United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-158 Sept. 1981
Project Summary
Fate of Toxic and
Nonconventional Pollutants in
Wastewater Treatment
Systems Within the Pulp,
Paper, and Paperboard
Industry
Bruce K. Wallin and Arthur J. Condren
Field studies were undertaken to
determine the fate of toxic and non-
conventional pollutants present in the
wastewaters discharged from the
pulp, paper, and paperboard industry.
A sampling and analysis program was
conducted at two deink mills and a
groundwood fine papers mill. Each
mill employed a wastewater treatment
.system which included primary clari-
fication, high rate biological treatment.
secondary clarification, and combined
primary/secondary sludge dewatering.
Through a sampling program of
primary clarifier influent, biological
treatment effluent, air emissions
above the aeration tanks, and de-
watered sludge solids it was the
objective of the study to complete a
mass balance of the pollutants under
study.
Analysis of primary ctarifier influent
samples was by both GC and GC/MS
techniques; analysis of the remaining
samples was GC method alone.
In general, 50 percent of the mass of
each pollutant found in the mill's raw
wastewaters were accounted for in
the program. The accountability of the
volatile organic pollutants ranged
from 27 to 55 percent. The account-
ability of semi-volatile pollutants
ranged from 6 to 933 percent with
three pollutants accounted for in
excess of 100 percent.
This report -was submitted in ful-
fillment of Contract No. 68-03-2605,
Work Directive No. 3, by the E.C.,
Jordan Co. under the sponsorship of
the U.S. Environmental Protection
Agency. This report covers the period
June 1978 to June 1980, and work
was completed as of June 1980.
This Project Summary was devel-
oped by EPA's Industrial Environ-
mental Research Laboratory, Cincin-
nati, 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
Program Objectives
Under Work Directive No. 3 the fate of
the toxic and nonconventional pollutants
present in the wastewaters discharged
by the pulp, paper, and paperboard
industry was to be determined. As
specified by the Agency, the E.G. Jordan
Co. was to sample "bottom sediments.
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air emissions and wastewater input and
output for biological treatment systems
treating unbleached kraft - hardwood
and softwood, bleached groundwood
integrated pulp mills and for NSSC only
pulp mills." These biological or physical-
biological treatment systems were to be
sampled for toxic pollutants and other
chemicals directed by the Agency but
including those toxic pollutants detected
during the EPA Effluent Guidelines
Divisions' Best Available Technology
Economically Achievable (BATEA)
Review Program.
Due to the budgetary limitations the
E.G. Jordan Co. initially recommended
that only semivolatile acid-neutral
compounds (SV-AN) be studied in Work
Directive No. 3. This recommendation
was made since available data indicated
that the volatile organics were removed
by aeration, and benzidine was the only
basic semivolatile organic detected
previously in pulp, paper, and paperboard
mill wastewaters. In the final formula-
tion of the work program it was
recommended that the raw wastewater
samples be screened by gas chroma-
tograph/mass spectrometry for all
volatile and acid-neutral semivolatile
organic pollutants previously under
study in the Agency's BATEA Review
Program. The compounds under investi-
gation are presented in Table 1.
Based on information gathered during
the Effluent Guideline Division's study,
the Jordan Company recommended
that the subcategory selection be
modified to include the following:
1. Bleached kraft,
2. Unbleached kraft (softwood),
3. Bleached groundwood, and
4. Deink.
The above recommendations were
made because the wastewaters from
these subcategories were known to
normally contain, among others,
measurable quantities of the toxic and
nonconventional organic pollutants of
concern.
The E.G. Jordan Co. also recom-
mended that only mills employing the
conventional activated sludge process
for wastewater treatment be considered
in the response to the work directive.
Aerated stabilization basin systems
were deemed unacceptable, because
'mass balances associated with sus-
pended solids in the treatment system
could not readily be addressed as a
result of the material partially settling
out in the system's aeration basins.
