United States
Environmental Protection
Agency
Environmental Research
Laboratory
Corvallis OR 97330
EPA-600'3 79-013
February 1979
Research and Development
Toxicity of
Pulp and Paper
Mill Effluent
A Literature Review
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development. U.S. Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4 Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/3-79-013
February 1979
TOXICITY OF PULP AND PAPER MILL EFFLUENT
A Literature Review
by
Floyd E. Hutchins
Western Fish Toxicology Station
Corvallis Environmental Research Laboratory
Con/all is, OR 97330
CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OR 97330
-------
DISCLAIMER
This report has been reviewed by the Corvallis Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
11
-------
FOREWORD
Effective regulatory and enforcement actions by the Environmental Pro-
tection Agency would be virtually impossible without sound scientific data on
pollutants and their impact on environmental stability and human health.
Responsibility for building this data base has been assigned to EPA's Office
of Research and Development and its 15 major field installations, one of which
is the Corvallis Environmental Research Laboratory.
The primary mission of the Corvallis Laboratory is research on the ef-
fects of environmental pollutants on terrestrial, freshwater, and marine eco-
systems; the behavior, effects and control of pollutants in lake systems; and
the development of predictive models on the movement of pollutants in the bio-
sphere.
This report reviews the current knowledge of acute and sublethal effects
of pulp and paper mill effluents on aquatic organisms. Toxic effects of
treated and untreated effluents as well as the primary toxic components from
kraft, sulfite, and groundwood effluents are covered. This review was con-
ducted to ascertain the need for further laboratory studies to provide toxic-
ity data for effective regulation of these effluents.
James C. McCarty
Acting Director, CERL
m
-------
ABSTRACT
This review of pulp and paper mill effluents considers the need for
additional toxicity data to insure effective effluent regulation. Effluent
characteristics and problems of toxicity testing particular to pulp and paper
mill effluents are discussed; however, the emphasis is on toxic effects of
these effluents to aquatic life.
Untreated pulp and paper mill effluents are very toxic to most aquatic
life. Concentrations as low as two percent can be acutely toxic to fish.
Sufficient treatment can render the effluent essentially nontoxic much of the
time; however, treatment processes used by most mills reduce toxicity but do
not eliminate it. Even effluents receiving "good" treatment may exhibit
sporadic and dynamic increases in toxicity (due in part to spills or dumping
of spent pulping chemicals). Sublethal exposures to aquatic organisms to pulp
effluent may affect a number of their physiological and behavioral functions.
The more sensitive functions, growth rate, coughing reflex, and temperature
tolerance, are affected at concentrations less than l/10th of the 96-hr LC50.
Many other systems such as respiration and circulation may be affected at
concentrations near l/10th of 96-hr LC50. The principal toxic components in
pulp and paper mill effluents are resin acids and fatty acids naturally occur-
ring in the wood pulp and, in effluents from bleaching processes, toxic chlor-
inated compounds predominate. Untreated effluents have caused considerable
environmental damage, but well-treated effluents have had minimal effects on
fish production, although shifts in biological diversity have occurred.
IV
-------
TABLE OF CONTENTS
LIST OF FIGURES AND TABLES vi
INTRODUCTION 1
CONCLUSIONS 2
RECOMMENDATIONS 3
LITERATURE REVIEW 4
PULPING METHODS 4
Kraft 4
Sulfite 4
Groundwood 6
EFFLUENT CHARACTERISTICS 6
Kraft 6
Sulfite 6
Groundwood 7
TOXICITY TESTING 7
ACUTE TOXICITY 10
Kraft 11
Sulfite 14
Groundwood 14
SUBLETHAL EFFECTS 15
Kraft 19
Sulfite 22
Groundwood 23
TOXIC COMPONENTS 23
Kraft 27
Sulfite 28
Groundwood 29
Process streams 29
Miscellaneous constituents 29
CONCLUDING STATEMENTS 32
REFERENCES 33
v
-------
FIGURE AND TABLES
page
Figure 1. Simplified schematic of pulp and paper mill processing ... 5
Table 1. Concentrations of pulp and paper mill effluent lethal to
aquatic life 12
2. Sublethal effects of pulp and paper mill effluents on
aquatic life 16
3. Principal toxic constituents in pulpmill waste streams
(from Leach and Thakore, 1977) 24
4. Concentration and acute toxicities of resin acids found in
softwood pulping and debarking effluents (from Leach and
Thakore, 1977) 25
5. Toxicity to juvenile coho salmon of long-chain fatty acids
present in debarking and pulping effluents (from Leach and
Thakore, 1977) 25
6. Toxic constituents in kraft mill caustic extraction
effluents (after Leach and Thakore, 1977) 26
7. Toxic neutral extractives found in various effluents (from
Leach and Thakore, 1977) 26
vi
-------
INTRODUCTION
The impact of pulp and paper mill discharges on receiving waters results
from the integrated action of oxygen demand, suspended and dissolved solids,
pH, color, and toxicity. This review of the literature emphasizes effects due
to toxicity. Because of the rapid progress in recent years in effluent treat-
ment and recovery of spent chemicals, the review concentrates on data pub-
lished since 1960. For information on earlier publications, one should see
the reviews by Van Horn (1961 and 1971). More recent reviews have been pub-
lished by Marier (1973) and Walden and Howard (1971). Davis (1976) has re-
viewed the progress in sublethal effects studies with kraft pulpmill effluents.
The latest review by Walden (1976) covers many publications and progress
reports from Canada that have not been included in other reviews. However,
the majority of the Canadian publications and progress reports, plus reports
not covered by Walden (1976) were obtained and cited in this review.
Most of the information on the impact of pulp and paper wastes on the
aquatic environment comes from laboratory studies under controlled conditions,
with limited data available concerning impacts of effluents in natural eco-
systems. However, sufficient studies have been conducted under natural
conditions to demonstrate that the effluent can be quite harmful if not
properly treated (Filimonova 1968; Washington, State of, 1967; Gregory and
Loch 1973a,b; Stone et aJL 1974; Dickman 1973; Leppakoski 1968). Adverse
effects on the environment have not been demonstrated with secondary-treated
effluents other than as a result of spills or other malfunctions, even though
many of these effluents are still acutely toxic at full strength to trout and
salmon. Dilution is the primary reason many effluents are apparently not
causing major adverse environmental effects, but failure to detect more subtle
and longer term effects may also contribute to the apparent lack of adverse
impacts.
-------
CONCLUSIONS
1. Large quantities (tons) of toxic and nontoxic materials are released into
receiving waters daily by each pulp mill.
2. Untreated pulp and paper mill effluent can be acutely toxic to fish at
concentrations as low as 2% by volume. Sufficient treatment can render
the effluent virtually nontoxic much of the time; however, treatment
processes used by most mills reduce toxicity but do not eliminate it.
3. Toxicity of the effluent to aquatic organisms other than fish is not
adequately known.
4. Toxicity of pulp and paper mill effluents is highly variable and treat-
ment reduces this variability but does not eliminate it.
5. Predictive value of the bioassay of pulp and paper mill effluents is
considerably reduced by the variable nature of these effluents.
6. Sublethal effects of pulp and paper mill effluents are varied. The
threshold concentration for sublethal effects appears to be near 1/10 of
the 96-hr LC50 concentration.
7. Except for bleaching effluents which contain several types of chlorinated
compounds, natural resin and fatty acids from wood are the principal
toxic components of pulp and paper mill effluents.
8. Other chemicals, especially fungicides, can add to the toxicity of the
effluents.
9. Untreated effluents have been shown to cause considerable environmental
damage, but well-treated effluents have had minimal effects on fish
production, although shifts in biological diversity indices have oc-
curred. The apparent lack of adverse effects may be due, in part, to the
masking effect of nutrient addition or the inability to detect subtle
adverse effects.
10. In artificial stream studies, kraft mill effluents have been shown to
increase production of fish and some fish food organisms at low effluent
concentrations, presumably through organic enrichment. At higher concen-
trations of effluent, production of fish and some fish food organisms can
be reduced.
-------
RECOMMENDATIONS
1. The toxicity of whole pulp and paper mill effluents to fish has been
adquately demonstrated and further bioassays do not appear to be needed
except in support of other studies or for effluent management.
2. Further research may be conducted to identify those aquatic organisms
more sensitive than fish to pulp and paper mill effluent.
3. The sporadic and dramatic increase in the toxicity of even "well-treated"
effluents appears to justify monitoring the toxicity of pulp and paper
mill effluents for proper management.
4. The effects of short-term, near-lethal exposures of pulp and paper mill
effluents to aquatic life are not known and should be determined.
5. Currently, bioassays are the only reliable method of assessing the efflu-
ent's toxicity. However, certain sublethal tests such as the "cough
reflex" in fish appear to have some merit as a monitoring tool. Chemical
assay of principal toxic components may soon serve to monitor toxicity of
the effluent.
6. Toxicity studies necessary to establish water quality criteria or efflu-
ent guidelines should be conducted for the principal toxic components in
pulp and paper mill effluents. (These compounds include the natural
resin acids and fatty acids, the insect juvenile hormone analogs and, in
effluents from mills using chlorine bleach, the chlorinated alcohols,
chlorinated lignins and chlorinated resin acids and fatty acids.) The
effects of the insect hormone analogs on aquatic insects should be deter-
mined.
7. The increase in the toxicity of pulp and paper mill effluents following
chlorination should be further investigated before requiring chlorination
of treated pulp and paper mill effluents.
8. To identify pollution problems, a toxicity survey of pulp mill effluents
may be necessary.
-------
LITERATURE REVIEW
PULPING METHODS
The toxicity and other characteristics of pulp mill effluents are largely
influenced by the pulping process and its efficiency, the type of wood pulped,
and the frequency of malfunctions or spills. Three methods of pulping, or
combinations and/or modification of these, are generally used. These are:
alkaline digestion, known as the kraft process; acid digestion, known as the
sulfite process; and the mechanical or groundwood process. A simplified
schematic description of these processes and their effluents is given in
Figure 1.
Kraft
Kraft pulp is produced by digestion of wood chips under heat and pressure
in a highly alkaline sodium sulfide solution. Digestion results in the forma-
tion of black liquor, containing the wood extractives and solubilized lignin,
which is separated from the fiber. Weak black liquor is produced in success-
ive washing stages, and only the most dilute wash waters are discharged to
sewers. The combined black liquors are concentrated in multi-effect evapora-
tors and the residue is burned in a chemical recovery furnace to retrieve
pulping chemicals. The furnace smelt is redissolved, adjusted to strength
with fresh chemicals and reused. Approximately 95% of the chemicals are
recycled and most soluble organics are burned in the recovery furnace. Con-
densates from the evaporators are recycled within the pulping process to
minimize water use and heat loss.
To produce a white paper the pulp must be bleached with a series of
bleaching and extraction steps. Acid bleaching solutions are generally chlor-
ine dioxide or aqueous chlorine, and extraction is with caustic sodium hydrox-
ide. Bleaching is followed by washing and drying to produce a finished pulp.
Some mills in Europe use ozone for bleaching which essentially eliminates the
toxicity associated with chlorinated compounds in bleaching waste.
This brief description does not reflect the complexity of the kraft
process. The design and location of the mill, the type of wood pulped, the
additives used and the plant operation influence the toxicity of the efflu-
ents.
Sulfite
The sulfite pulp is produced by acid digestion of woodchips in sulfite of
ammonia, sodium, calcium, or magnesium. The only other major difference from
the kraft process is that the digestion chemicals are not generally recovered,
but instead are dumped as sulfite waste liquor (SWL). Rosehart et aj. (1974)
-------
RAW
MATERIALS
LOGS
ACIDSULFITE OR
ALKALINE SULFATE
COOKING LIQUOR
GROUND WOOD
"WHITE WATER"
OR PROCESS WATERS
BLEACH LIQUORS
FRESH WATER
FRESH WATER
PROCESSES
WASTES
^-
*
DEBARKING
a CHIPPING
1
WOOD CHIPS
1
DIGESTION
OR "COOKING"
1
t. IlklOIIOIT Dill B
„ N*
^^^^m
*
J SCREENING
H a WASHING
^^^•IB
— >
BARKER WASTES
(bark a wood p
or (dis
EVAPORATION
a BURNING OR
BY-PRODUCT
RECOVERY
LIQUOR
RECOVERY
•articles)
HE WASTE LIQUORS
solved Pgnins a
chemicals)
* WASTES
J.CONDENSATE
* WASTES
"WEAK LIQUOR" OR WASH WATERS
(dissolved lignins a chemicals)
UNBLEACHED
PULP
BLEACHING
a WASHING
BLEACHING WASTES
(dissolved lignins a chemicals)
BLEACHED PULP
i
PULP DRYING
I
FINISHED PULP
(bales or rolls)
"WHITE WATER"
(suspended solids)
CONVERSION TO
PAPER PRODUCTS
"WHITE WATER"
(suspended solids)
FINISHED
PAPER PRODUCTS
si
MARKETS
Figure 1. Simplified schematic of pulp and paper processing.
5
-------
have reported on a sulfite process with good chemical recovery, relatively low
toxicity, and apparent operating economy. If this proves successful, the
sulfite process may regain some of its previous popularity.
Groundwood
Groundwood pulp is produced by mechanical grinding to separate the fibers
in lieu of chemical digestion. This process is generally used for low quality
paper such as newsprint or used in combination with other pulp to form prod-
ucts of intermediate quality. Groundwood pulp is not usually bleached.
EFFLUENT CHARACTERISTICS
Kraft
The kraft process uses tremendous volumes of water: older mills use
20,000 gal/ton of air-dried pulp in the pulping process plus 30,000 gal/ton in
the bleach plant; newer mills may use 30,000 gal/ton in the overall process.
Additional water is used in the paper-making process. Typical mills produce
200-600 tons of pulp per day, so the volume of effluent can be great; 20
million gallons of effluent per day (24 hr) are common. The average 5-day BOD
(biological oxygen demand) of kraft pulping effluent is in the range of 200-
300 mg/1 plus another 15-30 mg/1 from bleaching wastes. The combined efflu-
ents could contribute 20-40 tons of BOD per day if not treated. Many tons of
materials that do not exhibit a significant BOD are also dumped. Considering
the volume of effluent, it is obvious that large quantities of dissolved and
suspended materials are released into the aquatic environment. The pH of
kraft effluent is high, but is normally neutralized before discharge. Color
and foam can also cause water quality problems. In addition, fish below the
outfall may have an objectionable flavor and odor (Cook et aJL 1971).
The principal factors affecting toxicity of unbleached kraft effluent are
efficiency of pulp washing and frequency of spills or other malfunctions.
