EPA-600/2-78-031
February 1978 CM
Environmental Protection Technology Series
DERIV
BLEAC
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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 ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-78-031
February 1978
REMOVAL OF WOOD-DEEIVED TOXICS FROM
PULPING AND BLEACHING WASTES
Dwight B. Easty
LeRoy G. Borchardt
Bette A. Wabers
Institute of Paper Chemistry
Appleton, Wisconsin
Grant No. R-803525-0^
Project Officer
Ralph H. Scott
Wood Products Staff
Industrial Environmental Research Laboratory - Cincinnati
Corvallis, Oregon 97330
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO ^5268
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Ftoor
Chicago, IL 60604-3590
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory — Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorsement
or recommendation for use.
11
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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollution con-
trol methods be used. The Industrial Environmental Research Laboratory —
Cincinnati (IERL-CI) assists in developing and demonstrating new and improved
methodologies that will meet these needs both efficiently and economically.
This report "Removal of Wood-Derived Toxics from Pulping and Bleaching
Wastes" is intended to identify and quantify the presence of certain organic
compounds which appear to exert a toxic impact in the water environment.
These compounds derive from the extractable portion of wood substance and
consist of some of the resin acids and unsaturated fatty acids as well as
chlorinated organics from pulp bleaching. Through the cooperation of fifteen
mills in the United States samples were obtained for analyses. This report
contains the results of the analytical work. The findings indicate that
some treatment processes and in-plant measures are capable of destruction or
control of these organics. No attempt is made to relate the presence and
quantity of these organics to their effect on receiving waters.
David G. Stephan
Director
Industrial Environmental Research
Laboratory — Cincinnati
111
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ABSTRACT
Wood-derived compounds known to possess toxicity toward fish and to be
present in pulp mill effluents include resin and unsaturated fatty acids,
their chlorinated analogs, chlorinated guaiacols, and epoxystearic acid. The
objective of this investigation has been to assess the extent to which these
compounds are removed from pulp mill effluents by different waste treatment
systems in use in several locations in the United States. Effluents before
and after treatment were collected and submitted for determination of the
compounds of interest.
Nearly all of the waste treatment processes studied removed the toxic
compounds effectively. Although primary clarification had little effect on
these materials, aerated lagoons and air-activated sludge systems normally
removed from 80 to 100% of the resin and fatty acids and their chlorinated
analogs from kraft and sulfite mill effluents. Biological treatment facil-
ities which exhibited poorer fatty and resin acid removal were those which
received high loadings of fatty and resin acids and BOD. High loadings were
apparently reflected also in the lower percentage removal of the toxic com-
pounds in the two oxygen-activated sludge systems studied.
Large reductions in concentrations of the toxicants were observed fol-
lowing precipitation processes. Systems studied included lime precipitation
and tertiary treatments employing alum.
Reverse osmosis demonstrated essentially complete rejection of fatty
and resin acids. Performance of pilot ultrafiltration units was either good
or marginal, apparently depending upon the type of membrane used. Although
chloroform contents of the samples were affected minimally by ultrafiltration,
they underwent reductions of from 88 to 98% in all of the other treatment
systems studied.
This report was submitted in fulfillment of Grant No. R-803525-Ql| by The
Institute of Paper Chemistry under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period August 6, 197*5 to November
9, 197Tj and work was completed as of August 11, 1977-
IV
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CONTENTS
Foreword
Abstract iv
Figures vi
Tables vii
Abbreviations and Symbols viii
Acknowledgment x
1. Introduction 1
2. Conclusions 3
3. Recommendations k
k. Program Design 5
5. Development of Analytical Procedures 7
Fatty and resin acids 7
Bleach plant toxicants 7
Chloroform 12
Stability of fatty and resin acids 12
Stability of bleach plant toxicants 15
6. Procedures Used in Investigation 17
Sampling and sample preservation 17
Determination of fatty and resin acids 17
Determination of bleach plant toxicants 20
Determination of chloroform 21
7. Results of Analyses 22
8. Discussion 70
References 77
v
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FIGURES
Number Page
1 Gas chromatogram of U.B. kraft effluent 8
2 Gas chromatogram of bleach plant toxicants 11
3 Mill No. 1 reverse osmosis system 23
h Mill No. 2 ultrafiltration system 26
5 Mill No. 3 ultraf iltration system 28
6 Mill No. k waste treatment system 31
7 Mill No. 5 waste treatment system 35
8 Mill No. 6 color removal process 38
9 Mill No. 7 waste treatment system kl
10 Mill Wo. 8 waste treatment system kh
11 Mill No. 9 waste treatment system k&
12 Mill No. 10 waste treatment system 50
13 Mill No. 11 waste treatment system 5^
l4 Mill No. 12 waste treatment system 58
15 Mill No. 13 waste treatment system 6l
16 Mill No. ik waste treatment system 6U
IT Mill No. 15 waste treatment system 66
18 Removal of fatty and resin acids in activated sludge systems ... 7^-
19 Removal of fatty and resin acids in aerated lagoons 75
VI
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TABLES
Number Page
1 Participating Mills 5
2 Recovery of Fatty and Resin Acids from Mill Effluents 7
3 Extractability of Bleach Plant Toxicants 10
k Analysis of Effluents Stored at 3°C and pH 11 13
5 Analysis of Effluents at 22°C and pH 11 ik
6 Stability of Bleach Plant Toxicants 16
7 Mill No. 1 Data 25
8 Mill No. 2 Data 27
9 Mill No. 3 Data 30
10 Mill No. k Data 33
11 Mill No. 5 Data 36
12 Mill No. 6 Data 39
13 Mill No. 7 Data h2
Ik Mill No. 8 Data ^5
15 Mill No. 9 Data 1*9
16 Mill No. 10 Data 51
17 Mill No. 11 Data 55
18 Mill No. 12 Data 59
19 Mill No. 13 Data 63
20 Mill No. lit Data 65
21 Mill No. 15 Data 68
22 Summary of Waste Treatment Evaluation 71
23 Loading and Removal of Fatty and Resin Acids and BOD in
Biological Treatment Systems 73
VI1
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LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
bleach toxicants
BOD
°C
Clar.