Pure oxygen activated sludge systems
were also deemed inappropriate for
Table 1. Toxic and Nonconventional Pollutants in the Pulp, Paper, and
Paperboard Industry
Toxic Pollutants
Volatile Organics
benzene
bromoform
carbon tetrachloride
chlorobenzene
chloroform
dibromochloromethane
dichlorobromomethane
1, 1-dichloroethane '
1, 2-dichloroethane
ethylbenzene
methylene chloride
1, 1, 2, 2-tetrachloroethane
tetrachloro.ethylene
toluene
1, 1, 1-trichloroethane
trichloroethylene
trichlorofluoromethane
xylene
Nonconventional Pollutants
Resin acids
abietic acid
dehydroabietic acid
isopimaric acid
pimaric acid
Fatty acids
oleic acid
Bleach plant derivatives
dichlorodehydroabietic acid
monochlorodehydroabietic acid
3, 4, 5-trichloroguaiacol
tetrachloroguaiacol
Semivolatile Organics
acenaphthene
acenaphthylene
anthracene
bis{2-ethylhexyl)phthalate
butyl benzyl phthalate
2-chlorophenol
chrysene
2, 4-dichlorophenol
diethyl phthalate
di-n-butyl phthalate
2, 4-dinitrophenol
di-n -octyl-phthalate
fluoranthene
isophorone
naphthalene
p -chloro -m-cresol
pentachlorophenol
phenol
pyrene
2, 4, 6-trichlorophenol
investigation because of the enhanced
probability of molecular oxidation of the
subject pollutants by contact with high
concentrations of pure oxygen.
Eight mills in the aforementioned four
recommended subcategories were
contacted by the E.C. Jordan Co. and
asked to participate in the program. Of
the eight mills contacted, favorable
replies were received from three deink
fine paper mills and three groundwood
fine paper mills. The remaining two
mills did not desire to participate in the
program. Of the six favorable responses
three mills were selected to participate
in the program. Several of the respond-
ing mill personnel, in responding to the
E.C. Jordan Co.'s request to participate,
noted that, due to the level of pollutants
present and process variations, a
complete "pollutant closure" would be
difficult. However, personnel felt that
useful data would be gathered relative
to the toxic and non-conventional
pollutants. The mills participating in the
program are indicated below:
Subcategory
Deink
Deink
Groundwood-
bleached
Mill Name and
and Location
Bergstrom Paper
Company
Neenah, Wl
Wisconsin Tissue
Mills, Inc.
Menasha, Wl
St. Regis Paper
Company
Sartell, MN
To accomplish the goal of the work
directive, a sampling and analysis
program was developed which would
allow for the calculation of pollutant
mass balances across the three waste-
water treatment systems investigated.
Each system included primary clarifica-
tion, high rate biological treatment.
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secondary clarification, and combined
primary/secondary sludge dewatering.
Prior to finalizing the sampling and
analysis program, the E.G. Jordan Co.
reviewed with Agency representatives
the pollutants of potential concern in
the pulp, paper, and paperboard industry.
It was decided that raw wastewaters
would be screened by GC/MS for all of
the pollutants (see Table 1). The air,
sludge, and final effluent samples
would be analyzed by GC for those
pollutants detected in the raw waste-
water by GC/MS procedures.
The program utilized in this study
involved the collection of samples from
the following locations at each of the
three facilities investigated:
1. primary clarifier influent;
2. secondary clarifier effluent;
3. air emissions above the aeration
tanks; and
4. dewatered sludge solids.
Analysis of primary clarifier influent
samples was by both GC and GC/MS
techniques; analysis of the remaining
samples was by the GC method alone.
Origin of Specific Toxic
Compounds
Specific toxic compounds in the raw
materials and the wastewaters from
various mills in the pulp, paper, and
paperboard industry, and from the wood
products have been reported in the
literature. Most of the literature,
however, has dealt with the toxicity of
various resinous and fatty acids (see
Table 1).
One study found that resin acids
contribute substantially to the toxicity of
wastewaters from all pulping processes.