Improper washing and improper treatment of wash waters lead to high concentra-
tions of naturally occurring resin acids and fatty acids. Bleaching of pulp
usually reduces the concentration of resin acids but toxicity is usually not
reduced because some phenolic and other compounds are chlorinated that con-
tribute significantly to toxicity. The nature and toxicity of pulp effluent
constituents will be discussed later. The species of wood pulped also influ-
ences the characteristic of the effluent.
Sulfite
The sulfite process also requires large volumes of water and the BOD per
ton of pulp can be more than ten times that of the kraft process. It is
common to find the BOD of raw sulfite effluent near 2,000 mg/1 and that of
treated (lagooned) effluents near 1,000 mg/1. In fact, the BOD of sulfite
waste liquor (SWL) is so high (20,000-30,000 mg/1) that early investigators
attributed the principal toxicity of the liquor to BOD depleting the oxygen
levels in the test chambers. Generally the toxicity is less than that of
kraft waste on a volume basis, because fewer of the naturally occurring resin
acids survive the acid digestion process (Waiden 1976). If the ammonia base
-------
sulfite pulp is subsequently bleached with chlorine, highly toxic chloramines
can be formed. Color and foam are not the problem that they are in kraft
effluent but some taste and odor problems have been attributed to sulfite
effluents. The pH of the untreated effluent has been reported occasionally to
fall below 2 and even after treatment in lagoons, a pH of 4 is common.
Groundwood
Mechanical pulping requires about one-third the water used in chemical
pulping. The fiber size is usually larger and less fiber is lost in the
effluent. As a result, the BOD of the effluent is quite low, 70-80 Ib/ton
pulp or 500-1500 mg/1 for untreated effluent (Howard and Leach 1973b; Leach
and Thakore 1974c). Groundwood effluents which have received primary treat-
ment have a BOD of about 125 mg/1. The effluent is slightly acid with a pH of
5 to 6. The toxicity of groundwood mill effluent (GME) is due primarily to
natural resin and fatty acids.
TOXICITY TESTING
It will be worthwhile to examine some of the difficulties in assessing
the toxicity of pulp and paper mill effluents so that toxicity values presen-
ted later may be placed in perspective. One of the problems with bioassays of
pulp mill effluent is the variability of effluents, both within a given plant
and among plants (Howard and Wai den 1971; Wai den and Howard 1971; Wai den
et aJK 1971). Howard and Walden (1971) reported the mean survival time (MST)
of salmonids varied from 485 to 1298 minutes in full strength bleached kraft
mill effluents from seven British Columbia mills during a 40-day period.
Depending upon the mill, 21-82% of the samples were not acutely toxic. Gordon
and Servizi (1974) monitored the toxicity of a British Columbia bleached kraft
pulp mill effluent to sockeye and pink salmon through a year-long series of
consecutive 4-day bioassays. They found 94% of the samples were toxic at 90%
(v/v) concentration, 76% were toxic at 65% concentration, and 60% were toxic
at a 25% concentration. Treated effluents retained some of this variability.
With 29-hour aerobic fermentation 29, 15, and 8% of the samples were still
toxic at 90, 65, and 25% concentrations. Even with 99-hour treatment 7% of
the samples were toxic at 90% concentration. Bruynesteyn and Walden (1971)
found considerable variation in the toxicity of samples collected at intervals
as short as 15 minutes. Therefore, statements concerning toxicity of an
effluent must be made with caution if based on only a few samples. When only
a few samples are available one should ascertain that the mill was operating
"normally" with no shut downs or spills.
Another variable feature of pulp mill effluents is the toxicity added by
many chemicals used in addition to actual pulping chemicals. These chemicals
include anti-foam agents, anti-pitch agents, sizings, biostatic agents, etc.
A review by Conkey (1968) listed over 100 biostatic agents in use in 1968.
The groundwood process is defined as "non-chemical," but 21 chemical additives
were used in one mill (Gordon and Servizi 1974). The use of additives fluc-
tuates as need, price availability, and formulations change.
Another feature of pulp mill effluents which tends to make the reported
toxicity values less useful is the change in quantity and quality of the
-------
effluent in a relatively short period of time through mill expansion, change
of process or chemical recovery systems, or improved treatment. The pulping
industry in the United States generally has had considerable success in re-
ducing toxicity of their effluents. Therefore, this literature review has
concentrated on data published since 1960. Even toxicity data presented early
in this period may not be applicable to the current situation. For example,
one mill has expanded, and has added terpene recovery systems, secondary
aeration lagoon treatment and a polishing basin since initiation of Warren's
studies in 1960 (Warren et aj. 1974). It appears that, with the variability
within a mill and among mills of the same type, meaningful comparisons of
toxicity values reported in the literature are difficult to make.
Chemical assays are not yet feasible as a technique for assessing tox-
icity of pulp and paper mill effluents. Some toxicants have not been identi-
fied and consequently can not be determined chemically; moreover, chemical
assays of toxicants are toxicologically useful only when related to biological
responses. This "dose-response" relationship has not been adequately estab-
lished for chemicals in pulp mill effluents; therefore bioassays are currently
the only method of assessing toxicity of effluents (Betts 1976).
The bioassay of pulp and paper mill effluents poses special problems
because of low concentrations of toxicants, high BOD, and chemical instabil-
ity. Recently, Wai den and McLeay (1974) and Wai den et a_L (1975) have under-
taken a detailed study of the problems specific to the bioassay of pulp mill
effluents. Wai den et a_K (1975) suggested that the standard acute toxicity
test for pulp mill effluent should be a 96-hr exposure with solution replace-
ment every 24 hr and a fish loading density of less than 0.5 g/1. Sprague
(1969) has shown that 96-hr exposure to pulp mill effluents will adequately
assess acute toxicity. Minimum exposure time should be 24 hr if a good corre-
lation with 96-hr LC50 is to be maintained.
Solution replacement is necessary during the 96-hr exposure because of
loss of toxicants through degradation or uptake by the fish. The required
frequency of replacement depends on stability of the toxicants and fish den-
sity. Raw effluent requires more frequent replacement than do treated efflu-
ents. In a series of tests by Wai den et aJL (1975), depletion of toxicants by
the fish was slight at fish densities of 0.5 g/1 in static 96-hr tests with
primary treated effluent, however, fish densities of 2 g/1 required solution
replacement every 24 hr.
Solution replacement can be achieved either by static replacement of the
solution or by flow-through replacement. Static replacement simply entails
periodically placing the fish into a new solution of the desired concentra-
tion. The flow-through system provides a more constant exposure but requires
larger volumes of effluent. Betts et aJL (1967) devised a flow-through appar-
atus for replenishing test solutions which requires only a small volume of
effluent. However, the replacement rate was no greater than achieved by
direct transfer of the fish into a new solution every 12 hr. This flow-
through system required 10 times more effluent than simple static replacement.
Wai den et al_. (1975) reported very little difference in 96-hour LC50
values between flow-through bioassays and those with static replacement of the
8
-------
test solutions. Handling of the fish during transfer into new solutions every
12 hr did not appear to cause undue stress. In comparative tests, Walden and
McLeay (1974) reported that 96-hr LC50 values for 12-hr and 24-hr solution
replacement were similar, however, 96-hr LC50 values were considerably higher
with 48-hr replacement of test solutions.
Walden (1976) has classified various acute toxicity tests as to their
sensitivity in terms of toxic units. He assigned unity to the concentration
killing 50% of the fish in 96 hr with static replacement every 24 hr and a
fish density of 2 g/1. This sensitivity data may make it possible to compare
toxicity tests of varying duration, replacement rates, fish density, and
percent mortality.
The majority of acute toxicity tests reported do not conform to the
standard test proposed by Walden et a_K 1975. For practical reasons 24-hr
exposures are often used. In the interest of conserving time and effluent,
mean survival time (MST) in full strength effluent is often given as the end
point—a procedure recommended by Walden and McLeay (1974) for rapid effluent
monitoring since death is usually quite rapid and solution change is unnec-
essary.
The dissolved oxygen concentration in test solutions should be maintained
near 9.0 mg/1 at 15 C to avoid influences of reduced oxygen concentration on
toxicity of the effluent to salmonids (Ozburn et al_. 1973, 1974; Hicks and
DeWitt 1971). These high oxygen levels cannot be maintained with static
replacement of test solutions because of the high BOD and, therefore, oxygen
must be added. Procedures for adding oxygen can lead to depletion of unstable
toxic materials through volatilization and oxidation. Direct addition of
minimal amounts of oxygen through small tubes appears to be the best way to
maintain oxygen levels without considerable reduction in toxicity, although
some reduction is unavoidable (Walden and McLeay 1974; Blosser and Owens
1970).
Little information is available on the influence of pH on the toxicity of
pulp mill effluent. Ladd (1969) reported coho salmon (Oncorhynchus kisutch)
survived longer in bleached kraft mill effluent (BKME) when pH was between 8
and 9. Leach and Thakore (1974a) have shown that pH values just below 7
increased the toxicity of the resin acids in the effluent. High pH values in
ammonia-base sulfite wastes can cause toxicity due to un-ionized NH3 (Tabata
1965).
Most acute bioassays with salmonids have been conducted at temperatures
between 10 and 15 C. Walden et aj. (1975) proposed 15 C as a standard. High
test temperatures can increase the toxicity of the waste (Loch and MacLeod
1974). Solution replacement rate may have to be increased at higher tempera-
tures because of the increased rate of breakdown of toxic substances.
Effects of storage of the effluent prior to an assay must not be over-
looked. Davis and Mason (1973) have cited instances where toxicity declined,
remained the same or increased with storage. Degradation of toxic constitu-
ents can occur during storage even at temperatures near 0°C (Howard and Walden
1965; Servizi et aj. 1966; Webb and Brett 1972). This is particularly true of
-------
untreated effluent. If the effluent has received adequate secondary treat-
ment, storage at very low temperature is not necessary if oxygen can be kept
from the effluent (Waiden and McLeay 1974). For example, samples can be held
at temperatures up to 25 C for four days prior to the test with virtually no
loss of toxicity. Storage at elevated temperature under anaerobic conditions
can lead to the formation of hydrogen sulfide. The odor is evidence of the
problem and the sample should be discarded.
Low temperature during the treatment process can lead to inadequate
secondary treatment and increased toxicity. This is a particular problem in
most northern mills (Howard and Leach 1973b) although Seim et aj. (1977)
reported this may happen even in Oregon's temperate Willamette Valley.
Rainbow trout (Salmo gairdneri) have been suggested as the standard test
species on the basis of availability and ease of maintenance under laboratory
conditions. Considerable evidence shows that the rainbow is at least as
sensitive as any salmon. Warren and Doudoroff (1958) have suggested the guppy
(Poecila reticulata) be used for routine bioassays of pulp effluent because of
the difficulty in maintaining adequate oxygen concentration for sal mom* ds
without undue oxidation of the sample and because much less effluent is
needed for the guppy bioassay. Numerous other fish species have been used as
test animals and may have advantages in specific locations. Salmon between
ages of 50 and 450 days appear to have similar sensitivities to bleached kraft
effluent, however, salmon embryos are more resistant (Holland et al. 1960).
Based on the reaction of salmonids to some chemicals, ages between 20-40 days
(post-hatch) may be the most sensitive (Larson et al_. 1977).
Other problems associated with acute bioassays of pulp effluent include
slime growth on flow-through dilution apparatus and the color of kraft efflu-
ent. Vigorous treatment of kraft effluent reduces its toxicity considerably
but not its color. The high concentrations of treated effluent necessary to
kill fish are often so colored that the fish are difficult to observe.
ACUTE TOXICITY OF PULP AND PAPER MILL EFFLUENTS
Much data are available concerning acute toxicity of pulp and paper mill
effluents to fish, particularly salmonids, but information concerning the
effect of pulp effluents on invertebrates and algae is limited. Much of the
more recent toxicity data has come from private research groups sponsored by
the pulp and paper industry. In the United States, the National Council for
Air and Stream Improvement (NCASI) located at several universities throughout
the country, is responsible for the bulk of the toxicity information avail-
able. In Canada considerable work is being done on all phases of effluent
toxicity. B.C. Research personnel (Walden, Leach, McLeay, Thakore, and How-
ard) at Vancouver, British Columbia are responsible for a considerable portion
of our knowledge concerning the factors affecting the toxicity of kraft and
groundwood pulp mill effluents, including analyses of toxic constituents.
Wilson and Chappel of Bio-Research Laboratories, Ltd., Quebec, have done sim-
ilar work for sulfite mills. Much of the Canadian work has been published in
progress reports of the CPAR (Committee for Pollution Abatement Research), a
cooperative effort of the Canadian Department of Environment and the pulp and
10
-------
paper industry. Portions of these studies have been published. More infor-
mation will be forthcoming from NCASI and CPAR, as their programs continue.
Table 1 summarizes some of the 96-hr LC50 data available on whole un-
bleached and bleached kraft-, groundwood-, and sulfite-mill effluents. Also
included in this table are toxicity data for some of the major process streams.
Bark and woodroom leachates are included because they contain most of toxic
components found in unbleached kraft and groundwood effluents, however, these
components are more concentrated in the leachates than in whole effluents.
Sulfite waste liquor (SWL) data are included because they likewise contain
most of the toxic constituents present in whole effluent. However, the SWL
stream is many times more toxic than the whole sulfite mill effluent (SHE).
The 96-hr LC50 concentrations given in Table 1 are expressed as percent
by volume. The concentration of toxic materials in the effluent is usually
not known, therefore, the concentrations in the dilutions are also unknown.
Water use in relation to the volume of wood pulped will, to a large extent,
determine the concentration of toxic components. The concentration of sulfite
mill effluent has sometimes been given as mg/1 based on the Pearl Benson Index
(PBI) which is an indication of the amount of lignin present. PBI is not
currently used as an expression of concentration since it measures only one
group of compounds that contributes little to the toxicity of the effluent
(Walden and McLeay 1974). Expressing effluent concentrations in terms of
total resin acids has failed to predict acute toxicity, even though their
contribution to toxicity is quite high (60-80% for unbleached kraft), because
the composition of the total resin acids is variable. In addition, resin
acids are not the major toxicant in bleached pulp mill effluent (Leach and
Thakore 1977). In a study by Wilson and Chappel (1973), the toxicity of
sulfite wastes from several mills correlated well to the dissolved-solids
concentration, but not to volume-to-volume dilutions. Considering the varia-
ble factors influencing the toxicity of pulp effluent and the variable assay
procedures used, only very general conclusions can be made from a collection
of LC50 values such as those listed in Table 1.
Kraft
Whole, unbleached kraft mill effluent can be quite toxic, with 96-hr LC50
values of only a few percent by volume for salmonids held in effluents re-
ceiving only suspended solids treatment. Conversely, well-treated effluent
can be nontoxic even at full strength (Seim et a_L 1977; Tokar and Owens
1968). In the only study reviewed here where salmonid and non-salmonid fishes
were used to test with the same effluent, Tokar and Owens (1968) found young
guppies were slightly more sensitive than were juvenile Chinook (0. tshawy-
tscha). However, the guppies were exposed at a higher temperature (25C) than
the salmon (15C).
