United States
                    Environmental Protection
                    Agency
Industrial Environmental
Research Laboratory
Cincinnati OH 45268
                               •/ V \'
                   Research and Development
EPA-600/S2-84-120 Aug. 1984
&ERA         Project  Summary
                   Paper Production  and
                   Processing—Occupational
                   Exposure and  Environmental
                   Release  Study
                    Robert Soklow
                     This report presents an analysis of
                    chemicals and processes used during
                    the production and processing of paper
                    and paper goods with emphasis on the
                    workplace exposure and environmental
                    release  of   chemicals  from  these
                    operations. Reviews of chemical sub-
                    stances in the report are intended for
                    use in developing realistic exposure and
                    release scenarios associated with the
                    review of new chemical substances
                    used in the industry.
                     In this report, a  description of the
                    industry is presented along with profiles
                    of  the various process subcategories
                    occurring in the industry. A literature
                    search and discussions with know-
                    ledgeable persons in the industry during
                    the development of  the report  have
                    been  aimed at developing process
                    descriptions that address occupational
                    exposures to workers,  as well  as
                    information on the concentration of the
                    release of chemicals to the environment.
                    Process characteristics for each study
                    area,  including  raw  materials and
                    chemicals used, are  presented along
                    with the description of chemicals in
                    wastestreams and  other effluent
                    characteristics. Discussion of waste
                    control  and treatment  technologies
                    used throughout the industry are also
                    presented. The sources, effects and
                    control  of worker exposure  to
                    chemicals are described on an industry-
                    wide basis.  Specific case studies have
                    also been reviewed to  address detail
                    information on occupational exposures
                    to  workers  (including the number of
                    workers involved, duration of exposure,
                    and workplace concentrations).
  This Project Summary was developed
by EPA's Industrial Environmental Re-
search Laboratory. Cincinnati. OH, to
announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).

Introduction
  The full report presents the results of a
study to characterize the chemicals and
processes used during the production of
paper and paper goods, with emphasis on
work place exposure and environmental
release  from these  operations.  This
information will assist in the U.S. Environ-
mental   Protection  Agency's  (EPA's)
review of Premanufacture Notices (PMN)
under the Toxic Substances Control Act
(PL94-469).  PMN  review includes  a
review of exposure to humans and to the
environment during the manufacturing
and processing of chemicals.
  For this study, the pulp and paper
industry has been described in terms of
this industry's major  processing
technologies.  This  division of
technologies is based on the definition of
the paper industry as presented in recent
EPA studies to develop effluent limitation
guidelines and new source performance
standards,  and  to  analyze  related
economic impacts. For  this  study,
subcategories established by EPA have
been further grouped into study areas
best suited to  the organization of the
investigation of  process  and waste
chemicals.
  General crewing and exposure
patterns  in  each  study area   were

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developed  during this study  from  a
National Institute for Occupational Safety
and Health (NIOSH) project conducted to
survey, evaluate  and document worker
exposure to toxic chemicals and harmful
physical stresses and related controls to
exposure  used in the pulp and  paper
industry.  Detailed exposure  scenarios
were also  developed during this study
from case studies which review the most
documented   occurrences  of  worker
exposures  to specific chemicals and
associated processes. These exposure
scenarios provide detailed information on
the process  characteristics, number of
workers and their activities associated
with  the  process  and  associated
chemicals  and  the   concentrations  of
these chemicals that are likely to occur in
the work place during operator activities.
Since  the  case  studies presented may
serve to supplement  the approach taken
to  establish general  crewing and
exposure  patterns, the reader  is often
referred to  appropriate  case  studies
during discussions on the development of
general crewing and exposure patterns.
  Additional  information was obtained
from NIOSH and the Occupational Safety
and Health Administration (OSHA) for a
broad review of the sources and extent to
which workers are exposed to specific
chemicals. The review includes a listing of
•known carcinogens  to which  workers
 may be exposed and information on
accidents and fatalities due to chemical
hazards and acute exposures as well as a
description of human factors contributing
to such chemical hazards.
  Of the various sources  of data used to
identify process and waste chemicals, the
 most  comprehensive is  the   NIOSH
 National  Occupational Hazard  Survey
(NOHS) database for pulp and paper mills.
To  establish this database, NIOSH made
visits to many facilities throughout  the
industry  where  over  800  chemical
agents were identified and related to the
various production  and  manufacturing
operations  and  associated  worker
occupations.
  Each chemical identified during this
project is  presented in  the  Chemical
Profiles (Appendix A  of the full report)
along  with  pertinent information
summarizing discussions in the text as
well  as   other information   which
characterizes  the  chemical.  This
information includes its occurrence in the
industry as a use or waste chemical, its
description and physical properties, per-
missable air  and water concentrations,
synonyms and health effects and safety
data for those chemicals known  to be
 hazardous to workers. For many of these
 chemicals, additional discussion on their
 occurrence   throughout  the   industry
 and/or health effects is presented in the
 main body of the text.
  To acquaint the reader with general
 aspects of the pulp and  paper industry,
 the full report presents a brief overview of
 this industry's technology,  production,
 economics  and  projected growth,  and
 presents  a  definition of  product sector
 divisions  which  are  based  on  grade
 descriptions defined by the American
 Paper Institute.

