The carbon copying system which has served so well will
in the future have a reduced role in our ecology-conscious society.
The newer, more efficient, microcapsule copying systems have not as yet
been widely used. High cost of materials plus high waste in forms manufac-
ture have priced them well above the carbon systems. However, as more effi-
cient and more elegant ways are developed to manufacture and process these
carbonless systems, and the problems with carbon paper persist, the price
difference between the two will be minimal. A great deal of work has already
been done to make the carbonless systems more economically and ecologically
acceptable. The technical and economic feasibility of recycling carbonless
copying papers has also been demonstrated and is an additional attractive
feature of such systems.
The function of the microcapsule coatings in carbonless copying may be
illustrated by figure 2. When writing or printing pressure is applied to the
coated sheet, the capsules are ruptured and liquid marking fluid is trans-
ferred to the receiving sheet, making a sharp, smudge-free copy. However,
during the usual handling such as cutting, perforating, punching, etc.,
which such papers must undergo in their assembly into business forms, the
capsule coatings are prematurely damaged. This results in lower copying
efficiency and, frequently, discoloration of the business forms as the result
of smudging and offset. This problem has been minimized by the introduction
of certain inert materials into the microcapsule coatings (figure 3). The
particle size of these materials is slightly greater than that of the micro-
capsules and they act as "spacers," minimizing premature damage to the micro-
capsules as a result of incidental pressure or abrasion.
MICROCAPSULE STRUCTURE
Microcapsules can have a variety of physical structures but the
present discussion will be confined to the two shown in figure 4. Figure
4a shows a capsule in which A is the encapsulated material. All of the
428
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CO«THIO
BICilVIMO COOTIMO
WRITING OR PRINTING
niEssime
igure 2. Image formation by pressure transfer
from microcapsule (carbonless) coatings.
PA PI R
O MiCROCAPSULt
I ANI'bMUD&E SPACER
Figure 3. Antismudge materials in carbonless
copying.
429
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a. £:•-:-:-:-:-$ b.
Figure 4. Physical structures of microcapsules.
processes to be discussed encapsulate a liquid core which is preferred in
copying systems because of its superior pressure transfer characterisites in
comparison with solid or semi sol id core materials. EMs the capsule shell
material, generally a high-molecular-weight polymer. Figure 4b shows a
double-or dual-walled microcapsule. Again /\ is the encapsulated core
material, B^ is the inner shell wall, and (Ms the second or outer shell wall,
generally applied by a technique different from that for the inner shell.
MICROENCAPSULATION: MATERIALS AND TECHNOLOGY
In the following discussion, the objective will be to provide an under-
standing of the unique advantages of the microencapsulation technique in
carbonless copying, with some minor references also to its application in
other areas. Those areas include the food, pharmaceutical, cosmetic, chemi-
cal, petrochemical, and bioengineering industries.
Microcapsules can be described under three main headings:
1. Microcapsule wall materials,
2. Liquids suitable for mi encapsulation, and
3. Applications for microencapsulation.
Figure 5 lists capsule wall materials ranging from the naturally occurring
gelatin and zein to waxes, resins, and synthetic polymers. Many other
materials could be added to this list, including inorganic materials like
sodium silicate. In figure 6 there is a partial listing of liquids that can
be encapsulated by some or all of the wall materials in figure 5. Again, this
430
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GELATIN METHYLCELLULOSE
GUM ARABIC CELLULOSE NITRATE
POLYSTYRENE CELLULOSE ACETATE PHTHALATE
ALBUMIN POLYMETHYL METHACRYLATE
WHEAT GLUTEN STARCH ACID ESTERS
ZEIN POLYVINYL ALCOHOL
CARNAUBA WAX POLYVINYL PYRROLIDONE
BEESWAX PHENOL-FORMALDEHYDE
POLYESTER UREA-FORMALDEHYDE
MONTAN WAX POLYSULFONAMIDE
PARAFFIN WAX CANDELLILA WAX
POLYETHYLENE POLYCARBONATE
POLYAMIDE POLYURETHANE
POLYUREA
Figure 5. Microcapsule shell wall materials.