Kraft mill effluent (KME) can also be toxic to fish food organisms. Only
a limited number of studies have been reported where the same effluents were
used with both invertebrates and salmonids. Micro-crustaceans and insect
larvae appear to be only slightly more resistant than salmonids (Van Horn
et al_. 1949, 1950; Dimick and Haydu 1952; Livintsev 1967). Fahmy and Lush
(1974) showed a chironomid (Chironomus tentans) larva to be more sensitive
11
-------
TABLE 1. CONCENTRATIONS OF PULP AND PAPER MILL EFFLUENTS LETHAL TO AQUATIC LIFE.
Effluent type Species
Kraft (KME) Rainbow trout
n n
ti
i
n
Chinook salmon
u n
•i i:
Coho salmon
M u
Perch
Guppy
Oppossum shrimp
n u
Marine invertebrates
96hrLC50
(% by volume)
< 15
15-50
755 mg/1 (PB
26
> 100
< 15
4-24
> 100
7
40
> 100
18-32
24
4.5
4.7
2.6
3.7 (ave.)
Comments
Integrated newsprint
-, /
I)-'
Untreated newsprint
Biotreated
—
Primary treatment
Secondary treatment and stabilized (SKME)
Primary treatment Mill A
Mill B
SKME non-chlorinated effluent
SKME chlorinated effluent
—
Primary treatment
Untreated 17°C
26°C
Clams, mussels, sea worms, zooplankton
tested (abstracted article, details not
available)
Reference
Loch & MacLeod 1973
Loch & Bryant 1972
Jacobs & Grant 1974
Wilson 1975
Fahmy & Lush 1974
Loch & MacLeod 1973
Seim et al_. 1977
n ii
Tokar & Owens 1968
ii n n
Stiles 1977
U ii
Cook et al. 1971
Tokar & 0~wens 1968
Jacobs & Grant 1974
n n II
Donnier 1972
Daphnia & insect larvae "Toxic"
Insects and trout
Micro-crustaceans
Micro-crustaceans
Stonefly
Stonefly larvae
Phytoplankton
II
Kraft-bleached Rainbow trout
(BKME)
Chinook and Coho salmon
Chinook salmon
Sockeye salmon
n n
1
Atlantic salmon
II n
Guppy
Pontogammarus
n
"Toxic"
"Lethal"
"Toxic"
2.5
> 100
32
4-10
0.6
1.9-3.6
6.5
34-64
12-43
60; tests toxic 0
25* v/v
75i tests toxic @
90% v/v
12-15
12-15
14
34-36
12
Sensitivity: Chironomus > trout > gammarus
> mosquito
Slightly more resistant than salmonids
(Abstracted article — details not available)
Sensitivity: Gammarus > Daphnia > cyclops
Lethal cone. 0.1 x 24hr LC50 for guppy
Slightly more resistant than salmonids
Coccochloris sp. Untreated effluent
" Secondary treatment
...
Non-chlorinated effluent
Chlorinated effluent
Untreated
Secondary treatment
Demonstrated acclimation to toxicant
—
Biobasin treated
99 hr additional treatment
Untreated
Untreated
Untreated
—
A crustacean
Fahmy & LustTT974
Litintsev 1967
Wilson 1975
DeWitt 1963
Dimick & Haydu 1952
Rainville et al. 1975
n ~~~ n
Loch & MacLeod 1973
Seppovaara 1973
H II
Holland et al . 1960
Loch & MacLeod 1973
Howard & Walden 1965
Servizi et al. 1966
Gordon & Servizi 1974
Howard & Walden 1974
Sprague & McLeese 1968
Betts & Wilson 1966
Howard & Walden 1974
Gazdziauskaite 1971a
-------
TABLE 1. CONCENTRATIONS OF PULP AND PAPER MILL EFFLUENTS LETHAL TO AQUATIC LIFE, (continued)
Effluent type
Sulflte (SHE)
Sulfite (SWL)
Groundwood (GME)
Wood and debarking
leachates
Species
Pacific salmon
n n
Atlantic salmon
n M
Pacific salmon
n n
Rainbow trout
II M
II
1) II
Atlantic salmon
Pacific salmon
n M
Rainbow trout
Daphnia
Gammarus
Cyclops
Snail
Rainbow trout
n n
i:
•'
i:
96hrLC50
(X by volume)
2
3-45
25-60
11-24
15
0.7-1.45
2,340 mg/1 (PBI)
3,000 "
0.18-0.29
1.1-3.5
8-12
2,500 mg/1 (PBI)
1-2
Varied
25
14-18
18-32 (72 hr)
> 100
> 100
0.2-4
0.2-2
9-45
^ 1
1.5-6
0.2-10
Comments
Untreated; Na and Ca base mills
Untreated Mg base
Untreated, Na base, high yield
Untreated, Na base, low yield
NHi, base including bleachery wastes
—
Neutral sulfite semi-chemical process
Aged 5 days
Samples limited to red liquors, NH,, base
Mg base
Main sewer
—
Mixed hardwood and softwood — maritime mill
Mixed wood species — many mills
Groundwood and some BKME effluent
ii ii n n n
n i n
n
Fir and spruce wood, nontoxic when bio-
treated 3 days
Pine, fir, and spruce wood, nontoxic if
treated > 5 days
Dense hardwoods
Estimated LC50 from * survival in 1%
solution
Jackpine wood; > 5 day treatment required
to detoxify
Softwoods (bark leachates)
Reference
Rosehart et al. 1974
II II
Wilson & Chappel 1973
M It n
Rosehart et al. 1974
Kondo et aT.~T973
WilsonT97F
Grande 1964
Wilson & Chappel 1973
II n II
Wilson 1972
Leach & Thakore 1974c
Howard & Leach 1973b
Wilson 1975
n II
II
Howard & Leach 1973a
II
McKague 1975
Howard & Leach 1973a
Leach et a_K 1974
^/Concentration expressed as Pearl Benson Index, an index to the amount of lignin present.
-------
than rainbow if the chironomid had no sediment in which to burrow. Juvenile
amphipods (Gammarus pseudolimnaeus) were more sensitive than were adults, but
there were no differences in sensitivity among instars of either chironomid or
mosquito (Aedes aegyptii).
Rainville et aj. (1975) reported that untreated KME was as toxic to algae
as to salmon; however, secondary treatment rendered the effluent nontoxic to
algae, but slight toxicity to salmon was retained. Wilson (1975) reported
reduction of growth of green algae was a more sensitive test than was death of
Daphnia magna, Gammarus fasciatus or rainbow trout, all of which were much
more sensitive than the growth of bluegreen algae or death of Cyclops S£.
Reduced algal growth may have been the result of increased death rate of
cells.
Sulfite
Early investigators seldom demonstrated acute toxicity of sulfite efflu-
ents other than that caused by high oxygen demand. More recently, acute
toxicity of whole sulfite effluent to juvenile Pacific salmon (Oncorhynchus
spp.) and Atlantic salmon (Salmo salar) has been reported at concentrations as
low as 2-3% v/v, indicating that untreated sulfite effluent can be as toxic as
kraft effluent; however, many 96-hr LC50 values have been reported between 20
and 60%. Effluents from the NH4-base mills are not appreciably more toxic
than those from Na-, Ca-, or Mg-base mills (Rosehart et aj. 1974). However,
effluent from an NH4-base mill utilizing bleach process was five times as
toxic as unbleached NH4-base sulfite effluent (Wilson and Chappel 1973).
Lagoon treatment lowered the toxicity of whole effluent (including bleaching
effluent) to near that of unbleached raw effluent.
Very little recent work has been reported on acute toxicity of sulfite
wastes to invertebrates, particularly with whole effluent. Gazdziauskaite
(1971a,b) reported sulfite mill whole effluent was "toxic" at 12.5% to the
freshwater shrimp Pontogammarus. Numerous studies have been reported concern-
ing the effect of sulfite wastes on bivalves, but the effect studied has been
abnormal development, not death, although the abnormalities often resulted in
death (Stein et aJL 1959; Woelke 1960, 1965; WoelkeetaJL 1970).
Most studies with sulfite effluents have been conducted with spent sul-
fite waste liquor (SWL) stream rather than whole effluent. SWL constitutes
the majority of the whole effluent and contains most of the toxic agents.
With the exception of bleaching effluents which are uncommon in sulfite mills,
inclusion of other process streams usually lowers the toxicity of SWL (Wilson
and Chappel 1973).
Groundwood
Reports concerning the toxicity of mechanical pulping effluents are
limited. This may be due to the belief that chemicals used in the other
pulping processes are primarily responsible for the toxic effects. Relatively
few chemicals are used in the groundwood process yet effluents of these mills
can be as toxic as any chemically produced pulp effluent. The 96-hr LC50 for
untreated groundwood effluent averages 5-10% (Howard and Leach 1973b), and
14
-------
values as low as 1-2% have been reported (Leach and Thakore 1974c). The
toxicity is due to the natural resin acids and fatty acids (Row and Cook
1971). Leach and Thakore (1974c) surveyed a number of Canadian groundwood
pulp mills and reported toxicity was a function of waste recycle and type of
wood pulped. Pine effluents are considered most toxic, followed by fir and
spruce. Hardwood effluents are the least toxic when groundwood pulped. The
season the wood is cut also has some influence on the toxicity of the effluent
(Howard and Leach 1973b).
Potential toxicity of groundwood effluent to invertebrate species was
indicated in a study of newsprint operations which utilized groundwood pulp
and purchased kraft pulp. This effluent at 20 C was nontoxic to Cyclops at
100% but toxic to Daphnia at 14-18% and Gammarus at 18-32% as compared to 25%
for rainbow trout at 15 C. No deaths were observed with snails (Bithynia sp)
but they showed a strong avoidance reaction by crawling out of the test cham-
mers. Green and blue-green algae were also exposed to the effluent, and cell
biomass was reduced in concentrations >50% (Wilson 1975).
Bark- and woodroom- leachates contain most of the toxic constituents
found in groundwood effluent, show similar toxicities, and therefore are
included in the groundwood section. These effluents can be a process stream
in kraft and sulfite mills as well. Less water is used per ton of material
during the debarking and chipping process than during mechanical pulping so
the effluents from the woodroom and debarking plants are generally more toxic
on a volume basis. Acute toxicity values (96-hr LC50) of 0.2 to 2% were
reported for woodroom effluent when pine was processed and 9 to 45% when
hardwood was processed (Howard and Leach 1973a,b; Leach and Thakore 1974c).
Groundwood effluent and woodroom- and bark- leachates respond to biotreatment
in a similar manner. These effluents from pine processing required more than
5 days biotreatment to render the effluent "nontoxic" during the 96-hr acute
bioassay; effluents from fir, spruce, and hemlock required 3 to 5 days, and
those from hardwoods 1 to 3 days. Such detoxification does not guarantee that
the effluent will not have a long-term or sublethal effect on aquatic life.
SUBLETHAL EFFECTS
The objective of investigation of sublethal effects is to determine the
nature of sublethal stress or effects due to pollutants, and then to measure
the threshold levels below which no effect can be observed. Stresses are
usually cumulative; one stress may ultimately reduce an organism's capability
to meet other stresses and, therefore, can influence the organism's survival.
Not all sublethal effects of pollutants are necessarily detrimental. Sprague
(1971) reviewed general procedures for sublethal effects measurements and dis-
cussed the problem of ascertaining "safe" levels for pollutants.
Known sublethal effects of pulp and paper effluents are attributed to
conifer fibers, volatile reduced-sulfur compounds, and nonvolatile soluble
toxic components. Table 2 lists much of the recent data on sublethal effects
of whole pulp mill effluent on aquatic organisms. Most of the work has been
with salmonids, with only a few observations on invertebrates and algae. The
table is arranged by system affected. Because of the large variation in
toxicity of pulp mill effluents, sublethal effects are expressed as a fraction
15
-------
TABLE 2. SUBLETHAL EFFECTS OF PULP AND PAPER MILL EFFLUENTS ON AQUATIC LIFE.
cr>
Threshold concentration
Effects
RESPIRATORY
Coughing response elevated
ii M ii
ii
Ventilation volume increased
Oxygen uptake increased
n n n
CIRCULATORY
Arterial oxygen tension reduced
ii II II II
White blood cells reduced
Blood neutrophil count elevated
Hematocrit reduced
Small lymphocytes decreased
Neutrophil is Increased
Hematocrit reduced
Blood values reduced
II II li
ri ' ii :i
METABOLISM
Plasma glucose elevated
-* .'I
.,yu - .1
u i
Body protein decreased
Muscle protein depressed
Liver glycogen depressed
n
Liver RNA decreased
Blood and muscle lactate increased
Swimming ability reduced
n n n
Species
Rainbow trout
ii ii
Sockeye salmon
n n
Pontogammarus
Salmonids
Rainbow trout
Sockeye salmon
Coho salmon
n n
Sockeye salmon
Coho salmon
n n
n
Rainbow trout
Carp
Pontoqammarus
Coho salmon
1
i: in
Rainbow trout
ii ii
Coho salmon
Sparus
macrocephalus
Coho salmon
S. macroceph-
alus
Coho salmon
M It
Pontoqammarus
Effluent
type
KME
II
BKME
M
SME
SWL
BKME
II
KME
II
KME
II
SME
II
BKME
KME
II
BKME
II
KME
BKME
KME
BKME
KME
SME
fraction of
96-hr LC50
0. 08,0.18
0.5*7
0.1-0.2
0.2
0.33
— •
> 1.0
0.47
0.33
0.1
0.25
> 0.33
n
'
—
— .
0.8*/
0.1
0.0-0.3
0.1-0.25
II
0.1
—
0.1
0.25
0.1-0.2
% volume Comments
11 Immediate effect
Untreated; (treated no
effect)
Possible adaptation
Immediate effect
M II
12 LC50 independent of life
stage
100
No adaptation
n n
2.4 21 day expos.
200 day expos.
1.5 8 week expos.
25 day expos.
12 day expos, (returned
to normal in 25 days)
25 day expos.
Abstracted article
it n
12-25 Increased respiratory
quotient
44 Fish also stressed by
swimming
200 day expos.
Increased for 12 days;
decreased in 25 days.
200 day expos.
M n n
•
3.2-6.2 12-24 hr. expos, in
river
n if u n
1 II 1 :,.
200 day expos.