 Discussion
  In the full report, an industry descrip-
 tion is presented in  Section 3 which
 consists of  a brief overview of the pulp
 and paper industry's technology, produc-
 tion, economics and projected growth. An
 operations  analysis   is  presented  in
 Sections  4 and  5  for pulping  and
 papermaking,  respectively.  These
 analyses include a description of process
 equipment, raw materials, and process
 chemicals, including water consumption
 and other operating characteristics. The
 analyses  include  a  description of the
 environmental  release   of   chemical
 pollutants including an identification of
 chemical  by-products  and  effluent
 characteristics. Occupational exposure is
 discussed in Section  6 for the sources,
 effects and control of exposure on an
 industry-wide basis. In addition, a review
 of  previous case  studies  and general
 crewing and exposure patterns investi-
 gates  specific  occupational  exposure
 problems.   In  Appendix A,  chemical
 profiles are presented for process and
 waste chemical species identified in Sec-
 tions 4, 5, and 6. In Appendix 6, process
 control measures used to reduce waste
'loads  and improve process efficiencies
 are  discussed. In  Appendix C, specific
 waste treatment technologies used to*
 treat  'end of the pipe' effluents are
 discussed. A copy of  OSHA regulations •
 governing pulp and paper mills (29 CFR
 1910.261) is presented  in Appendix D.
 The full report also includes a glossary of
 terms commonly used throughout the
 text.
  For  many papermaking process and
 waste chemicals, a qualitative and quan-
 titative description  of their occurrence
 throughout the industry  is presented in
 the main body of the text and is based on
 the nature and limitations of information
 made  available  in  the literature.  Each
 chemical identified during this research is
 again  presented in the Chemical Profiles
 (Appendix A of the full report) along with
pertinent  information  summarizing  ^
discussions in the text as well as other
information  which  characterizes  the
chemical. In Appendix A of the full report
and throughout the text,  environmental
and  toxicity  data  are  not  emphasized;
rather,  scientific  criteria  from  which
impacts  can  be  determined   are
emphasized.   For  each   chemical  in
Appendix A of the full report, available
data  have been used  to profile  a
chemical's  occurrence in the industry as
a use or waste chemical, its description
and physical properties, permissable air
and water concentrations,  and synonyms.
For those chemical species known to be
hazardous to workers, additional items of
information profiled  include symptoms,
target organs, routes of entry, protective
equipment, respirator requirements, first
aid and medical  surveillance, as well as
any  appropriate information on  leaks,
spills and waste  disposal.
  For  many  chemicals   identified  as
significant   in  terms  of  occupational
exposure, additional  discussion of  their
health effects to workers  is presented in
Section 6 of the full report. The selection
of chemicals  for which  this additional
discussion   is presented  is  based on
several criteria. Many of these chemicals  ^
may be considered  potential  hazards  fl
because of their  known toxic effects and
the  existence  of  Federal  standards
limiting work place exposure,  including
recommended  NIOSH and  American
Conference of Governmental Industrial
Hygienists  (ACGIH) exposure levels. The
health effects of  other  chemicals are
discussed because of their wide-spread
occurrence  throughout   industry  in
general,  and  because of the  resulting
actual  or  anticipated chronic  worker
exposure. Some  of these  chemicals may
not produce specific toxic effects but may
be considered potentially  hazardous due
to  their  ability   to  produce  allergic
reactions  or due  to their  possible
presence in the workplace  as respirable
dusts.  In  the full  report. Section  6
discussions are, therefore, intended to
expound the identification  of  health
effects  of  selected  chemical  agents
presented in Appendix A.
  To  supplement  the development of
general crewing and exposure patterns,
detailed  exposure  scenarios  were
developed  during this study from  case
studies which review the most documen-
ted occurrences  of worker  exposures to
specific chemicals and associated
processes. The case studies are based on
Health Hazard Evaluation (HHE)  reports  ^
developed   by  NIOSH   which   were  ^