OLIVE OIL DIOXAN
COCONUT OIL CYCLOHEXANE
CASTOR OIL KEROSENE
CORN OIL PETROLEUM ETHER
SOYBEAN OIL PETROLEUM NAPHTHA
WHALE OIL MINERAL OIL
LEMON OIL ETHYL ACETATE
ORANGE OIL BUTYL ACETATE
TOLUENE DIMETHYL PHTHALATE
XYLENE DIBUTYL PHTHALATE
TURPENTINE TRICRESYL PHOSPHATE
PENTANE SI LI CONE OIL
HEXANE METHYL SALICYLATE
OCTANE CARBON TETRACHLORIDE
Figure 6. Liquid core materials for encapsulation
431
-------
listing is not complete and many more materials could be added, the
reasons and applications for microencapsulation are many and are limited
only by the imagination. In general, microcapsules are used most advan-
tageously to protect their contents from air, moisture, microorganisms,
and other contaminants. In this way, shelf life is increased and spoilage
reduced. The contents may be released by breaking, crushing, melting, dis-
solving or in some way rupturing the skin. In some cases also the shell
may allow the slow, prolonged release of its contents by diffusion through
the wall, or by decomposition of the wall in certain environments. Certain
other applications may require that the microcapsule contents be retained
permanently within the shell walls; this is also possible. Capsule walls
resistant to acid can be adapted to dissolve and release their contents in
an alkaline environment. Wall materials can be designed to allow the pas-
sage of some materials, while selectively blocking out others. With
CARBONLESS COPYING
DYESTUFFS
ADHESIVES
FERTILIZERS
INSECTICIDES
PESTICIDES
FLAVORS
FRAGRANCES
CLEANERS
VITAMINS
FOOD PRODUCTS
CURING AGENTS FOR RESINS
TOBACCO PRODUCTS
DURABLE-PRESS FABRICS
DENTAL PRODUCTS
PHARMACEUTICALS
ANIMAL FEED SUPPLEMENTS
PAPER MAKING
MEDICINAL PRODUCTS
LIGHT-SENSITIVE
PHOTOGRAPHIC MATERIALS
Figure 7. Applications of microencapsulation technology.
432
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microcapsule applications, if you can visualize it, you can do it!
Some possible applications of microencapsulation technology are shown
in figure 7. Many applications in these areas are aleady in use, many are
in advanced stages of development, and many more will develop in the future.
The technology of encapsulation is surely one of the most exciting develop-
ments of our time, and its fullest potential has yet to be realized.
REQUIREMENTS OF MICROCAPSULES FOR USE IN CARBONLESS COPYING
The encapsulation processes described here were developed principally
for business forms applications which limit the microcapsules1 size to the
1-10 microns range (figure 8). There is no reason why these processes could
not be modified or adapted to produce a larger sized capsule, however. In
all of the processes, the first step is to produce a stable emulsion of the
material to be encapsulated in a continuous phase comprising the film former,
or a component of the film former material capable of forming the shell of
the capsules. It is also desirable to have the microcapsules in the form of
a dry, free-flowing powder for ease and versatility of application to paper
or other substrates. This can generally be achieved with these processes by
spray-drying or by simple filtration and drying in some cases.
Microcapsule Size Range 1-10 microns
Non-Porous Thin Shell
Brittle Shell. Rupturable Under Pressure
Abrasion-Resistant Shell
Shell Inert To Encapsulated Materials
Shell Resistant To Environmental Changes
Biodegradable Shell
Figure 8. Microcapsule requirements for carbonless copying.
433
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The essential characteristic of the film former, of course, is that it
be insoluble in the material to be encapsulated. Also, the capsule wall
should be nonporous, to contain and protect the active capsule contents, and
abrasion resistant, to prevent premature rupture due to incidental scuffing.
A capsule wall having the physical characteristics of an egg shell would be
a fairly ideal structure. The capsule wall should also protect the contents
from environmental factors such as humidity and temperature variations, and
from the possible presence of other reactive or potentially harmful mater-
ials. All of the processes to be discussed encapsulate a liquid core since
this is preferred in copying systems due to its superior pressure transfer
characteristics in comparison with solid or semisol id core materials.
MICROENCAPSULATION USING COACERVATION TECHNIQUES
Coacervation is a phenomenon observed in colloid systems whereby a phase
separation into colloid-rich and colloid-poor layers takes place. It may be
considered as an intermediate stage in the precipitation or flocculation of
the colloid material from solution. Coacervates are colloid-rich solutions
(1).
The phenomenon of coacervation of hydrophilic colloids has been utilized
to produce microcapsules. Oil is first dispersed in small droplets in an
aqueous phase containing the hydrophilic colloid to produce a stable emul-
sion. At this point, the hydrophilic coacervate is caused to deposit around
the individual droplets; later steps dehydrate and harden the coacervate to
form a coherent shell around the droplet.
Figure 9 illustrates the process of encapsulation by simple coacervation
induced by the addition of a salt solution (2). The coacervate layer depo-
sits around the oil droplets as a fairly fragile coating which is then
hardened by pouring the mixture into water at a lower temperature, to gel
and set the colloid. The capsules can then be permanently hardened by a
suitable chemical treatment.
Another technique of encapsulation utilizes a method of complex
coacervation (3). This process makes use of the fact that two hydrophilic
colloids in an aqueous sol develop opposite electric charges at certain
concentration and/or pH, and coacervation takes place. Here again, the
434
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MAKE AN EMULSION OF OIL
AND A GELLABLE COLLOID
AQUEOUS SOL
T
COACERVATE BY ADDITION OF
AN AQUEOUS SALT SOLUTION
STEPS ABOVE THIS LINE PERFORMED AT TEMPERATURE
ABOVE MELTING POINT OF THE COLLOID SOL
GEL THE COLLOID BY POURING
COACERVATE MIXTURE IN COOL
SALT SOLUTION
f
WASH WITH WATER AND FILTER
TO REMOVE THE SALT
HARDEN FILTER CAKE WITH
SOLUTION OF FORMALDEHYDE
IN WATER
WASH WITH WATER AND FILTER
TO REMOVE RESIDUAL FORMAL-
DEHYDE
T
ADJUST WATER CONCENTRATION
TO DESIRED AMOUNT OR FILTER
AND DRY IF DESIRED
Figure 9. Simple coacervation by salt addition.
coacervation is performed at a certain temperature, followed by gellation
at a lower temperature and hardening of the coacervate layer around the oil
droplets. Figure 10 shows a photomicrograph of microcapsules produced by a
coacervation technique and coated on paper.