1.8-9.0
12-25 Abstracted article
Reference
Wai den et^ al_. 1970
Schaumburg et^ al_. 1967
Davis 1973
n M
'
Gazdziauskaite 1971a,b
Williams et_ aK 1953
Davis 1973
M II
McLeay 1973
Howard & McLeay 1972
Webb & Brett 1972
McLeay 1973
II M
Howard & Wai den 1967
Seppovaara 1973
II n
Gazdziauskaite 1971b
McLeay & Brown 1975
Howard & McLeay 1972
McLeay 1973
McLeay & Brown 1974
n n M
Howard & McLeay 1972
Fujiya 1961
Howard & McLeay 1972
Fujiya 1961
Howard & McLeay 1972
Howard 1975
Gazdziauskaite 1971a,b
-------
TABLE 2. SUBLETHAL EFFECTS OF PULP AND PAPER MILL EFFLUENTS ON AQUATIC LIFE, (continued)
Threshold concentration
Effects
BEHAVIOR
Avoidance
t
i
ii
iii
No avoidance
Drift Increased
Orientation to current
Alarm response slowed
Unresponsive
Feeding reduced
H H
n
n
1
No feeding
MORPHOLOGY, HISTOLOGY
Liver, kidney, Intestine
Liver
Opaque eyes
n ii
Abnormalities Increased
ii i
II 10
GROWTH
Growth rate reduced
M n ii
i
u i ii
n u i
Species
Sockeye salmon
Atlantic salmon
u n
Chinook salmon
n n
Lobster
Snail
Salmonids
Coho salmon &
Steel head
Gammarus
Sockeye salmon
u n
Coho salmon
n n
Chinook salmon
ii n
Pontogammarus
Lobster
Salmonids
Sparus
macrophalus
Chinook salmon
1
i n
Oyster
Clams
Oyster
Sockeye salmon
u H
Chinook salmon
II M
Effluent
type
BKME
KME
H
KME
II
BKME
KME & GME
SWL
KME
BKME
Ii
KME
n
LI
"
SME
BKME
KME
KME
KME
1
SWL
1
KME
BKME
KME
n
fraction of
96-hr LC50
0.8
0.37
0.0006
_-_
...
...
...
.__
—
—
0.8
0.4
0.15
0.1-0.2
0.14-0.36
0.1-0.3
—
—
...
—
___
—
—
0.05-0.1
0.14-0.35
0.1-0.3
—
% volume
50
5-10
50
> 20
—
...
100
> 1
—
—
—
—
12-25
> 10
100
3.2-6.2
*
33l
6.6
6-12 ma/1
(PBIF
1-3 mg/1
(FBI)
0.15-0.5
10-25
...
1.5
—
6
Comments
Bleachery wastes — not
whole effluent
Strong response
Vague response
Variable results
Bleachery wastes
Lowest level tested
Avoid low but not high
cone.
Variable results
Bleachery wastes
II II
Response lasted 2 wks.
Long term study
2 week expos.
LC50 Independent of life
stage
12-24 hr expos, in river
"Synthesized wastes"
7 day expos.
n i
u
> 20% Increase In
abnormalities
ii n n n
Mg. base most toxic
(untreated effluent)
8 wk expos.
—
...
—
...
Reference
Servlzl et al_. 1966
Sprague & Drury 1969
n n n n
Jones et al. 1956
Dimick et~Tl. 1957
McLeese~T970~
Wilson 1975
Dimick et al. 1957
Galtsoff et al. 1947
Servizi eFaT7l968
II ~~ ~~ n
Davis 1973
ii H
Ellis 1967
Tokar & Owens 1968
Gazdzlauskaite 1971a,b
McLeese 1970
Williams et al. 1953
Fujlya 1961
Holland e£al_. 1960
1
r
Woelke 1960
Woelke et a]_. 1970
1970. 1972
Webb & Brett 1972
Servizi et al. 1966
Ellis 1967 ~
Tokar & Owens 1968
Warren 1972
-------
TABLE 2. SUBLETHAL EFFECTS OF PULP AND PAPER MILL EFFLUENTS ON AQUATIC LIFE, (continued)
00
Threshold concentration
Effects
GROWTH (cont)
Growth rate reduced
• ii
1 '
1
•
" '
1
u i
n
j i
II II
II i
1
Growth efficiency reduced
M II II
PRODUCTION-ABUNDANCE
Production reduced
u
1 I
II
1
1 '
Production enhanced
<< i
U tt
n n
Diversity change
Species Effluent
type
Chinook salmon KME
Coho salmon '
Pontogammarus '
Oyster larvae
0.25
Several wk. exp. Davis 1973
70 day expos. Howard & McLeay 1972
—
McLeay 4 Brown 1974
15 Abstracted article Seppovaara & Hynnlnen 1970
25 (a green algae) Wilson 1975
...
—
—
...
50
50
50
50
50
a green algae) " "
a blue-green algae)
a green algae) ' "
a green algae) " '
a blue-green algae) "
10-25 8 wk. expos. * Webb & Brett 1972
0.06-0.12
0.19
0.08
0.03 mg/l BOD
0.75 mg/l BOD
A 1
— S/
0.2
1.5-3.0 mg/l
BOD
1.5 BOD
0.4-0.9 12 day expos. Tokar & Owens 1968
1.5 Lab streams; winter, Seim ejt al_. 1977
blotreated effluent
Lab streams (untreated Ellis 1967
effluent)
1.5 Lab streams (untreated Lichatowlch 1970
effluent)
0.35 Stream channel (prim. Warren et al. 1974
treatment)
u n :i
Outfall area (Cladocera FiHmonova 1968
and rotifers absent)
1.4 Lab streams (stabilized Lichatowlch 1970
effluent) Mill B
0.7-1.5 Lab streams (prim. '
treated effluent) Mill B
7.5 Lab streams (stabilized
effluent) Mill A
— 5 Stream channels Warren et al. 1974
(treated effluent)
0.2-5 Stream channels (treated
and untreated effluent)
— » Stream channels (un- Warren et al- 1974
treated effluent)
" — 100 Treated effluent channel Shlreman 1975
untested concentration, not a threshold value
2/Pearl Benson Index, an Index to the amount of Hgnin present
g^effluents were not acutely toxic, therefore effective concentrations were expressed as 5-day
^threshold concentration given as 0.5 of the 96-hr LC50 value for rainbow trout.
S/ " " " " 0.05 ' " " " Chinook salmon.
BOD.
-------
of the LC50 value for that organism. If known, the percents by volume (% v/v)
are included. In cases where 100% effluent was not acutely toxic the concen-
tration has sometimes been expressed as mg/1 BOD.
Because the data in Table 2 were derived from many effluents and over a
considerable period of time, meaningful comparisons between tests are diffi-
cult to make. However, one can see some general trends in threshold concen-
trations in terms of 96-hr LC50 values. If the same compounds causing acute
toxicity also cause the sublethal effects, threshold concentrations expressed
as a fraction of the LC50 values should compensate for the difference in the
concentration of the toxic constituents among these effluents and, thus, make
comparisons of sublethal tests among mills more meaningful. For example, the
threshold of sublethal effects of kraft mill effluents frequently appears to
be about 1/10 of the 96-hr LC50 (0.1 LC50) concentration but could be almost
any v/v concentration depending upon the mill sampled. Several sublethal
tests showed effects at concentrations below 0.1 LC50. These were: the cough
response in rainbow trout at 0.08 LC50 (Walden et al_. 1970); reduced salmon
production in laboratory streams at 0.08 LC50 (Ellis 1967); reduced growth of
sockeye salmon (Oncorhynchus nerka) at 0.05 LC50 (Servizi et al^. 1966); and
reduced temperature tolerance of Coho salmon at 0.06 LC50 (Howard and Walden
1974). These more sensitive tests should be considered when sublethal effects
of pulp mill effluents are to be studied.
Kraft
The effects of kraft mill effluents on respiration are evidenced by
increased coughing, ventilation volume and oxygen uptake rate (Walden et aj.
1970; Schaumburg et al. 1967; Davis 1973). These effects are exhibited rather
rapidly and can be used in short term tests. Davis (1973) has shown that
respiration effects diminish with long exposures and that the usefulness of
these effects in continuous monitoring as suggested by Schaumburg et al.
(1967) may be lessened. The threshold of the respiration tests is somewhere
near 0.1 LC50.
The circulatory system was affected by kraft effluent resulting in re-
duced arterial oxygen tension and white blood cell count, small lymphocyte
count, low hematocrit level, and elevated blood neutrophil count (Davis 1973;
Howard and McLeay 1972). McLeay (1976) has developed a sublethal test which
uses a "chemical profile" of biochemical responses in fish exposed to low
concentrations of kraft mill effluent. After a few hours exposure to sub-
lethal concentrations, blood parameters are significantly altered as are the
glycogen and lactic acid contents of several tissues. The biochemical tech-
niques have advantages because they have been completely automated by medical
science and only small blood samples are necessary. The effects of pulp mill
effluents on some of these biochemical parameters have also been reported to
show adaptation after several days of exposure and may indicate that no perma-
nent harm has been done to the fish (Davis 1973; McLeay 1973).
The effect of kraft mill effluents on metabolism in fish was evidenced by
elevation of plasma glucose and blood lactate levels and depression of body
protein, muscle and liver glycogen, and swimming ability. The range of sensi-
tivities of these tests was 0.1 to 0.3 LC50 concentration.
19
-------
Avoidance behavior often protects an organism from exposure to poten-
tially lethal toxic materials. Some salmonids appear to detect concentrations
of KME as low as 5% v/v but most avoid only much higher concentrations. Well-
defined avoidance occurred only at concentrations approaching lethal levels
(Dimick et aJL 1957; Jones et aJL 1956; Servizi et aJL 1968). The increased
drift of amphipods in streams containing 10% KME may have been an avoidance
reaction (Ellis 1967; Galtsoff et aJL 1947). Lobsters (Homarus americanus)
have been shown to avoid concentrations of 20% or more (McLeese 1973). Snails
(Bithynia) avoided, by escaping from the test containers, all concentrations
(unspecified) of KME and GME tested, but when escape was prevented they sur-
vived even at 100% concentrations (Wilson 1975).
Feeding behavior is also influenced by KME. Appetite of juvenile coho
and chinook salmon was reduced at concentrations of 0.1 to 0.36 LC50 (Davis
1973; Ellis 1967; Tokar and Owens 1968). Loss of attraction to food was
reported in lobster at concentrations greater than 10% v/v (McLeese 1973;
Galtsoff et aj. 1947).
Morphological and histological changes in fish following exposure to
kraft mill effluents have been observed. Holland et a^L (1960) exposed Chin-
ook to "synthetic" wastes (bench-produced pulp wastes) for seven days and
observed opacity of their eyes, discolored liver, and hemorrhages. Fujiya
(1961) held the fish, Sparus macrocephalus, in live-boxes below pulp mill
outfall for 12-24 hr. He reported considerable damage to the liver, kidney
and intestine, but these results could not be substantiated by McLeay (1973).
However Fujiya (1964) was subsequently able to duplicate his results and
concluded that either the mill's effluent was reacting with some unknown
constituent in the river water to produce the drastic effect or the effluent
was particularly toxic.
A stress imposed on an organism may lower its tolerance to other factors.
Howard and Wai den (1974) have shown that very low concentrations of BKME
(0.06-0.23 LC50) reduced the upper temperature tolerance in coho salmon.
Starvation time to death in coho salmon was reduced at 0.4 LC50 of untreated
BKME but treated BKME showed no effect at 0.7 LC50 (Brown and McLeay 1975).
The decreased starvation time would be indicative of increased metabolic rate.
Growth of fish is generally decreased by KME. Concentrations as low as
0.05 LC50 reduced growth in sockeye salmon (Servizi et aJL 1966). Other
authors have reported threshold values for reduced growth up to 0.35 LC50 for
salmonids (Table 2). Davis (1973) and Howard and McLeay (1972) observed
reduced growth in coho for several weeks, followed by growth enhancement.
Apparently the coho salmon adapted to the effluent and eventually gained some
benefit from it.
Warren et aK (1974) developed a growth test that appears to be very
sensitive. They used natural and artificial foods that, when uneaten, could
be recovered and the actual food consumption rate determined. Fish are fed a
series of rations from near-maintenance to satiation at each effluent concen-
tration and food consumption and growth are measured. Growth can be restric-
ted by decreased food intake (loss of appetite) or by a decrease in the effic-
iency of food utilization for growth, or both. The decrease in food utiliza-
20
-------
tion can be due to increased maintenance costs or decreased digestive effic-
iency. Kraft effluent has been shown to reduce appetite at concentrations as
low as 0.06 to 0.1 LC50 and to increase maintenance costs at 0.2 LC50 (Davis
1973; Borton 1970; Tokar and Owens 1968; Ellis 1967).
The growth of algae is typically increased by low concentrations of KME
due to nutrients in the effluents; however, at higher concentrations toxic
components counter the effect of the nutrients and even higher concentrations
reduce growth below that of the controls. The maximum increase in green alga
growth occurred at a 25% v/v concentration which is near the 96-hr LC50 con-
centration (26%) for rainbow trout. However, the growth of blue-green algae
was increased by all concentrations of effluent tested (Wilson 1975). Seppo-
vaara (1973) observed maximum increase in the growth of green algae with 15%
concentration of KME.
Growth and development of oyster larvae (Crassostrea gigas) were impaired
at concentrations of 0.15 to 0.5% untreated KME and 1.3% biotreated KME (Woelke
et al. 1972). Development and growth of salmonid embryos were more resistant
to KME than was growth of later life stages (Holland et al_. 1960).
For a number of years, researchers at Oregon State University have con-
ducted investigations on the effects of untreated and biotreated KME on the
productivity of laboratory streams and of 100 m stream channels dug in a
natural environment. These streams contained many of the algae and inverte-
brates found in small natural streams. Fish placed in these streams were not
artificially fed and their production was used as a measure of the produc-
tivity of the stream ecosystem. Initially, tests were conducted using KME
that received only primary treatment to remove solids; later KME receiving
secondary treatment in aeration ponds was tested and finally KME receiving
more extensive biotreatment in stabilization basins was studied.
In early studies, Ellis (1967) showed that production of Chinook salmon
was reduced in laboratory streams receiving primary-treated KME at a concen-
tration of 0.14 LC50 (0.75% v/v) in winter and 0.36 LC50 (1.5%) during spring
and summer. These effects were more pronounced at higher fish densities. The
reduced fish production was attributed to toxic effects of the effluent on the
fish because the food supply of the fish increased.
More recently Seim et aJK (1977) reported that fish production was re-
duced in laboratory streams receiving 1.5% biotreated effluent during the
winter but production increased during other seasons at levels up to 4%, with
the greatest increase at 1%. Enhanced production during the summer was attri-
buted to enrichment effects and diminished toxicity from better biotreatment.