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performed following written requests by
employers or employee representatives
to  NIOSH  to  investigate  specific
occupational  exposure problems.  The
HHE  investigations  are  aimed  at
components of processes  suspected of
localized impacts to workers. One such
HHE,  for example,  addresses worker
exposure hazards at the paper coating
preparation station  of a printing paper
production process. The general crewing
and exposure patterns and case studies
provide   detailed  information  on  the
process  characteristics,   number  of
workers  and their  activities associated
with the process and associated chemi-
cals  and the  concentrations  of these
chemicals that are  likely to occur in the
workplace  during   operator  activities.
Environmental monitoring  data is often
used to quantify the findings. In addition,
the  use or  misuse  of  protective
equipment,  engineering  controls  and
procedures  typically  used   to  limit
exposure are described. Most of the case
studies   include medical  histories of
worker health  problems associated with
each process.
  Since the detailed exposure scenarios
developed in this study account for only
segments  of  the  paper   industry,
additional information has been obtained
from NfOSH and OSHAfora broad review
of the  sources  and  extent  to  which
workers  are  exposed  to  specific
chemicals and other significant material
agents. This broad review includes a list-
ing of  known carcinogens  to  which
workers may be exposed and the identifi-
cation of specific occupations  involving
exposure to these chemicals. A broad
review of accidents and fatalities due to
chemical hazards and acute exposures is
also derived from NIOSH and OSHA liter-
ature and includes a  description of
human   factors  contributing  to  such
chemical hazards.
  In the full report, specific aspects of the
environmental release of chemicals are
addressed in discussions on occupational
exposure  (Section  6).  A  general
description of the environmental release
of chemicals is presented in Sections 4
and 5 in terms of  the paper industry's
major  processing   technologies.  This
division of technologies is  based on the
definition of  the   paper  industry  as
presented in  recent EPA  studies to
develop effluent limitation guidelines and
new source performance standards, and
to analyze related  economic  impacts.
These studies are based on the process
subcategories  of the pulp,  paper  and
paperboard industry as established in 40
CFR, Part 430, by grouping mills which
employ  similar production and process
techniques.  Such a grouping has been
established  so that  EPA can develop
uniform national effluent limitations and
standards which would  affect similar
mills in  a similar  fashion  in terms of
modifications required and costs incurred.
For this study, subcategories established
by EPA  have been further grouped into
study  areas  best  suited  to  the
organization of this study's investigation
of process and waste chemicals. To make
such a grouping, attention has been given
to similarities and dissimilarities in pro-
cess components (stages) occurring
throughout the various subcategories. In
this regard, consideration has been given
to significant  variations  in  materials
used, wastes created and other process
characteristics.
  For each study area, a generic process
flow diagram  has been developed to
illustrate overall  process characteristics.
With each flow diagram, a set of tables
has  been developed  to  characterize
process   and  waste  chemicals  and
materials,  effluent  conditions  and
process   control  technologies  used
throughout  the  process.  All process
components listed within the prescribed
formats of these tables are shown on the
flow diagram  in the full  report. The
generic flow diagram and corresponding
table sets serve  to develop a context in
which  detailed profiles  of  the product
processes are illustrated.
  For each study area,  internal process
control technologies  are itemized and
illustrated on the process flow diagram.
These  technologies  which  are  also
discussed in Appendix B of the full report,
are  commonly  employed  within the
industry  to  control pulping, bleaching,
washing, liquor recovery and papermak:
ing operations. Their occurrences and'
general effectiveness as described in this
report have been  identified in various
effluent  limitations  development
documents.
  For each study area, the investigation
of  effluent  BOD,   TSS,  and   other
conventional,  nonconventional,   toxic,
and  priority pollutants  occurring  as
multimedia emissions, includes efforts to
quantify these materials in process waste
streams.   A  discussion   of  effluent
characteristics is presented to illustrate
the relative  and  qualitative relationship
between BOD  and  TSS  and  the
occurrences  of  associated waste
chemicals. Chemicals are listed  which
are generated (pollutants, by-products) by
the process, as well as those which are
used by the process. The effectiveness of
external waste treatment to reduce the
final  concentrations  of chemicals  in
effluent streams is addressed in the full
report (Sections 4 and 5 and Appendix C).
Appendix C discusses effluent treatment
technologies  and  describes the  many
types of wastewater treatment systems
used   throughout   the  industry  and
presents examples  of  existing
commercial applications as well as pilot-
scale case studies.