MICROENCAPSULATION BY AREA-FORMALDEHYDE CONDENSATION
Liquid droplets can be encapsulated within a water-insoluble, nonther-
moplastic synthetic polymer by chemical condensation of a water-soluble
resin from an emulsion continuous phase (see figure 11). The marking fluid
435
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Figure 10. Electron photomicrograph of coacervation
microcapsules coated on paper.
(oil) is emulsified in an urea-formaldehyde solution at room temperature.
The stable emulsion is then acidified and heated to promote the condensation
of the urea-formaldehyde resin material forming a tough, water-insoluble
shell around the emulsion oil droplets. The resultant microcapsule slurry
may then be neutralized and stored; or the capsules separated by filtration
or spray-drying to produce a free-flowing powder (4). A photomicrograph of
capsules prepared by this technique is shown in figure 12.
MICROENCAPSULATION BY INTERFACIAL POLYCONDENSATION
This process (5) makes use of a modification of known interfacial poly-
condensation techniques to produce a thin, high-molecular-weight polymer film
as the capsule shell. These techniques are well described in the literature
references appended to this paper (6-19). Essentially, the process
comprises bringing two reactants together at a reaction interface where
polycondensation occurs virtually instantaneously to form a thin film
436
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UREA-FORMALDEHYDE
RESIN SOLUTION
EMULSIFY. ACIDIFY
AND HEAT
AQUEOUS SUSPENSION OF
ENCAPSULATED MARKING FLUID
SPRAY DRY
FREE FLOWING POWDER OF HARKING FLUID
ENCAPSULATED IN RIGID SHELL
Figure 11. Microcapsule formation by condensation of a water-
soluble resin as emulsion continuous phase around liquid
core droplets, followed by spray-drying.
insoluble in the parent media of the reactants. The polycondensation tech-
nique can produce a capsule shell consisting of high-molecular-weight poly-
mer insoluble in organic solvents and infusible at hot melt coating temper-
atures. A particular advantage of the process also is that it provides a
method of encapsulating water or water-soluble substances. Figure 13 shows
some classes of polymer which can be prepared by this technique and which
have been used in encapsulating a variety of materials.
437
-------
Figure 12. Photomicrograph of urea-formaldehyde microcapsules
prepared by condensation and spray-drying.
The interface for the reaction is provided by emulsifying one react-
ant for the condensation polymer in a continuous phase containing the
second reactant. The substance to be encapsulated will also be contained
in the dispersed phase. However, in order to control the formation of
the capsules, one reactant for the condensation polymer, together with
the substance to be encapsulated, is first emulsified in a continuous
phase, and thereafter an additional continuous phase containing the sec-
ond reactant is added to the emulsion. The polymer shell will then form
at the interface of the dispersed substance and encapsulate the material.
438
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Linking Structure
In Polymer
Reacting Groups In
Intermediates
POLYAH IDE
-N-C-
-N-H
dlamlne
CI-C-
dlcarbony)
chloride,
POLYURETHANE
0
i u
-N-C-O-
-0 -H * 0 :C=N-
blspheno) dl-lsocyanate
MO
POLYSULFONAMIDE -N-S-
0
POLYESTER
0
N
-o-c-
I
-N-M
dfamine
-0-H
blsphenol
Ci-S-
It
0
dlsulfonyl
chloride
Cl-C-
dicarbonyl
chloride
POLYCARBONATE
0
-0-C-O
-0-H
blsphenol
0
CI-C-CI
phosgene
POLYSULFONATE
-0-1-
o
-0-M
blsphenol
0
dlsulfonyl
chloride
Figure 13. Chemical classes of polymers useful in micro-
encapsulation by interfacial polycondensation.
Figure 14 shows the sequence of steps in this encapsulation process. Micro-
capsules prepared by this method are shown in figure 15 as seen through the
microscope. Figure 16 is an electron photomicrograph of the same micro-
capsules coated on a paper substrate.