In all the laboratory stream studies conducted at Oregon State University
none of the reductions in total fish food organisms observed could be directly
attributed to either untreated or treated KME, although the abundance of some
organisms would sometimes change. Increases in fish food organisms could
often be attributed to both untreated and treated KME. The reduction in fish
production or biomass in these streams may be due to loss of appetite or
reduced food conversion to growth (Tokar and Owens 1968).
21
-------
Trout and salmon production in artificial stream channels was not influ-
enced by any concentration of KME tested (Warren et a_L 1974). Snail popula-
tions increased with all effluents tested. Density of "fish-food" organisms
(collectively) was not affected, although some shifts in species abundance did
occur. Caddis fly larvae (Hydrosyche) and amphipod (mostly Crangonyx) popula-
tions declined with primary treated effluent. Amphipod densities increased
with better treated effluents (Botton 1974; Warren 1972). No effect of KME
could be shown on the hatchability of salmon eggs in these channels (Mower
1974). Initially these channels contained concentrations of primary treated
effluent of about 0.22%, (-v 0.25 LC50 for salmonids). Subsequently, the
streams were dosed with biotreated effluent to obtain a 0.74% (~ 0.01 LC50)
concentration. As the mill effluent was improved through internal modifica-
tion and more extensive biotreatment, the dosing rates were increased to
obtain concentrations as high as 5% (100% effluent was not toxic in 96-hr
tests). The 5% rate is many times (25-50) the concentration likely to exist
in the Willamette River near Albany, Ore. at low flow, provided the effluent
is completely mixed.
Warren et aj_. (1974) stated that fish production was not reduced in
either the laboratory streams or the artificial stream channels by any efflu-
ent concentration not also causing growth reduction in salmonids during simple
laboratory growth studies. Growth in laboratory tests appears to be a more
sensitive test than is fish production in artificial streams. Growth studies,
however, would not have predicted the enhanced fish production in the streams.
The enrichment and associated increased production observed in some tests may
be undesirable in some watersheds where increased eutrophication would be a
problem.
The National Council for Air and Stream Improvement (NCASI) is initiating
studies in Georgia with outside artifical stream channels similar to those
used by Warren. Warm-water species will be tested but no reports are cur-
rently available.
Sulfite
Sublethal effects of sulfite wastes have received much less attention
than those for kraft wastes because not many sulfite mills are being construc-
ted and the effluent is not very toxic after BOD-reduction treatment. Because
of the low toxicity of sulfite mill effluent (SME) many studies have been
conducted with the spent sulfite waste liquor (SWL) stream which contains most
of the toxic components. Table 2 lists many of the reported sublethal effects
of both SME and SWL on aquatic organisms. The sublethal concentrations of SME
and SWL reported in the literature usually have not been related to lethal
concentration as has been the case with KME. Therefore sublethal concentra-
tions of SME and SWL listed in Table 2 are expressed as percent by volume or
by the Pearl Benson Index (FBI) which is an index to the amount of lignin
present. The table is organized by system affected, however, the text will be
presented by author since a small number of investigators have done most of
the work.
Williams et aJL (1953) described the sequence of effects of acutely toxic
concentrations of SWL on fish prior to death. Many of these syndromes have
22
-------
been observed by others during sublethal tests. In an abstracted article,
Seppovaara (1973) reported that "blood values" of rainbow and carp were re-
duced by sublethal levels of SME. The concentrations tested were not given in
the abstract. In another paper he reported the production of green algae was
reduced by concentrations greater than 15% SME (Seppavaara and Hynninen 1970).
A Russian author, Gazdziauskaite (1971a,b) studied the effects of SME on
freshwater shrimp (Pontogammarus). He observed reduced growth at 1.5%, re-
duced reproduction at 3-12%, and at 12-25%; increased respiration rate, re-
duced feeding behavior, reduced "blood values", and in some cases immobiliza-
tion. It should be noted that in this series of tests, growth was the most
sensitive index of effect.
The effect of sulfite waste liquor (SWL) on the oysters (Ostrea lurida)
and Crassostrea gigas) and clams (Tresus nutalli and Protheca stamina) have
received considerable study as these animals are quite sensitive to SWL
compared to Salmonids (Stein et aj. 1959; Woe Ike 1960, 1965, 1976; WoeIke
et aJL 1970, 1972). Concentrations above 55 mg/1 (PBI) inhibit spawning;
however, lower concentrations can stimulate spawning, but the resulting spawn
shows a higher percentage of abnormal larvae. Concentrations as low as 0.15-
0.5% or 1-3 mg/1 (PBI) increase the number of abnormalities. Magnesium-
sulfite mill effluent was more toxic than ammonia-sulfite mill effluent at pH
7. At high pH (above 9) the ammonia-sulfite mill effluent was more toxic
indicating that ammonia was causing the toxicity.
Groundwood
Few references are available regarding the sublethal effects of whole
groundwood mill effluent. Woelke (1976) examined the effect of groundwood and
debarker wastes on the development of embryonic oysters and reported that the
no-effect concentration was near 1.3% v/v. Wilson (1975) presented some
sublethal effects data on effluents from a newsprint plant that manufactured
groundwood pulp and purchased some BKME. Snails avoided the lowest effluent
concentration tested by crawling out of the test chamber, but were not killed
by full strength effluent when escape was prevented. Algal growth was also
influenced by this effluent. Maximum stimulation of growth in algae occurred
at 25% concentration for untreated effluent and 75-100% for treated effluent.
TOXIC COMPONENTS
Toxic components of pulp and paper effluents are complex mixtures of
organic and inorganic moieties (naturally occurring and added or formed during
pulping processes). Only recently have specific components been isolated and
identified, mostly through the work of the Canadians. Many of these compo-
nents have been tested for toxicity. Several naturally occurring resin acids
are responsible for the majority of toxicity in non-bleached pulp effluent.
Chlorinated compounds contribute the majority of toxicity in bleached pulp
effluent. Tables 3 through 7 list the principal toxic constituents, their
toxicity to salmonids, relative contributions and approximate loading in
untreated pulping effluents.
23
-------
TABLE 3. PRINCIPAL TOXIC CONSTITUENTS IN PULPMILL WASTE STREAMS (from Leach and Thakore 1977)
ro
-p.
Effluent and 96-hr LC50 range (%v/v) Major Contributor and Loading (kg/ton)-1
a/
Debarking (0.2-40)
Mechanical pulping (2-10)
Kraft pulping (2-40)
(unbleached white-
water)
Sulfite waste liquor
Acid bleach
(chlorination stage) (10-80)
Caustic extraction (2-40)
Resin acids
Resin acids
Resin acids
(0.02-0.05) Resin acids
Chlorolignins
Chlorinated phenols
Chlorinated resin acids
Chlorinated stearic acids
(0.02-0.35)
(0.02-1.1)
(0.5)
(0.9)^
(0.02-0.91)
(0.02-0.01)
(0.08-0.37)
Other identified
contributors
Diterpene alcohols
Diterpene alcohols
Unsaturated fatty
acids
Juvabiones
Unsaturated fatty
acids
Juvabiones
Pitch dispersants
- Weight of major contributor produced per ton of wood debarked
- Limited sample size, may not be representative
-------
TABLE 4. CONCENTRATIONS AND ACUTE TOXICITIES OF RESIN ACIDS FOUND IN SOFTWOOD
PULPING AND DEBARKING EFFLUENTS (from Leach and Thakore 1977)
Resin Acid
96-hr LgS.0
2.0-22.1
3.4-22.9-/
2.6-16.0
2.6-15.7-
0.7-19.9 67.4
0.4-22.1 51.8
0.6-17.2 8.7
Concentration Ranges (mg/1) in Effluents
(mg/1)- Debarking Mechanical Kraft Sulfite^'
Pulping Pulping Waste Liquor
Abietic 0.41
Dehydroabietic 0.75
Isopimaric 0.22 2.4-33.$ 2.7-35.0^
Palustric 0.55 — 2.8-7.7
Pimaric 0.32 0.8-7.6 < 0.1-5.9
Sandaracopimaric 0.36
Total 0.3-0.5 10.4-78 12.1-61.8
No. of Samples — 88 24
No. of Mills — 10 2
0.2-8.7
9.8
2.3-54.8 141.8
21 1
10 1
-Toxicant solutions renewed every 4-8 hr; test fish was coho salmon
-''value is for SWL; not whole SME. Wilson and Chappel (1973) found total
resin acid concentrations were generally less than 10 mg/1 for SME.
- Includes neoabietic acid
- No solution replacement; test fish was rainbow trout
TABLE 5. TOXICITY TO JUVENILE COHO SALMON OF LONG-CHAIN FATTY ACIDS PRESENT
IN DEBARKING AND PULPING EFFLUENTS (from Leach and Thakore 1977)
Fatty Acid Palmitic Stearic Oleic Linoleic Linolenic Palmitoleic
Carbon No. Cic Ci« Ci« Ci« Ci« Ci«
LT50 (min)-7 > 96 h
at 12 mg/1
> 96 h 2000
220
160
150
-''time to death for 50% of the test fish
25
-------
TABLE 6. TOXIC CONSTITUENTS IN KRAFT MILL CAUSTIC EXTRACTION EFFLUENTS-/
(after Leach and Thakore 1977)
Compound
Trichloroguaiacol
Tetrachl oroguai acol
Monochloro-
dyhydroabietic aci
Dichloro-
deyhydoabietic aci
Epoxystearic acid
Dichlorostearic acid
96-hr LCSO^7
(mg/1)
0.75
0.32
d 0.6
d 0.6
1.5
2.5
Concentra-
tion Range
(mg/1)
0.2-1.2
0.2-1.1
ND^-4. 3
ND-2.5
1.5-17
ND-13
Toxic
Units
(max)
1.6
3.4
7.2
4.2
11.3
5.2
Loading
kg/day
1-26
1-18
<0.5-35
<0.5-20
8-136
27-113
Range
kg per
ton pulp
<0. 01-0. 06
<0. 01-0. 04
<0. 01-0. 07
<0. 01-0. 04
0.03-0.18
0.05-0.19
- 17 samples from 9 mills
- Test fish juvenile rainbow trout (S_. gairdneri).
replacement.
-not detected
Bioassay with no solution
TABLE 7. TOXIC NEUTRAL EXTRACTIVES FOUND IN VARIOUS EFFLUENTS (from Leach and
Thakore 1977)
Diterpene Alcohols
Compound
Pimarol
Isopimarol
Dehydradrobi etol
Abietol
96-hr LCSO^7
(mg/1)
0.3
0.3
0.8
1.8
Insect Juvenile Hormone Analogs
Compound 96-hr LC50-
Ong/i)
Juvabione
Juvabiol
A4'-Dehydro juvabione
Duhydro juvabione
1.5
1.8
0.8
2.0
- Bioassays withou
it solution replacement;
test fish was juvenile rai
nbow trout
- Bioassays with solution replacement every 4 hr; test fish was juvenile rain-
bor trout - Leach et al. (1975)
26
-------
Kraft
Early work demonstrated that bivalent sulfur compounds were present in
lethal quantities in kraft mill effluents (Van Horn 1961, 1971; Van Horn
et aj. 1949, 1950). These compounds include hydrogen sulfide and methyl
mercaptan which are toxic at very low concentrations. The acute toxicity of
hydrogen sulfide to goldfish (Carassius auratus) and salmonids is in the range
of 0.036 to 0.087 mg/1 (Adelman and Smith 1972; Smith and Oseid 1972). Methyl
mercaptan toxicity is similar to that for hydrogen sulfide. Because of the
volatile nature of these compounds, most are lost to the atmosphere during
aeration treatment that the majority of pulp effluents in the U.S. now re-
ceive. Ng et a_K (1974) have shown that the relative contribution of these
volatile substances to acute toxicity was only 5.4% in samples which were not
biologically treated; such treatment would reduce the contribution even fur-
ther. Chevalier (1973) emphasized that LC50 values for hydrogen sulfide
measured by flow-through bioassays are about one-half those measured by static
bioassays because of the volatility of hydrogen sulfide.
The non-volatile fraction contains most of the toxic components in KME.
Rogers (1973) and Leach and Thakore (1974a) documented the contribution of
the majority of non-volatile compounds to the toxicity of KME. Bioassays were
run at each stage of extraction to insure that all toxic materials were re-
tained. Eighty percent of the toxicity was due to resin acids and three
unsaturated fatty acids in KME from hemlock and fir pulping wastes.
The acute toxicity of the more common resin acids and fatty acids in KME
is given in Tables 4 and 5. The toxicity of resin acids was greater at pH 6.4
than pH 7.5 (Leach and Thakore 1977). Straight-chain fatty acids contributed
18% of the non-volatile toxicity in KME from hemlock and fir wood (Leach and
Thakore 1973). None of these fatty acids alone were found to be toxic at the
concentrations present in the original sample.
Various other toxic components in KME have been reported, although their
contribution to toxicity is usually not known. Banks (1969) isolated an
extremely toxic diol (structure not determined); Marvel 1 and Werner (1963)
isolated 4 (p-Tolyl)-l-l penantol from the condensate stream; and Werner
(1963) isolated a toxic sulfur-containing compound from black liquor wastes.
In non-chlorinated KME, lignin and its degradation products show little
or no toxicity (Brebion et al_. 1957). Various simple phenolic compounds in
KME are quite toxic to fish, but they do not appear to contribute to effluent
toxicity at concentrations present in KME.
Chlorine is commonly used to bleach kraft pulp. The KME has a high
chlorine demand. Much chlorine is reduced to chlorides and some binds with
other compounds. Chlorination reduces toxicity of resin acids, presumably
through oxidation (Wong 1976; Leach and Thakore 1975b). Only the more stable
pimaric and dehydroabietic acids survive chlorination in significant amounts.
If kraft pulp is acid-chlorine bleached, lignin and related compounds can
become quite toxic, and constitute a major portion of the toxicity of bleach-
ery effluent (Waiden 1976). The exact nature of chlorinated lignins are not
27
-------
known. Other toxic components that have been identified in bleaching wastes
are: tetra-chloro-o-benzoquinone and trichloro-vertatole (Das et a_L 1969;
Rogers 1973) and two chlorinated catechols (Servizi et aJL 1968). With caus-
tic extraction, resin acids, ligins, phenols and stearic acid can be chlor-
inated (Leach and Thakore 1974b, 1975a). These compounds were generally toxic
at less than 1 mg/1 and accounted for 80% of the toxicity of the original
sample of BKME (Table 6). When these compounds were combined in original
concentrations they yielded a concentration-toxicity curve identical to that
obtained for the original sample.
The neutral fraction of BKME contains some toxic components; however,
their contribution to toxicity is small (Table 7). Alcohols and aldehydes
related to the resin acids are present (Leach and Thakore 1975a,b). Rogers
and Mahood (1974) have identified diterpene aldehydes and ketones in BKME in
which resin acids were absent and they suggested that resin acids may be
converted to these compounds during the bleaching process. Wilson and Renner-
felt (1971) implicated terpenes from BKME in fish tainting. Warren et al.