cm3
Cone.
day
EPA
-1
Floe.
ft
ft/sec
gal/day-ft2
GC/MS
gpm
ha
He
in.
Institute
kg
kg/cm
kw
Ib
m
m2
m_3/day
M gpd
yg
ml/g
MLSS
urn
NCASI
NHB
NSSC
PCB
percentage removal
— trichloroguaiacol, tetrachloroguaiacol, epoxystearic
acid, dichlorostearic acid, monochlorodehydroabietic
acid, dichlorodehydroabietic acid
— five-day biochemical oxygen demand
-r- degrees Centigrade
— clarifier (in Fig. 9, 13)
— cubic centimeter
— concentrator (in Fig. 13)
—i- food to microorganism ratio, Ib BOD/day/lb MLSS
— Environmental Protection Agency
— degrees Fahrenheit
-- flocculator (in Fig. 13)
— feet
— feet per second
— gallons per day per square foot
— gas chromatography/mass spectrometry
— gallons per minute
— hectares
i— helium
— inch
— The Institute of Paper Chemistry; Appleton, Wis.
— kilogram
i— kilograms per square centimeter
— kilowatt
— pound
— meter
— square meters
— cubic meters per day
-- million gallons per day
— microgram
— milliliter per gram
-- mixed liquor suspended solids
— micrometers
— National Council of the Paper Industry for Air and
Stream Improvement
— North Holding Basin — Mill 13
— neutral sulfite semichemical
i— Primary Control Basin — Mill 13
-p 100 (raw concentration-final concentration)/raw
concentration
Vlll
-------
ppb
ppm
psi
RO
SHE
SS
U.B.
UF
C
E
H
D
0
parts per billion
parts per million
pounds per square inch
reverse osmosis
South Holding Basin - Mill 13
suspended solids
unbleached
ultrafiltration
chlorination
caustic extraction
hypochlorite
chlorine dioxide
oxygen
Stages of
bleaching
sequence
IX
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ACKNOWLEDGMENTS
The authors gratefully acknowledge the contributions of the following
people:
Personnel in the participating mills who collected, preserved, and
shipped samples and who provided background information on the mills' waste
treatment systems.
Administrators in the mills who supported this work by authorizing their
mill's participation.
J. M. Leach of B. C. Research and R. R. Claeys of NCASI who provided
samples of the compounds of interest.
R. 0. Blosser and R. R. Claeys of NCASI, R. H. Scott of EPA, L. H.
Keith, formerly of EPA and now with Radian Corp., and H. S. Dugal and T. W.
Joyce of The Institute of Paper Chemistry for valuable consultation.
R. R. Claeys of NCASI for chloroform determinations and H. Nowicki of
Calgon for GC/MS analyses.
x
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SECTION 1
INTRODUCTION
Organic compounds exhibiting a toxic effect on fish have long "been known
to exist in pulping and bleaching wastes. Types of compounds found to be
present in pulp mill effluents and to contribute to effluent toxicity include
resin acids, chlorinated resin acids, uiisaturated fatty acids, other acidics
(epoxystearic acid, dichlorostearic acid), and chlorinated phenolics (l-*0.
The toxicity of these compounds and of mill effluents has been studied exten-
sively in Canada; this work was recently reviewed by Walden and Howard (5)
and Leach and Thakore (6). The current investigation has been prompted by
the increasing concern with toxic materials in the United States.