For pressure-sensitive copying systems, it is desirable to have micro-
capsule walls which are impermeable to the encapsulated solvent. Where
pesticides, fertilizers, perfumes, or other functional ingredients have
been encapsulated, it may be desirable to have a controlled degree of
439
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MARKING FLUID CONTAINING
FIRST REACTANT
EMULSIFIES IN AQUEOUS
SOLUTION
SECOND REACTANT IN
AQUEOUS SOLUTION
AQUEOUS SUSPENSION OF ENCAPSULATED
MARKING FLUID
SPRAY DRY
FREE FLOWING POWDER OF MARKING FLUID
ENCAPSULATED IN POLYMER SHELL •
Figure 14. Microcapsule formation by
interfacial polycondensation.
porosity or permeability in the capsule walls to allow the slow release of
the encapsulated materials. The versatility of this process allows such
control over the final product. For example, experiments in our labora-
tories have shown that encapsulated volatile solvents such as toluene and
xylene can be contained without measurable loss at temperatures close to
their boiling points for periods in excess of 24 hours. Alternatively,
the capsules can be designed to lose 10 percent, 20 percent, 30 percent or
more of encapsulated ingredient under the same conditions and over the
440
-------
8>
Figure 15. Photomicrograph of interfacial polycondensation microcapsules
Figure 16. Electron photomicrograph of interfacial poly-
condensation microcapsules coated on paper.
441
-------
80-
Figure 17. Loss of xylene from interfacial microcapsules at 110° C.
same time period. Figure 17 shows data obtained by this technique indi-
cating the control that can be exercised over the capsule wall permeabil-
ity.
The efficiency of encapsulation is measured by determining the
amount of unencapsulated or "free" solvent. The free solvent is extracted
from the capsule slurry by mixing it with an inert extracting solvent. The
quantity of free solvent in the extracting medium is then measured by either
gas or liquid chromatographic techniques. The total solvent in the system
is determined by extracting the capsule slurry with a reactive agent, which
will remove the solvent through the capsule walls. The amount of total
solvent is also determined by gas or liquid chromatography. The ratio of
free solvent to-total solvent is the percent of free solvent and a measure
of the encapsulation efficiency. The polycondensation process can be con-
trolled at an encapsulation efficiency of at least 98 percent quite readily.
442
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Water can also be encapsulated by this process. In one technique, a
solution of one reactant in water can be extruded into a solution of the
second reactant for the condensation polymer in a water-immiscible solvent,
forming small droplets of water within the solution and instantaneously
encasing them in a polymer skin that forms at the interface. A second
technique consists of forming a water-in-oil emulsion or dispersion and
thereafter adding a solution of the second reactant in oil. The reaction
at the interface will encase the water within a polymer shell.
It is interesting to note that microencapsulation can be effected by
this technique so as to yield capsule walls which may be safely ingested.
Recently, pesticides encapsulated by this technique have been approved by
the Environmental Protection Agency for first commercial marketing (ref. 20),
The microcapsules were approved for use on cotton, alfalfa, and corn, and
provide slow, controlled release of pesticide by diffusion through the
capsule walls. This approach offers safer, more efficient, more economi-
cal, and more controlled use of pesticides.
DUAL-WALLED MICROCAPSULES
Dual-walled microcapsules, in which the wall or shell is constructed
of two thicknesses of material, usually of different chemical constitution,
have been prepared in several different ways. In all of these methods,
however, the techniques for forming the individual walls are essentially
separate and independent from one another. The processes consist of
superimposing one distinct wall-forming process upon the product of another
wall-forming process, each process requiring control of reaction conditions
with little or no relation to the requirements of the other.
The unique feature of this process (ref. 19) of forming dual-walled
microcapsules is that the technique for producing the inner wall of the
microcapsule automatically initiates the process for forming the outer
wall. In the first stage of the process, a proteinaceous film former is
deposited from an aqueous solution around core droplets on nonaqueous sol-
vent in an emulsion as the result of a reaction with a protein-insolubiliz-
ing reactant in the core droplets. Acid is released as a byproduct of
this reaction, lowering the pH of the aqueous emulsion phase. A second
hydrophilic colloid in the aqueous phase then undergoes coacervation with
443
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the remaining proteinaceous colloid upon reduction of pH to within a pre-
determined range, and thus an outer skin is formed on top of the first.
This complex coacervation mechanism was discussed earlier and is well
documented in the patent literature and elsewhere (refs. 1,3).
The procedural steps for making dual-walled microcapsules by this
method are shown in figure 18. Following the emulsification step, a thin
film or skin can be observed around each droplet on microscopic examina-
tion. When a sample of these droplets containing mineral oil, for example,
is air-dried on a microscope slide and immersed in toluene, little or no
oil is extracted. This confirms that the inner wall has formed as an
impermeable layer around the oil droplets. When the product after the
HARKING FLUID CONTAINING
FIRST REACTANT
AQUEOUS SOLUTION OF TWO
I ON IZABLE COLLOIDS
INTERFACIAL FILM AROUND HARKING
FLUID DROPLETS
COACERVATE LAYER AROUND INTERFACIAL FILM
SPRAY DRY
DRY. FREE FLOWING POWDER OF DUAL
WALLED HICROCAPSULES CONTAINING MARKING FLUID
Figure 18. Dual-wall microcapsule formation.
444
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cooling steps of the process is examined microscopically, the formation
of the second wall layer can be seen. This wall has a considerably
greater thickness than the inner wall and is gelatinous in appearancer-
it can readily be distinguished from the inner wall under the microscope.