(1974) showed that BKME with added terpene recovery system exhibited reduced
toxicity and permitted increased fish biomass in artificial streams.
The toxic effect of components of KME on aquatic organisms other than
fish have received little attention. Wilson (1975) reported the 96-hr LC50
for Daphnia exposed to linoleic and dehydroabietic acid in soft water was 3.2
and 4.2 mg/1 and in hard water was 5.2 and 7.4 mg/1. These values are much
higher than those for salmonids. He also studied the effect of these acids on
the growth of algae (Scenedesmus) and reported stimulation at 5.6 mg/1 and
retardation at 10 mg/1. Researchers for the NCASI (1947) have also studied
the effects of KME components on Daphnia. Daphnia are quite sensitive to
methyl mercaptan (1.5 mg/1, 48 hr LC20), hydrogen sulfide (1.7 mg/1, 28 hr
LC20), fatty acid fraction (6 mg/1, 48 hr LC20) and resin acid fraction (10
mg/1, 48 hr LC20). Several species of freshwater minnows were even more
sensitive to these compounds.
No references were found concerning the effects of chlorinated components
in BKME on non-fish species.
Sulfite
Only recently have attempts been made to ascertain the toxic moieties of
sulfite waste effluents. Wilson and Chappel (1973) identified approximately
half of the total toxicity from a high-yield sodium-sulfite mill effluent.
The normal resin acids constitute about 26% of the total toxicity or one-half
of the identified toxicity. Two phenolic type compounds, eugenol and trans-
isoeugenol represent about 20% of the total toxicity; another unidentified
phenolic compound was responsible for 8% of the total toxicity. Nelson and
Hemingway (1971) also found appreciable quantities of resin acids in bisulfite
waste liquors.
More resin acids appear to survive the pulping process in high-yield than
in low-yield sulfite mills, and thus high-yield effluents are generally more
toxic than low-yield effluents (Waiden 1976). The differential survival of
resin acids between the two pulping process may explain why Kvasnicka and
28
-------
Mclaughlin (1955) found no resin acids present in waste from low-yield sulfite
pulping of spruce, but found a number of toxic phenolic compounds. The toxic-
ities of these compounds were not reported, but the compounds include: cyeme;
tetrahydrocadalane; 2-furoic acids; vanillin; vanillic acid; 2-conidendrin
melene; vanilloyl acetyl; dehydroconferyl alcohol; 3,3' dimethoxy 4,4' dihy-
droxystilbene; and 25 other phenolic compounds.
Groundwood
Resin acids have been implicated as principal toxic constituents in
groundwood effluents (Row and Cook 1971, Zitko and Carson 1971). Recent
studies by B.C. Research (Vancouver, Canada) have identified a number of resin
acids as major contributors to toxicity (Table 3 and 4). This acid fraction,
which included abietic, dehydroabietic and palustric acids, contributed the
major portion of the toxicity. Minor constituents included pimaric, sandara-
copimaric, isopimaric and neoabietic acids and the unsaturated fatty acids—
oleic, linoleic and linolenic. Up to 35% of the toxicity in some samples was
from the neutral fraction (Leach and Thakore 1974c; Leach et al_. 1975). These
materials include the diterpene alcohols, pimarol and isopimarol, and several
juvabione compounds. The juvabiones are juvenile-insect-hormone analogs and
may be particularly toxic to aquatic insects, but such tests have not been
conducted (Table 7).
Proper treatment can greatly reduce the resin acid concentration. Acti-
vated sludge treatment of groundwood effluent reduced the average concentra-
tion of resin acids from 28 mg/1 to 2.2 mg/1, whereas, aeration in a lagoon
only reduced the resin acid concentration to 18.1 mg/1 (Howard and Leach
1973b).
Process streams
Process streams other than the pulping effluent show toxicity. For some
time it has been known that high levels of resin acids are present in barking
effluent (Zitko and Carson 1971). More recently, McKague (1975) identified
many of the toxic materials in softwood debarking effluents. The acid frac-
tion containing the resin- and fatty-acids accounts for 90% of the toxicity.
The neutral components showing some toxicity include a number of wood alco-
hols. Leach et al. (1974) have completed a definitive study on the toxic
constituents in the effluents from woodrooms (debarking, grinding and storage)
at several mills. Jackpine woodroom effluents had the highest resin acid
concentration (35.7 mg/1) and were the most toxic. The lowest toxicity and
the lowest resin acid level (5.4 mg/1) were in effluents from barking and
storage of hardwoods. Hemlock, fir, and spruce effluents were intermediate.
Miscellaneous constituents
One component of all pulping processes which has caused major environ-
mental damage in the past has been high suspended solids consisting mainly of
wood fibers. Numerous references describing the extent and effect of fiber
mats in receiving waters were cited by Springer and Atalla (1974). Even
though fish can tolerate high levels of suspended solids, woody fibers can be
acutely toxic to fish. Groundwood fibers are more toxic to fish than chemi-
29
-------
cally produced fibers, but lethal doses of fibers are rarely released from the
mills (Smith et aJL 1965). MacLeod and Smith (1966), Kramer and Smith (1965,
1966), and Smith and Kramer (1964) reported 72-hr LC50 values between 738 and
2,000 mg/1 for fathead minnows (Pimephales promelas). In addition, the high
BOD of the fibers lowers the oxygen level which in turn lowers the 72-hr LC50
concentration of fibers to 272 and 738 mg/1 at oxygen levels of 3 and 5 mg/1.
Conifer fibers are more toxic than hardwood fibers to recently hatched fathead
minnows (Smith and Kramer 1964). Wood fibers have no effect on the developing
fish embryo if the ventilation of the eggs is not reduced (Kramer and Smith
1965, 1966).
Sublethal effects can occur at fiber concentrations present in some
untreated effluents, but in well-treated effluents fibers are rarely a prob-
lem. At fiber concentrations as low as 100 mg/1 a variety of sublethal ef-
fects have been reported: growth reduction, increased coughing, increased
metabolic rate and increased numbers of mucous cells in the gill (Smith et al.
1965; Kramer and Smith 1965; MacLeod and Smith 1966). The cough response was
more sensitive to fiber than were respiration, swimming performance and hema-
tocrit level. The threshold concentration was 25 mg/1 for the cough response
and >100 mg/1 for the other tests (MacLeod and Smith 1966). Brown trout and
rainbow trout were more sensitive than were walleye (Stizostedion vitreum) and
fathead minnows (Kramer and Smith 1965, 1966). Betts and Wilson (1966) recom-
mended that total suspended solids should not exceed 36 mg/1 for the protec-
tion of salmonids.
The discharge of fibrous materials has been greatly curtailed, but large
quantities of other suspended and dissolved materials are still being re-
leased. These materials exert a significant BOD, even after treatment, and
can contribute to low oxygen concentrations in lakes, bays, and slow-moving
rivers. Even though these materials are not acutely toxic to fish, many will
settle out, forming sludge beds, and may have deleterious effects on the
bottom fauna (Washington, State of 1967). Definitive studies of these eco-
logical effects are lacking. The dissolved solids are non-toxic per se, but
can induce stress through alterations in osmoregulation (Tsai 1973).
Rosehart et a_L (1974) warned that products such as dyes, coating lat-
tices, alum, retention aids, beater aids, surface sizings and wet-strength
resins can all contribute to the toxicity of effluents. Firipi and Scalata
(1973) attributed a large portion of the toxicity to slimicides and fungi-
cides. Pentachlorophenol has generally replaced mercury compounds as a fungi-
cide thus increasing the effluent's acute toxicity to fish. Horning (1974)
examined 29 dyes used in the pulp and paper industry and found 96-hr LC50's as
low as 0.047 mg/1 (for basic violet). Gordon and Servizi (1974) have bio-
assayed 22 chemical additives used in the kraft process and found seven to be
toxic to salmonids at levels likely to be found in the effluent. Wilson
(1972) concluded that metals normally do not contribute to the toxicity of
effluents from sulfite mills.
Chiorination of the treated mill effluent has been suggested to control
high coliform and Klebesiella pneumonia levels that develop during treatment.
Such chlorination can increase effluent toxicity through the formation of more
persistent chloramines in the presence of ammonia, especially in ammonium-
30
-------
sulfite plants. Seppovaara (1973) reported that chlorination of pine and
beachwood pulp effluent increased the toxicity 10 to 20 times. A well-treated
kraft mill effluent which was not acutely toxic at full strength to salmon,
was acutely toxic at 18% v/v one hour after adding 1 mg/1 chlorine even though
no chlorine or chloramine could be detected (Stiles 1977). Chlorination of
phenolic compounds was suspected.
Pulp mill effluents can cause a phenol-like flavor and odor in fish
flesh. Shumway (1968) reported that the flavor of coho salmon was impaired by
concentrations of untreated KME as low as 1.5% when the fish were exposed for
72 to 96 hr. In an extensive study by Domtar Fine Paper, Ltd, Cook et a_L
(1971) reported perch (Perca flavescens) flesh to be tainted by 10% but not by
0.3% effluent. The effluent came from an integrated mill producing both kraft
and sulfite pulp. A study by NCASI (1973) demonstrated that, with heavy
chlorine treatment, phenolic structures are ruptured and tainting qualities
destroyed but, with smaller chlorine doses, some phenolic compounds were
chlorinated although the flavor of fish flesh was not altered significantly
from that of fish held in unchlorinated pulp effluent.
The color and foaming of pulp mill effluents, especially kraft mill
effluent, are esthetically undesirable. Even at a 5% dilution of well-treated
KME, a concentration that showed no adverse effects on fish production in
artificial streams, the color was judged objectionable (personal communica-
tion).* Stone et aj. (1974) reported that color could reduce photosynthesis
below a pulp mill outfall. Parker and Sibert (1973) also reported that color
from BKME restricted light to the halocline. Color can be removed with lime
treatment (Spruil 1974), but the resulting effluent was more toxic to chiron-
omids (Wilson 1975).
* W. K. Seim, Dept. of Fish, and Wildl. Oregon State University, Con/all is.
31
-------
CONCLUDING STATEMENTS
The toxicity of whole pulp and paper mill effluents has been adequately
demonstrated. The variability in toxicity within and among mills severely
limits the predictive value of these assays. Bioassays still have a place,
however, in the management of these effluents. Because of the sporadic nature
of effluent toxicity, frequent bioassays or other monitoring methods should be
a condition of discharge permits. Certain sublethal tests, especially the
"cough reflex," appear to have some merit as a monitoring tool. As techniques
progress in the identification and quantification of the major toxic com-
ponents in the effluents, it may be possible to reduce reliance on bioassays.
As yet, bioassays appear to be the best way to assess toxicity of complex
effluents. Research to find important species that are more sensitive to pulp
effluents may be productive.
One of the major problems yet to be solved with pulp and paper mill
effluent is the sporadic and dramatic increases in toxicity of "adequately"
treated effluents. These sporadic toxic discharges have great potential to
damage the aquatic environment. The effects of sporadic near-lethal doses are
not known and should be studied.
The majority of pulp and paper mill effluent studies have been sponsored
or co-sponsored by the industry. Many of these studies have been on newer
mills in order to demonstrate the potential for low toxicity in their efflu-
ents. Effluents from older, more polluting mills may have been overlooked
and a review of the literature may underestimate the potential environmental
damage from these mills. A survey of these less frequently studied mills may
be justified.
32
-------
REFERENCES
Adelman, I. R. and Smith, L. L. , Jr. (1972). Toxicity of hydrogen sulfide to
goldfish (Carassius auratus) as influenced by temperature, oxygen and
bioassay techniques. J. Fish. Res. Bd. Canada. 29:1309.
Banks, R. (1969). I. Isolation of certain toxic components of kraft mill
waste and attempts to determine their structure. Ph.D. Thesis, Oregon
State Univ., Corvallis.
Betts, J. L. (1976). Regulation and waste characterization. Proceedings of
seminars on water pollution abatement technology in the pulp and paper
industry. Environment Canada. EPS, Ottawa.
Betts, J. L., Beak, T. W. , and Wilson, G. G. (1967). A procedure for small-
scale laboratory bioassays. J. Water Pollut. Control Fed. 39:89.
Betts, J. L. and Wilson, G. G. (1966). New methods for reducing the toxicity
of kraft mill bleachery wastes to young salmon. J. Fish. Res. Bd.
Canada. 23:813.
Blosser, R. 0. and Owens, E. L. (1970). A guide to the short-term bioassay
of mill effluents. Tech. Bull. No. 233, NCASI, New York, N.Y.
Borton, D. C. (1970). Effects of biologically stabilized kraft mill effluents
on juvenile coho salmonids growth. M. S. Thesis, Oregon State Univ.,
Corval1i s.
Borton, D. C. (1974). Effects of primary treated and biologically stabilized
kraft mill effluent on the production, biomass and growth rates of juve-
nile salmonids in three stream channels. Ph.D. dissertation, Oregon
State Univ. , Corvallis.
Brebion, B. , Chopin, J. , and Humbert, F. (1957). Toxicity to fish (minnows)
of some phenolic derivatives formed by the decomposition of lignin in
paper pulp factories. Chem. Ind. 77:1110.
Brown, D. A. and McLeay, D. J. (1975). Effects of bleached kraft mill efflu-
ent on the survival of starved juvenile coho salmon (Oncorhynchus
kisutch). J. Fish. Res. Bd. Canada. 32:2528.
Bruynesteyn, A. and Walden, C. C. (1971). Origin of toxicity and biochemical
oxygen demand (BOD) in the bleached kraft process. CPAR Report 10-1.
Canadian Forestry Service, Ottawa, Ontario.
33
-------
Chevalier, J. R. (1973). Toxicity of sodium sulfite to common shiners:
Dynamic bioassay. TAPPI. 56(5):135.
Conkey, J. H. (1968). Relative toxicity of biostatic agents suggested for
use in the pulp and paper industry. 1968 Review. American Paper Insti-
titute, New York, #3170.
Cook, W. H. , Farmer, F. A., Kristransen, 0. E., Reid, K., Reid, J., Rowbottom,
R. , and Domtar Fine Paper Ltd. (1971). Effect of pulp and paper mill
effluents on taste and odor of water and fish. Can. For. Ser. , CPAR
Project Final Rept. 12-2 CA.
Das, B. S. , Reid, S. G. , Betts, J. L. , and Patrick, K. (1969). Tetrachlor-o-
benzoquinone as a component in bleached kraft chlorination effluent toxic
to young salmon. J. Fish. Res. Bd. Canada. 26:3055.
Davis, J. C. (1973). Sublethal effects of bleached kraft pulp mill effluent
on respiration and circulation in sockeye salmon (Oncorhynchus nerka).