A similar study summarized the resin
and fatty acid contents of major wood
species used in the industry. The
results, summarized in Table 2, show
that pines have by far the highest acid
content of species studies.
The content of total resin acids was
also observed to vary within the major
species groups. One study showed a
substantial variation in resin acid
content for trees of different ages. It was
shown also that resin acid content was
a function of tree diameter, i.e., the
larger the diameter, the higher the resin
acid content.
Also of concern are heavy metals.
These primarily originate from pigments
added in paper coating and glazing
operations. There is a lack of literature
on specific toxicity of additives used in
various papermaking operations.
Table 2. Typical Resin and Fatty Acid Contents of Raw Wood Types
Total resin acids Total fatty acids
Species
(Percent by weight
oven dried wood)
(Percent by weight
oven dried wood)
Pines
Other softwoods
Hardwoods
1.5%
0.1%
negligible
1.0%
0.1%
0.5%
Detergents used for deinking of
wastepaper also contribute to toxicity. It
was determined that several such
detergents were lethal to fish at a
concentration of 4.0 mg/l. Polychlor-
inated biphenyls (PCB), formerly used in
the manufacture of carbonless copy
paper and printing inks, remain in some
wastepaper mill effluents because of
wastepaper recycling. The New York
State Department of Conservation
conducted a study concerning PCB in
wastepaper mill effluents. Of the 40
New York mills using wastepaper, 18
were determined to be potential direct
dischargers of PCB. Final effluent
samples from these mills were analyzed
monthly from October 1976 to Septem-
ber 1978. The results of this study
indicated that final effluent PCB con-
centrations were generally below one
microgram/liter (/ug/l) and that the
concentration was reduced by biological
treatment.
Conclusions and
Recommendations
The objective of the program was to
determine the fate of a number of toxic
and nonconventional pollutants normally
present in pulp, paper and paperboard
wastewaters. Through a detailed sam-
pling program of influent and effluent
wastewaters, air emissions, and solid
wastes, it was the objective to complete
a mass balance of the pollutants.
In general, 50 percent of the mass of
each pollutant found in the mill's raw
wastewaters were accounted for in the
program. The accountability of the
volatile organic pollutants ranged from
27 to 55 percent. The accountability of
semivolatile pollutants ranged from 6 to
933 percent 'with three pollutants
accounted for in excess of 100 percent.'
Based on the accountability of pollu-
tants experienced in the program, it is
apparent that the objective was not
achieved due to several factors. These
factors include:
1. biochemical transformation;
2. laboratory analysis;
a. quantity of pollutants,
b. detection limits.
c. sample matrix, and
d. analytical procedures;
3. sampling procedures; and
4. capability to accurately estimate
air and sludge emissions.
The impact of several of the factors
encountered in this program may be
minimized with continued research and
controlled conditions.
Future studies of the fate of toxic and
nonconventional pollutants in industrial
wastewaters should strive for improved
accountability of pollutants under study.
It is unrealistic to anticipate 100 percent
accountability; however, through more*
controlled conditions, more advanced
sampling techniques, and higher reso-
lution analytical techniques, improved
accountability should be a realistic goal.
Sampling procedures in future pro-
grams should consider flow proportional
aliquots (wastewater), composite or
individual samples of sludge (solids),
and a more efficient air emissions
sampler (air).
A statistical design of the sampling
program should be considered for future
programs. Through consideration of
known variables, the sample sites,
frequency and number of samples could
be considered so that the results will
have a known reliability.
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Bruce K. Wallin and Arthur J. Condren are with E. C. Jordan Co.. Portland. ME
04112.
Michael D. Strutz and Donald L. Wilson are the EPA Project Officers (see
below).
The complete report, entitled "Fate of Toxic and Nonconventional Pollutants in
Wastewater Treatment Systems Within the Pulp, Paper, and Paperboard
Industry," (Order No. PB 81-247 405; Cost: $11.00, subject to change) will be
available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
US GOVERNMENT PRINTING OFFICE; 1981 —559-017/7376
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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