Samples of such microcapsules containing mineral oil have been immersed
in hot toluene for up to 2 hours; the washed samples released copious
quantities of oil under pressure. Also, similar microcapsules can con-
tain xylene at temperatures close to its boiling point without appre-
ciable loss. Figure 19 shows single-walled microcapsules after the
first shell-forming reaction, and dual-walled microcapsules after the
coacervation step.
o
9 '
(a) Single wall.
(b) Dual wall.
Figure 19.
Single-walled microcapsules after the first she11-forming
reaction (a), and dual-walled microcapsules after the
coacervation step (b).
445
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REFERENCES
1. J. E. Vandegaer, "Microencapsulation - Processes & Applications,"
Plenum Press, p. 21 et seq.
2. B. K. Green, U.S. Patent Reissue 24,889.
3. B. K. Green and L. Schleicher, U.S. Patent 2,800,457.
4. N. Macaulay, U.S. Patent 3,016,308.
5. H. Ruus, U.S. Patent 3,429,827.
6. P. W. Morgan, Soc. of Plastics Engineers J., Vol. 15 (1959), p. 485.
7. E. L. Wittbecker and P. W. Morgan, J. Polymer Sci., Vol. 40 (1959),
p. 289.
8. P. W. Morgan and S. L. Kwolek, J. Polymer Sci.. Vol. 40 (1959), p. 289.
9. R. G. Beaman, P. W. Morgan, C. R. Koller, E. L. Wittbecker, and
E. E. Magat, J. Polymer Sci., Vol. 40 (1959), p. 329.
10. M. Katz, J. Polymer Sci., Vol. 40 (1959), p. 337.
11. V. E. Shashoua and W. E. Eareckson, J. Polymer Sci.. Vol. 40 (1959),
p. 343.
12. C. W. Stephens, J. Polymer Sci., Vol. 40 (1959), p. 359.
13. E. L. Wittbecker and M. Katz, J. Polymer Sci., Vol. 40 (1959), p. 367.
14. J. R. Schaefgen, F. M. Koontz, and R. F. Tietz, J. Polymer Sci.,
Vol. 40 (1959), p. 377.
15. S. A. Sundet, W. A. Murphey, and S. B. Speck, J. Polymer Sci., Vol. 40
(1959), p. 389.
16. W. E. Eareckson, J. Polymer Sci., Vol. 40 (1959), p. 399.
17. D. J. Lyman and S. Lup Jung, J. Polymer Sci., Vol. 40 (1959), p. 407.
18. P. W. Morgan and S. L. Kwolek, J. Polymer Sci.. Vol. 62 (1962), p. 33.
19. G. Baxter, U.S. Patent 3,578,605.
20. Chemical & Engineering News, July 29, 1974, p. 15.
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SESSION SUMMATION
Robert H. Downie
Session Chairman
I think what you have heard today illustrates a number of things. I
think you have gained an insight into the developmental cycle of some proc-
esses that are going on in the graphic arts and some understanding and ap-
preciation of the painstaking step-by-step compromises that have to be made.
We have illustrated among ourselves the healthy competition of tech-
nologies and the range of options open to us. We have described some meth-
ods that we are using to tackle the problems that are raised by the environ-
ment. Also illustrated were the agonies of the trading of properties that
go on. One aspect that possibly was not evidenced was that the cost of de-
velopment described in these four papers, when added together, has to be in
excess of $25 million. The level of activity has been impressive. It al-
ways impresses me that the pressure from the marketplace has often run far
ahead of any pressure that we get from any other source. A lot that you
fellows talk to us about, and one of the understandable agitations we get,
is that we often feel as though you're teaching your granny how to suck eggs.
We do appreciate the role and the task that we all have. We are apply-
ing ourselves most diligently to tackling it. I work very diligently with
the Environmental Conservation Board of the Graphic Arts, which is a group
of large printers who got together to work in tackling our problems with
the environment. I happened to chair the OSHA committee of that Environ-
mental Conservation Board, and I have been very gratified at the progress
and the accomplishment that we have had in 2 brief years, with volunteers on
that committee meeting once every 2 months. A little thing that came back
to me was that if a first-rate company has a first-rate insurance company
monitoring what it is doing, it is awfully close to doing what OSHA requires
and OSHA regulations are no great problem to meet. I am comforted that,
as we come to appreciate each other's viewpoint and start to get a hands-on
relationship with problems, many of the seeming ideological or practical
differences will disappear.
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24 September 1975
Conference Summation
Farley Fisher, Ph.D.
General Chairman
448
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CONFERENCE SUMMATION
Farley Fisher, Ph.D.
General Chairman
This concludes our conference. I hope you have all learned something:
maybe not as much as I have, but I hope you have all found it profitable.