J. Fish. Res. Bd. Canada. 30:369.
Davis, J.C. (1976). Progress in sublethal effects studies with kraft pulp-
mill effluent and salmonids. J. Fish Res. Bd. Canada. 33:2031.
Davis, J. C. and Mason, B. J. (1973). Bioassay procedures to evaluate acute
toxicity of neutralized bleached kraft pulp mill effluent to Pacific
salmon. J. Fish. Res. Bd. Canada. 30:1565.
Dewitt, J. W. , Jr-. (1963). Effects of pollutional conditions on stream
organisms with special emphasis on stonefly naiads. Dissertation Ab-
stracts XXIV. 9:3507.
Dickman, M. S. (1973). Total dissolved electrolyte effects on periphyton.
J. Water Pollut. Control Fed. 45:2211.
Dimick, R. E. and Haydu, E. P. (1952). The effect of kraft mill waste
liquors and certain of their components on certain salmonid fishes of the
Pacific Northwest. Tech. Bull. No. 51, NCSI, New York, N.Y.
Dimick. R. E. , Warren, C. E. , Jones, B. F-, Doudoroff, P., and Amberg, H. R.
(1957). Some preliminary observations on the avoidance reactions of
salmonid fishes to pulp mill effluents. Tech. Bull NO. 93, NCASI, New
York, NY.
Donnier, E. (1972). Toxicity of pulp and paper mill effluents on sea en-
vironments. Rev. Int. Oceangr. Medicale. 28:53. (ABIPC 44:6249).
Ellis, R. H. (1967). Effects of kraft pulp mill effluent on the production
and food relationships of juvenile chinook salmon in laboratory streams.
Tech. Bull. No. 210, NCASI, New York, NY.
34
-------
Fahmy, F. K. and Lush, 0. L. (1974). Sensitivity of major aquatic food chain
organisms to treated kraft mill effluents. CPAR Rep. No. 356-1.
Canadian Forestry Service, Ottawa, Ontario.
Filimonova, Z. I. (1968). Effects of effluents from pulp and paper mills on
zooplankton in natural waters. Sanit. Gidrobiol. Vodn. Toksikol. 2:197.
(Ab. Bull. Inst. Paper Chem. 40:3059u).
Firipi, M. and Scarlata, V. (1973). Study on fish, toxicity and biodegrada-
bility of paper mill wastes in relation to biocides used. Proc. EVCEPA
Conf. Rome. 15:449.
Fujiya, M. (1961). Effect of kraft pulp mill wastes on fish. J. Water
Pollut. Control Fed. 33:968.
Fujiya, M. (1964). Physiological estimation of the effects of pollutants
upon aquatic organisms. Advances Water Pollution Research Vol. 3. pp.
315. Pergamon Press, Oxford.
Galtsoff, P. S., Chipman, W. A., Engle, J. G., and Calderwood, H. N. (1947).
Ecological and physiological studies of the effect of sulfate pulp mill
wastes on oysters in York River, Virginia. Fish. Bull. No. 43, U.S. Fish
and Wildlife Service, Washington, D.C.
Gazdziauskaite, I. B. (1971a). Effects of effluents from the Sovetsk and
Neman mills on the biology of Pom:ogammarus robustoides. (1) Vitality.
(2) Respiration intensity. Liet. TSR Mokslu. Adad. Darbai Ser. C No.
2:93. (Ab. Bull. Paper Chem. 43:10694).
Gazdziauskaite, 1. B. (1971b). Effect of effluents from the Sovetsk and Neman
sulfite pulp and paper mills on the fertility of Pontogammarus robus-
toides (Grimm) sars. Rybokhoz. Isuch. Vnutr. Vodoemov No. 6:29-31.
(Ab. Bull. Inst. Paper Chem. 43:3026).
Gordon, R. W. and Servizi, J. A. (1974). Acute toxicity and detoxification of
kraft pulp mill effluent. International Pacific Salmon Fisheries Comm.
Progress Report 31, New Westminster, B.C., Canada, #4380.
Grande, M. (1964). Water pollution studies in the river Otra, Norway—
effects of pulp and paper mill wastes on fish. Int. J. Air Wat. Pollut.
8:77.
Gregory, L. A. and Loch, J. S. (1973a). Benthos survey in the North Sas-
katchewan River in the vicinity of the Prince Albert Pulp Company,
Prince Albert, Saskatchewan. Can. Dept. Environ. Fish and Marine Serv.
Tech. Report No. CEN T-72-2.
Gregory, L. A. and Loch, J. S. (1973b). Benthos studies on the Winnipeg
River in the vicinity of the Abitilic Manitoba Paper Company, Pine
Falls, Manitoba. Can. Dept. Environ. Can. Fish and Marine Ser. Tech.
Report No. CEN T-73-3.
35
-------
Hicks, D. G. and DeWitt, J. W. (1971). Effects of dissolved oxygen on kraft
pulp mill effluent toxicity. Water Res. 5:593.
Holland, G. A., Lasater, J. E., Neumann, E. D., and Eldridge, W. E. (1960).
Toxic effects of organic and inorganic pollutants on young salmon and
trout. Res. Bull. No. 5. State of Washington Dept. of Fish, Olympia,
WA.
Horning, R. A. (1974). The effect of selected dyes in the environment.
TAPPI. 57:135.
Howard, T. E. (1975). Stamina of juvenile coho salmon in pulp mill effluent
and in water after effluent exposure. J. Fish Res. Bd. Canada. 32:789.
Howard, T. E. and Leach, J. M. (1973a). Identification and treatment of
the toxic materials in pulp and paper woodroom effluents. CPAR Rep. No.
148-1, Canadian Forestry Service, Ottawa, Ontario.
Howard, T. E., and Leach, J. M. (1973b). Identification and treatment of the
toxic materials in mechanical pulping effluents. CPAR Rep. No. 149-1.
Canadian Forestry Service, Ottawa, Ontario.
Howard, T. E. , and McLeay, D. J. (1972). Sublethal effects of bleached kraft
mill effluents to fish. CPAR Report No. 9-2. Canadian Forestry Service,
Ottawa, Ont.
Howard, T. E. and Walden, C. C. (1965). Pollution and toxicity character-
istics of pulp mill effluents. TAPPI. 48:135.
Howard, T. E. and Walden, C. C. (1967). Hematocrit variation at sublethal
concentrations of kraft mill wastes. Presented at the 97th Ann. Conf.
Am. Fish Soc. , Toronto, Ontario.
Howard, T. E. and Walden, C. C. (1971). Effluent characteristics of bleached
kraft pulp mills. Pulp Paper Mag. Canada. 72:T3.
Howard, T. E. and Walden, C. C. (1974). Measuring stress in fish exposed to
pulp mill effluents. TAPPI. 57(2):133.
Jacobs, F. and Grant, G. C. (1974). Acute toxicity of unbleached kraft mill
effluent to the opossum shrimp, Neomysis americana. Water Res. 8(7):439.
Jones, B. J. , Warren, C. E. , Bond, C. E. , and Doudoroff, P. (1956). Avoid-
ance reactions of salmonid fishes to pulp mill effluents. Sewage Ind.
Wastes. 28:1403.
Kondo, R., Sameshima, K. and Kondo, T. (1973). Spent semichemical pulping
liquor (3). Toxicity characteristics of SCP spent liquor and reduction
of its toxicity. Japan TAPPI. 10:476. (ABIPC 44:12026).
Kramer, R. H. and Smith, L. L. (1965). Effects of suspended wood fiber on
brown and rainbow trout eggs and alevins. Trans. Am. Fish. Soc. 94:252.
36
-------
Kramer, R. H. and Smith, L. L. (1966). Survival of walleye eggs in suspended
wood fibers. Prog. Fish-Culturist. 28:79.
Kvasnicka, E. A. and Mclaughlin, R. R. (1955). Identification of spruce
sulphite liquor components. Can. J. Chem. 33:637.
Ladd, J. M. (1969). Effects of pH on the acute toxicity of kraft pulp mill
effluent to juvenile coho calmon, Oncorhychus kisutch. M.S. Thesis,
Humboldt State Coll., Arcata, CA.
Larson, G. L. , Hutchins, F. E. and Lamperti, L. P. (1977). Laboratory deter-
mination of acute and sublethal toxicities of inorganic chloramines to
early life stages of coho salmon Oncorhynchus kisutch. Trans. Am. Fish.
Soc. 106(3):268.
Leach, J. M. , Gietz, W. C. , and Thakore, A. N. (1974). Identification and
treatment of the toxic materials in pulp and paper woodroom effluents.
CPAR Rep. No. 148-2, Canadian Forestry Service, Ontowa, Ontario.
Leach, J. M. and Thakore, A. N. (1973). Isolation of the toxic constituents
of kraft pulp mill effluents. CPAR Rep. No. 11-3, Canadian Forestry
Service, Ottawa, Ontario.
Leach, J. M. and Thakore, A. N. (1974a). Isolation of the toxic constituents
of kraft pulp mill effluents. CPAR Rep. No. 11-4, Canadian Forestry
Service, Ottawa, Ontario.
Leach, J. M. and Thakore, A. N. (1974b). Identification fo the toxic con-
stituents in kraft mill bleach plant effluents. CPAR Report No. 245-1,
Canadian Forestry Service, Ottawa, Ontario.
Leach, J. M. and Thakore, A. N. (1974c). Identification and treatment of the
toxic materials in mechanical pulping effluents. CPAR Rep. No. 149-2,
Canadian Forestry Service, Ottawa, Ontario.
Leach, J. M. and Thakore, A. N. (1975a). Isolation and identification of
constituents toxic to juvenile rainbow trout (Salmo gairdneri) in caustic
extraction effluents from kraft pulp mill bleach plants. J. Fish. Res.
Bd. Canada. 32:1249.
Leach, J. M. and Thakore, A. N. (1975b). Identification of the toxic con-
stituents in kraft mill bleach plant effluents. CPAR Rep. No. 245-2,
Canadian Forestry Service, Ottawa, Ontario.
Leach, J. M. and Thakore, A. N. (1977). Compounds toxic to fish in pulp mill
waste streams. Prog. Water Tech. Vol. 9, 787.
Leach, J. M. Thakore, A. N. and Manville, J. F. (1975). Acute toxicity to
juvenile rainbow trout (Salmo gairdneri) or naturally occurring insect
juvenile hormone analogs. J. Fish. Res. Bd. Can. 32:2556.
37
-------
Leppakoski, E. (1968). Some effects of pollution (pulp and paper) on the
benthic environment of Gullmarsfjord. Helohlander Wiss. Meeresunters
(17) 291, Water Poll. Abs. (46) 576.
Lichatowich, J. A. (1970). Influences of kraft mill effluents on the pro-
duction of salmon in laboratory stream communities. M.S. Thesis, Oregon
State Univ. , Con/all is.
Livintsev, A. N. (1967). Effect
factory on aquatic organisms.
Abstr. 42:1710).
of waste waters from a wood hydrolyzing
Biol. Nauk. 10(3):2022. (Water Pollut.
Loch, J. S. and Bryant, W. J. (1972). Toxicity and other
acteristies of unbleached kraft mill effluents. Report
Div. Br. , Fish. Service. Environ. Can., Winnipeg, Man.
pollution char-
No. TR72-3 Res.
Loch, J. S. and MacLeod, J. C. (1973). Fish toxicity survey of four prairie
province pulp mill effluents. Tech. Report No. CEN T-73-4. Fish and
Marine Service, Environmental Canada, Ottawa, Ontario.
Loch, J. S. and MacLeod, J. C. (1974). Factors affecting acute toxicity
bioassays with pulp mill effluents. Can. Dept. Environ. Fish and Marine
Service, Tech. Rept. No. CEN T-74-2.
MacLeod, J. C. and Smith, L. L. (1966). Effect of pulpwood fiber on oxygen
consumption and swimming endurances of the fathead minnow (Pimephales
promelas). Trans. Am. Fish. Soc. 95:71.
McKague, A. B. (1975). Identification and treatment of the toxic materials
in pulp and paper woodroom effluents. CPAR Report No. 148-3. Canadian
Forestry Service, Ottawa, Ontario.
McLeay, D. J. (1973). Effects of 12-h and 25-day exposure to kraft pulp mill
effluent on the blood and tissues of juvenile coho salmon (Oncorhynchus
kisutch). J. Fish. Res. Bd. Canada. 30:395.
McLeay, D. J. (1976) A rapid method for measuring the
mill effluents and other toxicants to salmonid
temperature. J. Fish. Res. Bd. Canada. 33:1303.
acute toxicity of pulp
fish at ambient room
McLeay, D. J. and Brown, D. A. (1974).
changes in juvenile coho salmon
bleached kraft pulp mill effluent
Canada. 31:1043.
Growth stimulation and biochemical
(Oncorhynchus kisutch) exposed to
for 200 days. J. Fish. Res. Bd.
McLeay, D. J. and Brown, D. A. (1975). Effects of acute exposure to bleach
kraft pulp mill effluent on carbohydrate metabolism of juvenile coho
salmon (Oncorhynchus kisutch) during rest and exercise. J. Fish. Res.
Bd. Canada. 32:753.
McLeese, D. W.
effluent.
(1970). Behavior of lobsters exposed to bleached kraft mill
J. Fish. Res. Bd. Canada. 27:731.
38
-------
McLeese, D. W. (1973). Response of lobsters (Homarus americanus) to odor
solution in the presence of bleached kraft mill effluent. J. Fish. Res.
Bd. Canada. 30:279.
Marier, J. (1973). The effects of pulp and paper wastes, with particular
attention to fish and bioassay procedures for assessment of harmful
effects. NRCC No. 13501. Nat. Res. Council of Canada, Ottawa, Ontario.
Marvell, E. N. and Werner, R. (1963). 4-(p-tolyl)-pentanol in Douglas fir
pulping products. J. Org. Chem. 28:1542.
Mower, B. F. (1974). Growth and production of salmonids exposed to a sta-
bilized kraft mill effluent in experimental stream channels. M.S.
Thesis, Oregon State Univ. , Corvallis, OR.
NCASI. (1947). The toxicity of kraft mill wastes to typical fish food
organisms. National Council for Air and Stream Improvement. Tech. Bull.
No. 10.
NCASI. (1973). The measurement of phenolic substances and the significance
of their presence in pulp mill effluents on taste and odor in receiving
waters. Tech. Bull. NCSAI No. 268.
Nelson, P. J. and Hemingway, R. W. (1971). Resin in bisulfite pulp from
Pinus radiata wood and its relationship to pitch troubles. TAPPI. 54:
968.
Ng, K. S. , Mueller, J. C. , and Walden, C. C. (1974). Study of foam separa-
tion as a means of detoxifying bleached kraft mill effluents, removing
suspended solids and enhancing biotreatability. CPAR Rep. No. 233-1
(part I), Canadian Forestry Service, Ottawa, Ontario.