Conclusions and
Recommendations
  Of  the  many chemicals used  and
released during pulp and paper process-
ing, some are important in terms of both
occupational exposure (as process and
waste chemicals) and environmental
release (emission, effluent and solid
waste chemicals). However, many chem-
icals are known to  be significant in only
one of these areas.
  Among the chemicals released to the
environment,   many toxic,  nonconven-
tional and priority pollutants have been
identified  in  pulp  and paper industry
discharge  waters.  Their  occurrences
throughout  the  industry  have  been
reviewed in the full report. This review
includes  discussions   illustrating  the
relationship  between   these pollutants
and  conventional pollutants (Biological
Oxygen Demand, Total Suspended Solids
and pH) and water  usage. These discus-
sions are centered on data obtained from
previous effluent guidelines development
studies designed to verify and quantify
the presence of conventional, noncon-
ventional,  toxic, and  priority chemical
pollutants in  industry discharges. Data
(when available) are expressed in ranges
to account for variations in process
conditions.
  Information obtained from the industry
broad review of chemicals and associated
processes  indicates   that  the  most
significant occupational exposure
problems associated with papermaking
chemicals include fatal exposures to high
concentrations of hydrogen sulfide and
other sulfur compound emissions, as well
as  carbon   monoxide  and  chlorine
exposures.  OSHA  sampling tests have
revealed that these chemicals frequently
exceed   OSHA  standards,   thus
contributing to problems of short-term,
accidental  and   acute  exposure.
Regarding long-term illness in pulp and
paper mill workers,  more information is
needed due to a lack of relevant epidemi-
ologic studies. In addition, plant visits are
essential to assess quantitatively the

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uses and hazards of the numerous chem-
ical  additives used throughout  the  in-
dustry.
  Although  the  literature  discusses
general  categories  of  additives,  the
problem is to  determine which are in
wide-spread use and, of those in wide-
spread use,  which are toxic under the
conditions of use. In short, there is a
surprising lack of quantitative informa-
tion on the use and exposure effects of
additives throughout the industry.
   Moreover, trie  distinction is  seldom
 made between  the  quantity  of  such
 materials  applied  and  the  quantity
 present  in  the  final  product.  Most
 additives are furnished to the mills by
 chemical suppliers who have technical
 service representatives to advise on the
 proper methods for handling and applica-
 tion. Since each pulp furnish and each
 paper machine has individual character-
 istics that must be  understood  for best
 results, the quantity  of  additives used
 may be quite  variable. Extensive, addi-
 tional  study is  therefore  required  to
 quantify  the   ranges   of  usage  and
 describe the process variations contribu-
 ting to such ranges for the many additives
 used throughout the industry.
   For  the vast majority of chemicals,
 information on  work  place  emission
 sources, worker exposure and other char-
 acteristics is scarce. Needs to gather such
 data have been tempered by the fact that
 many chemicals occur  in  such  small
 quantities that  worker exposure prob-
 lems have not been seriously considered.
   Regarding the development of general-
 ized  job   descriptions  and  crewing
 patterns, it should be noted that wide
 variations in these categories create job
 descriptions  that  are  generally  not
 comparable, since  mills combine  work
 tasks depending on  equipment layout,
     automation and complexity.  Hence, the
     number of required workers and the tasks
     they perform vary considerably through-
     out the industry. Occupational exposure
     characteristics for each machine type
     might  therefore  be  most   accurately
     determined on a plant by plant basis for
     each paper type. The study area analyses
     presented in Sections 4 and  5 of the full
     report  include discussions and  illustra-
     tions  of equipment,  machinery and
     process operations that can  serve as a
     guide to assess the need for further work
     to characterize occupational  exposure in
     operations not addressed fully by the
     development of  general  crewing  and
     exposure patterns, or in the case studies
     of  specific occupational problems  pre-
     sented in Section 6 of the full report.
        Studies similar to  that described in
     Section 6 {Gas Concentrations in Kraft
     Mill Work Areas) of the full report, can be
     applied  throughout  the   industry to
     quantify worker exposures  to the wide
range of organic and inorganic process
chemicals and by-products, escaping to
the work area. This type of investigation
can also   be  used  to  assist  the
development of  training  programs  and
safety procedures designed to control or
limit worker exposure. Such  activities
would   serve  to bolster  the  benefits
obtained  from  the  existing  training
programs  and  safety  procedures
discussed in this report.
  For many of the chemicals presented in
Appendix A of the  full  report, certain
items of data are not available  in the
literature and are therefore missing from
the Chemical  Profiles. Moreover, the
exact nature of the industrial occurrence
of  many chemicals (many of which are
identified by the NOHS walk through) is
not characterized. For these chemicals,
additional   research  is   required to
establish  completely  the  items of
information presented by the Chemical
Profiles.
         Robert Soklow is with S-CUBED, La Jolla, CA 92038-1620.
         M. J. Stutsman is the EPA Project Officer (see below).
         The complete report, entitled "Paper Production and Processing—Occupational
           Exposure and Environmental Release Study, "(Order No. PB 84-215 730; Cost:
           $46.00, subject to change J will be available only from:
                 National Technical Information Service
                 5285 Port Royal Road
                 Springfield, VA22J61
                 Telephone: 703-487-4650
         The EPA Project Officer can be contacted at:
                 Industrial Environmental Research Laboratory
                 U.S. Environmental Protection Agency
                 Cincinnati, OH 45268
                                            U S GOVERNMENT PRINTING OFFICE. 1984 — 759-015/7782
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300

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