Before we close, I would like to express my appreciation to our four
session chairmen: Dr. Burachinsky, Dr. Schaeffer, Mr. King, and Mr. Downie;
and to our roster of speakers who I think have done a very nice job of
presenting us with an awful lot of material. I would also like to thank all
of you who attended, who participated from the floor, asked questions, and
made comments. I would like to thank the staff of the Holiday Inn, Valley
Forge, for their cooperation and the facilities they provided us, and the
Montgomery County Convention and Visitors Bureau for their assistance in
manning the registration desk and helping some of us out with some arrange-
ments. I owe thanks to a few organizations who gave us considerable assist-
ance in putting this program together: the Graphic Arts Technical Foundation,
the Gravure Research Institute, the Association of Photographic Manufacturers,
the National Association of Printing Ink Manufacturers, and the Printing
Industries of America.
At this point, I am supposed to give some general summation and impres-
sions from the conference. This is always very embarrassing because, I am
told that I am to summarize a conference, but I am not to say anything that
might be interpreted as a government policy. So, I have to make that caveat
and say that I am speaking for myself. I am not the kind of person who can
sit here for 2-1/2 days and immediately have everything figured out and know
exactly what it all means. I have to go home and sit down with the record
and think about a lot of the things I have heard.
I do have just a couple general impressions that I will share with you.
One is that I really have the impression, Dr. Muggli's comment notwithstand-
ing, of an industry which, at least on the surface, is really quite innova-
tive. It is not an industry that is opposed to new techniques and new ways
of doing things. This impresses me because I know of a lot of industries of
449
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which that simply is not true. I think that this innovation holds out a very
great promise, but we have to remember it also carries with it an attendant
risk. This is true environmentally as well as economically. Every new
advance is somewhat untried. No matter how much we worry about it, no matter
how much we test it out beforehand, no matter how much thought and commisera-
tion and debate we have, whenever something new really comes into use we find
out things about it we just did not know before.
And so we do have to keep our guard up. We do have to take all the
care we can. And we really have to trust a little bit to luck if we are
going to improve, to make a better future and not a poorer future for our-
selves and the people who follow us.
I also have the feeling that the industry is at least aware of some of
its problems, and those it is aware of, it is making a serious attempt to
deal with.
It is also very instructive that we have learned that people who made
environmental improvements as recently as 5 years ago, despite the advice of
their bankers that it was a waste of money, have found themselves coming
out smelling very nice in the money market. This tells us something that
I think any third grader knows but which we tend to forget when we grow up;
namely, that waste is waste.
All this stuff that EPA, the various States, and other people are com-
plaining about dumping in the environment because they don't like it there
is in many cases useful stuff. Throwing it away is just not a commonsense
thing to do. We have to make an effort. After all, the best way to deal
with waste is to realize that it need not be a waste, that maybe it is a
useful commodity in its own right. I think we have seen some very good
examples of that here, and I hope that we can keep on moving in this
direction.
I've probably said enough for the time being. Before I adjourn the
meeting, however, I would like to open it up for comments from the floor for
one last time, in case anybody does have something they have not had a
chance to say up to now.
MR. FREDERICK WOOTTON (Prince George's County Health Department, Cheverly,
Maryland): I have sat here for 2-1/2 days and have enjoyed it. I
don't know if I really have enough information to put out. Sixty-five
450
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percent of all your taxes are going to the military. I should point
out that, being a health person, I believe that possibly we could
divert some of these funds to some of the research that you all have
said has cost you so much.
MR. DAVID FRIEDMAN (Food and Drug Administration, Washington, D.C.): We
have heard several comments by some speakers that there is an adversary
atmosphere between industry and the various government agencies, and
that there should be more cooperation. I want to suggest to everyone
that the relationship need not be antagonistic; we are not out to "get"
anyone. If industry and trade organizations would cooperate, would
give us the information we need—before new developments are in progress,
when new techniques are being developed—if they would work with the
various environmentally active agencies, industry might be able to find
out what not to do. It is a lot easier to reformulate before environ-
mental damage, or before commitment in the marketplace, than it is
afterwards. We are out to try to prevent problems, and not simply
deal with them once they are known to exist.
MR. THEOPHILUS R. CARSON (Food and Drug Administration, Washington, D.C.):
I would like to commend Dr. Fisher and Mr. Ayer for the wonderful job
they did in getting this together as fast as they did. I had to take
someone else's place; that is why I am here.
MR. AL JASSER (Anchor Chemical Company, Hicksvilie, New York): I want to
commend you, Dr. Fisher, for the conference. I have one plea from
industry. The problem you have stated at another time was that there
is no communication. This young man from FDA again repeated that there
should be cooperation. Industry is always willing to cooperate with
government if it can understand what government wants. If the language
in the Federal Register, for example, were such that my staff could
understand it without lengthy conferences, we would be well along in
the way of cooperation. We are very happy to cooperate. Is there
something that you can do in seeing to it that the directives, orders
and prospective regulations are in clear, simple language so that we in
business don't have to take a special course?
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GENERAL CHAIRMAN FISHER: I would point out to you, first off, that I am a
chemist myself; most of the government people here, I imagine, are
technical people of one type or another. Most of the industrial people
here, I imagine, are technical people of one type or another—engineers,
chemists, and so on. But the fact of the matter is that the government
is run by lawyers. They write the Federal Register. Business is not
really run by scientists and engineers either. Business is run by
businessmen. I think all we can really strive to do is maintain communi-
cation at the technical level so that we at least know what we are
supposed to be doing. I know it's just a plain fact of life that when
you get into the higher levels of management in either government or
industry, a lot of information can get obscured.