Ozburn, G. , Kraft, J. , and Somppi, L. (1973). Procedure for short-term
bioassay tests on industrial effluents of low oxygen content. Can. Gov.
Zool. 51(7):794.
Ozburn, G. , Kraft, J., and Somppi, L. (1974). Short-term bioassays of low 02
content effluents. Pulp and Paper Mag. Can. 75(9):(T318).
Parker, R. R. and Sibert, J. (1973). Effect of pulp mill effluents on dis-
solved oxygen in a stratified estuary. (1) Empirical model. (2) Numer-
ical model. Water Res. 7:503.
Rainville, R. P., Copeland, B. J. and McKean, W. T. (1975). Toxicity of
kraft mill wastes to an estuarine phytoplankton. J. Water Poll. Cont.
Fed. 47:487.
Rogers, I. H. (1973). Isolation and chemical identification of toxic com-
ponents of kraft mill wastes. Pulp Paper Mag. Canada. 74:T303.
Rogers, I. H. and Mahood, H. W. (1974). Removal of fish-toxic organic solute
from whole kraft effluent by biological oxidation and the role of wood
39
-------
extractives. Tech. Rep. No. 434, Fish Res. Bd. Canada, West Vancouver,
B.C.
Rosehart, R. G. , Ozburn, G. W., and Mettinen, R. (1974). Origins of toxicity
in sulphite pulping. Pulp and Paper Mag. Canada. 75:63.
Row, R. and Cook, R. H. (1971). Resin acid soaps—toxicity and treatability.
Presented at the 6th Air and Stream Improvement Conf., Tech. Sect., Can.
Pulp Paper Assoc. , Quebec City, Quebec.
Schaumburg, F. D. , Howard, T. E. , and Walden, C. C. (1967). A method to
evaluate the effects of water pollutants on fish respiration. Water Res.
1:731.
Seim, W. K. Lictatowich, S. , Ellis, R. , and Davis, J. E. (1977). Effects of
kraft mill on production of juvenile salmon production in laboratory
stream communities. Water Research 11:189.
Seppovaara, 0. and Hynninen, P. (1970). On the toxicity of sulphate mill
condensates. Paperi ja Puu. 52:11. (Ab. Bull. Inst. Paper Chem. 41:
487).
Seppovaara, 0. (1973). The toxicity of the sulfate pulp bleaching effluents.
Paperi ja Puu. 55:713. (Ab. Bull. Inst. Paper Chem. 44:10910).
Servizi, J. A., Gordon, R. W. , and Martens, D. W. (1968). Toxicity of two
chlorinated catechols possible components of kraft pulp mill bleach
wastes. Progress Report No. 17, Int. Pacific Salmon Fish Comm. New
Westminster, B.C.
Servizi, J. A., Stone, E. T. , and Gordon, R. W. (1966). Toxicity and treat-
ment of kraft pulp bleach plant waste. Prog. Rep. 13, Int. Pacific
Salmon Fish. Comm., New Westminster, B.C.
Shireman, J. V. (1975). Utilization of a kraft effluent channel by fish and
aquatic organisms. TAPPI Environmental Conf., Denver, CO., p. 185.
Shumway, D. L. (1968). Flavor of jack coho salmon. NCSAI Tech. Bull. No.
217.
Smith, L. L. and Kramer, R. H. (1964). Some effects of paper fibers on fish
eggs and small fish. Proc. 19th Ind. Waste Conf., Purdue Univ., Lafay-
ette, In.
Smith, L. L. , Kramer, R. H. , and MacLeod, J. C. (1965). Effect of pulp wood
fibers on fathead minnows and walleye fingerling. J. Water Pollut.
Control. Fed. 37:130.
Smith, L. L. and Oseid, D. M. (1972). Effect of hydrogen sulfide on fish
eggs and fry. Water Res. 6:711.
40
-------
Sprague, K. B. (1969). Measurement of pollutant toxicity to fish. I. Bio-
assay methods for acute toxicity. Water Res. 3:793.
Sprague, J. B. (1971). Measurement of pollutant toxicity to fish. III.
Sublethal effects and "safe" concentrations. Water Res. 5:245.
Sprague, J. B. and Drury, D. W. (1969). Avoidance reactions of a salmonid
fish to representative pollutants. Advances in Water Pollution Research,
Vol. 4, pp. 169. Pergamon Press, Oxford.
Sprague, J. B. and McLeese, D. W. (1968). Toxicity of kraft pulp mill
effluent for adult and larval lobsters, and juvenile salmon. Water Res.
2:753.
Springer, A. M. and Atalla, R. H. (1974). Cellulosic deposits in benthal
environments: Occurrence, evaluation and decomposition. TAPPI. 1:120.
Spruil, E. L. , Jr. (1974). Color removal and sludge disposal [Process] for
kraft mill effluents. Paper Trade Journ. 158(33):24.
Stein, J. E., Petersen, R. E., Denison, J. G., Clark, G. M., and Ellis, I. E.
(1959). The spawning of Olympic oysters (Ostrea lurida) kept in spent
sulphite liquor (SSL). Olympia Research Div. Report Rayonier, Inc.
Shelton, WA.
Stiles, D. (1977). Effects of chlorinated biologically stabilized kraft mill
effluent on the mortality and growth of coho salmon. M.S. Thesis, Oregon
State Univ., Corvallis.
Stone, D. , Griffing, T. C., and Knight, M. C. (1974). Biological monitoring
of the Fraser River near Prince George, B.C. Pulp and Paper Mag. Can.
75(c):100.
Tabata, K. (1965). Systematic studies on toxic components in industrial
wastes with reference to the tolerance of aquatic lives. II. On acute
toxic components in digested waste from ammonium-base semi chemical pulp
mills. Bull. Tokai Reg. Fish. Res. Lab. #42. 11-16. (Japanese with
English summary).
Tokar, E. M. and Owens, E. L. (1968). The effects of unbleached kraft pulp
mill effluents on salmon. I. Growth, food consumption and swimming
ability of juvenile chinook salmon. Tech. Bull. No. 217, NCASI, New
York, N.Y.
Tsai, Chu-Fa. (1973). Water quality and fish life below sewage outfalls.
Trans. Am. Fish. Soc. 102:281.
Van Horn, W. M. (1961). Aquatic biology and the pulp and paper industry.
(Report No. 1), Tech. Bull. No. 148, NCSAI, New York, N.Y.
Van Horn, W. M. (1971). Aquatic biology and the pulp and paper industry
(Report No. 2). Tech. Bull. 251, NCASI, New York, NY.
41
-------
Van Horn, W. M. , Anderson, J. B. , and Katz, M. (1949). The effect of kraft
pulp mill wastes on some aquatic organisms. Trans. Am. Fish. Soc. 79:55.
Van Horn, W. M. , Anderson, J. B. , and Katz, M. (1950). The effect of kraft
pulp mill wastes on fish life. TAPPI. 33:209.
Walden, C. C. (1976). Review paper. The toxicity of pulp and paper mill
effluents and corresponding measurement procedures. Water Res. 10:639.
Walden, C. C. and Howard, T. E. (1971). The nature and magnitude of the
effect of kraft mill effluents on salmon. Proc. Int. Symp. Ident.
Measurement of Environmental Pollutants, p. 363. Nat. Res. Council of
Canada.
Walden, C. C. , Howard, T. E. , and Froud, G. D. (1970). A quantitative assay
of the minimum concentration of kraft pulp mill effluents which affect
fish respiration. Water Res. 4:61.
Walden, C. C. , Howard, T. E., and Sheriff, W. J. (1971). The relationship of
kraft pulp mill operating and process parameters to pollution character-
istics of the mill effluents. Pulp Paper Mag. Canada. 72:T82.
Walden, C. C. and McLeay, D. J. (1974). Interrelationships of various bio-
assay procedures for pulp and paper mill effluents. CPAR Report No. 165-
1. Canadian Forestry Service, Ottawa, Ontario.
Walden C.C ., McLeay D. J. and Monteith D. D. (1975) Comparing bioassay
procedures for pulp and paper effluents. Pulp Paper Mag. Canada 76,
T130-T134.
Warren, C. E. (1972). Laboratory and controlled experimental stream studies
of the effects of kraft effluents on growth and reproduction of fish.
Tech. Bull. No. 259, NCASI, New York, N.Y.
Warren, C. E. and Doudoroff, P. (1958). The development of methods for using
bioassays in the control of pulp mill waste disposal. TAPPI. 41:211.
Warren, C. E. , Seim, W. K. , Blosser, R. 0., Caron, A. L., and Owens, E. L.
(1974). Effect of kraft effluent on the growth and production of salm-
onid fish. TAPPI. 57(2):127.
Washington, State of. (1967). Pollutional effects of pulp and paper mill
wastes in Puget Sound, State of Washington Pollution Control Comm.,
Olympia. 474 pp.
Webb, P. W. and Brett, J. R. (1972). The effects of sublethal concentrations
of whole mill bleached kraft pulp mill effluent on the growth and food
conversion efficiency of underyearling sockeye salmon. J. Fish. Res. Bd.
Canada. 29:1555.
Werner, A. E. (1963). Sulfur compounds in kraft pulp mill effluents. Can.
Pulp and Paper Ind. 16(3):35.
42
-------
Williams, R. W. , Mains, E. W. , Eldridge, W. E. , and Lasater, J. E. (1953).
Toxic effects of sulfite waste liquor on young salmon. Res. Bull. No.
1. State of Washington Dept. of Fisheries, Olympia, WA.
Wilson, B. and Rennerfelt, J. (1971). Technical and economic evaluation of
internal versus external paper mill wastes treatment. Pulp and Paper
Mag. Canada. 72:84.
Wilson, M. A. (1975). Assessment of the sensitivity of major aquatic food
chain organisms to newsprint mill effluents which are not acutely toxic
to fish. CPAR Report No. 328-1, Canadian Forestry Service, Ottawa,
Ontario.
Wilson, M. A. and Chappel, C. I. (1973). Reduction of toxicity of sulphite
effluents. CPAR Report No. 49-2, Canadian Forestry Service, Ottawa,
Ontario.
Wilson, R. C. H. (1972). Acute toxicity of spent sulphite liquor to Atlantic
salmon (Salmo salar). J. Fish. Res. Bd. Canada. 29:1225.
Woelke, C. E. (1960). Effects of sulfite waste liquor on the normal develop-
ment of Pacific oyster (Crassostrea gigas) larvae. Res. Bull. No. 6,
State of Washington Dept. of Fisheries, Olympia, WA.
Woelke, C.E. (1965). Bioassays of pulp mill wastes with oysters. Biological
Problems in Water Pollution, Third Seminar. Tech. Rep. No. 999-WP-25.
Robert A. Taft Sanitary Engineering Center, U.S. Public Health Service,
Cincinnati, OH.
Woelke, C. E. (1976). Measurement of water quality with the Pacific oyster
embryo bioassay. Water Quality Criteria, ASTM STP 416. Am. Soc. Testing
Materials, Philadelphia, PA.
Woelke, C. E. , Schink, T. D. , and Sanborn, E. W. (1970). Development of an
jm sjtu marine bioassay with clams. Ann. Rep. to the U.S. Fed. Water
Quality Admin., Dept. of the Interior Grant No. 18050 DOJ, Washington,
D.C.
Woelke, C. E. , Schink, T., and Sanborn, E. (1972). Effect of biological
treatment on the toxicity of three types of pulping wastes to Pacific
oyster embryos. Report prepared under EPA contract No. 68-01-377, Wash-
ington, D.C.
Wong, A. (1976). Physical-chemical treatment—Proceedings of Seminars on
water pollution abatement technology in the pulp and paper industry.
Environmental Protection Service: Can. EPS 3-WP-76-4.
Worster, H. E. and Pudek, M. F. (1973). Effects of oxygen pulping on toxic-
ity and color of effluents. Pulp and Paper Mag. Can. 95:793.
Zitko, V. and Carson, M. V. (1971). Resin acid and other organic compounds
in groundwood and sulfate mill effluents and foams. Ms. Rep. Ser. No.
1134, Fish. Res. Bd. Canada, Biological Station, St. Andrews, N.B.
43
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
REPORT NO.
EPA-600/3-79-013
2.
3. RECIPIENT'S ACCESSION NO.
TITLE AND SUBTITLE
TOXICITY OF PULP AND PAPER MILL EFFLUENT
A Literature Review
5. REPORT DATE
February 1979 issuing date
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
Floyd E. Hutchins
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
Western Fish Toxicology Station
Corvallis Environmental Research Laboratory
1350 S.E. Goodnight Avfe
Con/all is, Oregon 97330
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
2. SPONSORING AGENCY NAME AND ADDRESS
Corvallis Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis, Oregon 97330
13. TYPE OF REPORT AND PERIOD COVERED
literature review
14. SPONSORING AGENCY CODE
EPA/600/02
5. SUPPLEMENTARY NOTES
Project Officer: F.E. Hutchins, 8-420-4735, Corvallis, OR (comrn. (503)757-4735)
6. ABSTRACT
This review of pulp and paper mill effluents considers the need for additional toxicity
data to insure effective effluent regulation. Effluent characteristics and problems of
toxicity testing particular to pulp and paper mill effluents are discussed; however,
the emphasis is on toxic effects of these effluents to aquatic life. Untreated pulp and
paper mill effluents are very toxic to most aquatic life. Concentrations as low as two
percent can be acutely toxic to fish. Sufficient treatment can render the effluent
essentially nontoxic much of the time; however, treatment processes used by most mills
reduce toxicity but do not eliminate it. Even effluents receiving "good" treatment may
exhibit sporadic and dynamic increases in toxicity (due in part to spills or dumping of
spent pulping chemicals). Sublethal exposures of aquatic organisms to pulp effluent ma;
affect a number of their physiological and behavioral functions. The more sensitive
functions, growth rate, coughing reflex, and temperature tolerance, are affected at con
centrations less than l/10th of the 96-hr LC50. Many other systems such as respiration
and circulation may be affected at concentrations near l/10th of the 96-hr LC50. The
principal toxic components in pulp and paper mill effluents are resin acids and fatty
acids naturally occurring in the wood pulped, and in effluents from bleaching processes
toxic chlorinated compounds predominate. Untreated effluents have caused considerable
environmental damage, but well-treated effluents have had minimal effects on fish pro-
duction, although shifts in biological diversity have occurred.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Pulp mill effluent, water-pollution, acute
toxicity, subacute toxicity, bioassay,
physiological effects, toxic components,
review
Pulp mill effluent toxi-
city review
06/F
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report/
UNLIMITED
21. NO. OF PAGES
50
20. SECURITY CLASS (This page)
UNLIMITED
22. PRICE
EPA Form 2220-1 (R.v. 4-77)
44
------- |