Recent research has revealed that these toxic, wood-derived compounds
are biodegradable to varying degrees (7) and that they can be removed from
effluents by biological and physicochemical detoxification processes (8,9)•
It became of interest, therefore, to learn the extent to which these materi-
als are degraded or removed in several pilot and mill-scale waste treatment
systems presently operating in different locations throughout the United
States. Waste treatments selected for study were membrane processes (re-
verse osmosis and ultrafiltration), precipitation processes originally de-
veloped for color removal (alum and lime treatments), air-activated sludge,
oxygen-activated sludge, and aerated lagoons. In mills where these secondary
and tertiary processes are preceded by primary clarification, the effect of
the primary treatment on the compounds of interest was also studied. This
reported work relates only to the presence, quantity, and fate of the spe-
cific compounds listed below; no attempt was made to develop a cause-effect
relationship in receiving waters.
Resin acids:
Abietic
Dehydroabietic
Isopimaric
Pimaric
Chlorinated resin acids:
Monochlorodehydroabietic
Dichlorodehydroabietic
Unsaturated fatty acids:
Oleic
Linoleic
Linolenic
-------
Unsaturated fatty acid derivatives:
9,10-Epoxystearic acid
9,10-Dichlorostearic acid
Chlorinated phenolics:
3,^ , 5-Trichloroguaiacol
3,^,5,6-Tetrachloroguaiacol
Halomethane:
Chloroform
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SECTION 2
CONCLUSIONS
Nearly all of the waste treatment systems studied in this investigation
removed essentially all of the compounds of interest quite effectively.
Greater than 90% removal of fatty and resin acids was achieved in eight out
of thirteen mill-scale treatment facilities studied. Only three mills had
detectable amounts (>Uo ppb) of bleach toxicants (chlorinated fatty acids,
resin acids, and guaiacols) in their final effluents. Amounts of chloroform
in final mill effluents (8-75 PPt>) were in the range that has been reported
for some municipal drinking waters (2-152 ppb).
Very little removal of fatty and resin acids or bleach toxicants occur-
red during primary clarification. These compounds were apparently not
associated with the suspended solids removed.
Raw effluents from the two sulfite mills in the program contained lower
levels of fatty and resin acids than raw effluents from the kraft mills.
Amounts of bleach toxicants in the sulfite mill raw effluents were near or
below the detection limit. Concentrations of all of these compounds were
effectively reduced during secondary treatment.
Most lagoons and air-activated sludge systems achieved high percentage
removals of fatty and resin acids from kraft mill effluents. Systems which
exhibited poorer performance received high loadings of BOD and of fatty and
resin acids. High loadings of fatty and resin acids appeared also to have
influenced the lower percentage removal of these toxic compounds in the two
oxygen-activated sludge facilities studied.
The relative ability of biological waste treatment processes to degrade
bleach toxicants paralleled their ability to remove fatty and resin acids.
In each case, percentage removal of the bleach toxicants was less than the
percentage removal of their unchlorinated analogs.
The one lime precipitation system studied demonstrated a percentage re-
moval of fatty and resin acids that greatly exceeded its percentage removal
of BOD. Laboratory-scale alum precipitations, used as tertiary treatments,
reduced fatty and resin acids and bleach toxicants to below detection limits.
Reverse osmosis demonstrated essentially complete rejection of fatty and
resin acids. Rejection of bleach toxicants by a pilot ultrafiltration system
with a dynamic membrane was good. An ultrafiltration unit with a synthetic
polymer membrane was much less effective.
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SECTION 3
RECOMMENDATIONS
Investigations into the production and fate of potentially toxic com-
pounds emanating from pulp and paper mills should "be continued. In some
instances, in-plant waste control systems applied to specific process streams
within the mill might be considered a desirable means of removing these wood-
derived compounds from raw wastes and ultimately from effluents. To assure
efficient use of in-plant control facilities, the production of the com-
pounds of interest by the various potential sources within the mill should be
investigated and documented. Among specific streams to be analyzed in a
recommended future survey are wet barking wastes, condensates, machine white
water, and effluents from screen rooms, decker, chlorination, and caustic
extraction. From such a study involving several mills would be developed an
account of the contribution of the mills' unit processes to the total load
of wood-derived toxicants in their raw wastes.
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SECTION U
PROGRAM DESIGN
Mills invited to participate in this study were selected and initially
contacted "by the Project Officer. In many cases these mills had conducted
or were conducting projects on their waste treatment facilities under partial
EPA sponsorship. The mills which participated in this project (listed by
code number), and their pulping process, location, and waste treatment
process studied are shown in Table 1.
TABLE 1. PARTICIPATING MILLS
Mill no.