I would like to make one more comment which I have heard made
privately on a number of occasions. Dr. Schaeffer and I have discussed
it at some length. That is, many of these engineering advances that
we have heard discussed here, many of the fancy pollution control
devices, are really practical only in large installations. But, in
fact, we are dealing with an industry which has an awful lot of small
installations. In a sense, we have been a little unfair, because I
really do not think we have.,addressed the problems of these small opera-
tors. Many of the things which we did discuss are not practical from
their point of view. I think that is an area which requires more
thought and a little more effort.
If there are no further comments, I will call the meeting
adjourned. I want to thank you all for your cooperation and attendance.
452
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Submitted Papers —
Not Presented at Conference
453
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COMMENTS FROM A SCREEN PRINTING INK AND PRESSURE-SENSITIVE-FILM
MANUFACTURER: GENERAL FORMULATIONS - DIVISION OF GENERAL RESEARCH
John H. Sommer*
Screen printing owes its existence to three qualities lacking in
most other methods:
1. inexpensive short runs,
2. bright sharp colors, and
3. durable or long-lived printing for outdoor exposure.
Screen printers, and their end products to a significant extent, are differ-
ent from the other branches of the printing industry. The printers them-
selves differ in that the vast majority of them operate very small shops
with limited facilities. It is not too costly to get into the screen print-
ing business. The end products are very often used in outdoor applications
requiring relatively long life and, not infrequently, exposure to a variety
of chemicals or corrosive conditions. Therefore, it is important to screen
printers that they have outdoor-durable inks. This ultimately means to
exclude, for examples, cadmium and lead chromate pigments. This in turn
makes it difficult for the screen printer to supply durable name-plates,
direction labels, and emblems. Less durable but so-called innocuous pig-:
ments could be used by overlaying the printing with a clear protective
film. This is already being done to extend the life of emblems made with
durable pigments. However, very few shops have the overlaying equipment,
and overlaying makes a more expensive emblem and consumes more material.
Outdoor-durable screen printing inks very often necessitate solvents
for vehicle systems that aid in making durable signs. These may have low
MAC values and/or may be excluded on the Rule 66 basis. Ultimately, the
inkmaker is limited to what the pigment, resin, and solvent producers supply
to him, and even if rectified products from these producers are forthcoming,
the inkmaker still has left the recompounding or formulating of ink systems
and weathering tests, which is time consuming.
*Division Vice President of General Formulations Company, Division of
General Research, Inc., Sparta, Michigan.
454
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But what is a rectified ink—an ink that is logically considered safe?
As quantitative data are gathered on toxicity at all levels, what are the
parameters that determine acceptability? With all the logic and morality in
the world, we need facts in order to make a judgment that it is more important
to eliminate cadmium and lead chromate pigments from the world than to dis-
allow motorcycles and cars to be driven, or bathtubs to be used, or alcohol
to be ingested, at least in excess.
I realize that it is the proper function of the Office of Toxic Sub-
stances of EPA to make inquiries. Along with State-related departments, it
has already done and is doing, in general, a good job in having industry
clean up its act, and it is delving further. I do think, though, that no
one, Including EPA, wants safety to reach its logical conclusion, which
would be to stay in bed and reach out for food as needed. So you come to
the horns of a dilemma. At what point do we say we will allow a certain
percent of all living plant and animal life to die from what we call, for
want of better terminology, an abnormal death or disability? Indeed, what
is normal death? I ask this because when most of us hear of the death
of someone we know, we often say, "Well, that person did this or that which
contributed to his or her demise." What is the virtue of doubling our life
spans when we are rapidly overcrowding the earth? My point is that in our
society, we do allow people to conduct themselves in ways that consciously
or subconsciously determine their own ends. This is the free enterprise
system and if you do not like that terminology, then it is a "free democratic
society." It is, however, our duty as member of so-called scientific, in-
dustrial, political, and educational societies to apprise people of their
options and in as quantitative a way as possible indicate to them their chances
of survival upon being exposed to this or that environment.
This precipitates the thought that life and living are horribly compli-
cated and that a person, upon being apprised of his options, will most cer-
tainly proceed to other options—ad infinitum.
Our society is torn in several directions: 1) We are told we must con-
serve energy; 2) We are told to, and indeed, we wish to maintain or increase
our well-being in terms of material goods and our health; 3) We are told and
shown that our morality and ethics need improvement at all strata of society;
4) We are told also that we must not pollute. Our society is frustrated.
We feel rotten about it. What do we do?
455
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Nothing will be solved overnight, but it would appear that inasmuch as
we do allow our fellow man to shorten his life in so many ways, it should
follow that all the experts should do is advise people, as we gain knowledge,
to allow them to choose their options, and, in dangerous situations in-
stitute an enforceable cessation of exposure.
Philosophers and/or religious leaders have not been very effective in
guiding our lives to a high moral and ethical plane and certainly the politi-
cal arena has not helped, nor apparently have the educators. It follows,
therefore, that science and industry should show a selfless consciousness
in upgrading the morality and ethics of our society. This does not necessari-
ly mean we should eliminate cadmium and lead chromate pigments (again only
as examples). We should join all forces in society and evaluate priorities
based on their relative effects in a rational, logical manner devoid of
self-interests. Then if a segment of industry suddenly becomes mortally
wounded (we must admit past mistakes), that segment should be helped to
rally and redirect its energies. If we do not do this, it will be a parry-
and-thrust process of fighting for self-interests and we shall continue
to fight each other, in a sophisticated way of course, but in a way not at
all dissimilar to the cavemen. Science and industry need a new image, and
what better way of achieving this image than a sincere show of altruism for
mankind.
I do not think the above has been a digression from the agenda of this
meeting. Rather it is a beseeching to EPA that as individuals of professions
and as members of society we be given the full overview of environmental
protection and what needs to be done first, second, etc. We are reasonable
people and, like anyone else, upon being shown the light and being assured
of no calamitous result to our workers and our companies, we will proceed in
an effective way to accomplish what needs to be accomplished.
It is understood, of course, that the protection of the environment
(and mankind by inference) can and should be pursued in more than one area,
and I still refer to cars, motorcycles, etc., as polluters, killers, and
extravagant wastes of natural resources. I may be wrong, but they do make
a potential ban of lead chromate a little ridiculous.
Science and industry have eliminated many problems of environmental
pollution and in the process have created new ones. For example, the
transition from coal-operated engines and horse-drawn vehicles to internal
456
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combustion engine vehicles was a remarkable and revolutionary accomplishment
but virtually devoid of environmental considerations.
Now, however, pollution potential or consequences are considered and
it follows as night does the day that science and industry will consider the
environment as a new component to be dealt with in technological advancement.
Many of us have already upgraded our plants in terms of cleaner air
and lower noise levels. More is being done, but it costs money, and in a
competitive society it can only proceed to the extent that competition dic-
tates the amount of money available from profit. At the present time there
is a squeeze that makes improvement difficult or minimal, and in many cases
financially impossible. In fact, the impact of more and more restrictions
makes it increasingly difficult for small businesses to start, and indeed
for existing small businesses to continue.
In summing up our attitude, I would suggest the following approach to
environmental protection as our industry affects it.
1. Assemble facts regarding mortality and injury rate per degree of
exposure to each substance. Evaluate these in the full overview
of protection priorities. Publish the information and above all
make it readily available. To do this, prepare a confidential,
not-to-be-signed questionnaire for each segment of the printing
industry and for individual manufacturers. Ask them what solvents,
pigments, monomers, and additives are used and what problems are
encountered. Every manufacturer feels he has secret formulations
and/or processes that he wants kept secret—whether this is right
or wrong—and he wants any problems minimized.
2. If hard facts or conclusive ones are not truly convincing or avail-
able, then on an interim basis require raw material suppliers and
ink manufacturers to list potential hazardous substances, or, do
what is required of the tobacco industry: publish a disclaimer
saying, "The use of this product may be hazardous to your health."
This, of course, is being done, but it can be more complete.
Obviously, this later approach is ineffective in stopping pro-
duction of a product, but the comment does give the individual a
warning and the option of not using it.
3. If conclusive facts are ava^able and condemning, then by, all means
consider the problems facing the producer and user in confronting
457
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the cease-and-desist order and assure them of aid in the transi-
tion, both technologically and economically. It is this unknown
that puts us on the defensive—rightly or wrongly, this is a
point that cannot be over-stressed. Asking for governmental aid
is an anathema to most of us, but if our processes and procedures
are interfered with, it is a reasonable socialistic request to
keep the system viable.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/1-75-005
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
CONDUCTING CONFERENCES ON ENVIRONMENTAL ASPECTS OF
CHEMICAL USE IN VARIOUS INDUSTRIAL OPERATIONS. Environ
mental Aspects of Chemical Use in Printing Operations
5. REPORT DATE
January 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8 PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Center for Technology Applications
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina
10. PBOGHAM ELEMENT NO.
2 LA 3 28
27709
11. CONTRACT/GRANT NO.
68-01-2928
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
Environmental Protection Agency
Room 715, East Tower (WH-557)
401 "M" Street, S.W., Washington, D. C.
13. TYPE OF REPORT AND PERIOD COVERED
Proceedings. Sept. 21-23, 1975
14. SPONSORING AGENCY CODE
20460
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This conference was the last in a series of three on the environmental
impact of chemicals in various industrial operations.
The objective of this conference was to cover and discuss current
chemical use, functions of chemicals in the operations, byproducts likely
to be introduced, known health or environmental contamination. More
specifically, papers were presented and discussions held that covered
industrial emissions and effluent surveys, chemicals and their effects,
reclamation and disposal and academic programs.
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