1
2
3
h
5
6
7
8
9
10
11
12
13
lU
15
Pulping process
Semi chemical
Bleached kraft
Bleached kraft
Unbleached and
bleached kraft
Unbleached kraft
Unbleached kraft
and semichemical
Bleached sulfite
Bleached kraft
Unbleached kraft
and semichemical
Bleached sulfite
Bleached kraft
Bleached kraft
Bleached kraft
Unbleached kraft
Bleached kraft
Location
Northern midwest
Southeast
South
East
South
South
East
Northwest
South
Northwest
Northern midwest
East
West
Northwest
South
Waste treatment process
Reverse osmosis
Ultrafiltration
Ultrafiltration
Oxygen-activated sludge
Oxygen-activated sludge
and alum treatment
Lime treatment
Activated sludge
Activated sludge
Aerated lagoon
Aerated lagoon
Aerated lagoon
Activated sludge
Aerated lagoon
Aerated lagoon
Aerated lagoon and
alum treatment
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Analytical methodology necessary for the conduct of this project existed
before the project began. However, it was essential to reaffirm, as shown
later in this report, that these methods could be used successfully on the
types of samples analyzed in this investigation. Where instrumentation need-
ed for a determination was not available at the Institute, the determination
was performed by a subcontractor. Thus, the chloroform determinations were
run at the West Coast Regional Center of the National Council of the Paper
Industry for Air and Stream Improvement (NCASI), and determinations of the
other chlorinated compounds and epoxystearic acid were performed by Calgon
Corporation. For most mills in this program, shipping time and sample insta-
bility precluded sending samples to Appleton for BOD determinations. Conse-
quently, BOD's were run at the participating mills.
Although all of the compounds of interest were determined in effluents
from mills with bleaching, only the unchlorinated compounds were sought in
effluents from mills without bleaching. Most of the toxicity in first caus-
tic extraction stage bleach effluent has been reported to result from chlor-
inated resin and fatty acids, chloroguaiacols, and epoxystearic acid (U).
Therefore, only these compounds, and not their unchlorinated analogs, were
determined in caustic extraction stage effluents in this project.
As noted later in the report, techniques had to be tested for preserving
and shipping samples containing the compounds of interest. In order to
characterize properly most of the facilities under study, samples were taken
over periods of 8-12 hours and in three rounds of sampling separated by two-
week periods. The character of some sample streams permitted use of alter-
nate schedules, and in some cases sampling was delayed by mill upsets and
equipment problems. In a few instances extra samples were taken which were
of particular interest to the participating mill. Samples from Mill 7 were
taken and analyzed in duplicate.
The design and conduct of this investigation have been devoted exclu-
sively to the determination of the compounds of interest in the waste treat-
ment facilities under study. Conclusions regarding the environmental impact
of these compounds on the receiving streams must await the attention of
other investigators.
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SECTION 5
DEVELOPMENT OF ANALYTICAL PROCEDURES
FATTY AND RESIN ACIDS
The method used for determining fatty and resin acids has been described
in two NCASI bulletins (10, 11). The earlier of these reports was based on
research conducted in this laboratory under NCASI sponsorship. In the most
recent bulletin a liquid chromatographic method is described for the separa-
tion of neutral compounds from methyl esters before gas chromatographic (GC)
analysis. This technique was used frequently in the present analysis of mill
effluents. The completeness of separation was evaluated by passing a solu-
tion containing known quantities of oleic, abietic, and isopimaric acid
through the column. Recoveries of 9^ to 102 percent were obtained. A
typical GC curve of an untreated mill effluent is shown in Fig. 1.
The method without the separation of the neutrals was tested by spiking
mill effluents with oleic and isopimaric acid, and the recoveries were de-
termined (Table 2).
TABLE 2. RECOVERY OF FATTY AND RESIN ACIDS FROM MILL EFFLUENTS
Oleic acid (ppm) Isopimaric acid (ppm)
Total Total Total Total
Sample Present Added present found % Present Added present found %
Pulp mill
effluent 9.U 17.1 26.5 25.U 96 3.5 8.7 12.2 12.1 99
Lagoon
effluent 3.68 1.71 5.39 5.38 100 1.78 0.87 2.65 2.25 85
The extensive studies by the Institute (10) and NCASI (ll) on the deter-
mination of fatty and resin acids were considered adequate to validate this
procedure and avoid any further testing.
BLEACH PLANT TOXICANTS
In the analysis of bleach plant effluents, the following compounds were
to be measured:
-------
Dehydroacietic Acjd
Abietic Acia
Isopimaric
0)
d
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03
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3, 1*, 5-Trichloroguaiacol
3,U,5,6-Tetrachloroguaiacol
9,10-Epoxystearic acid
9,10-Dichlorostearic acid
Monochlorodehydroabietic acid
Dichlorodehydroabietic acid
Methods for the isolation and measurement of these materials appeared in
a report by B. C. Research for the Canadian Department of the Environment (lj).
In that report the compounds were isolated from kraft mill caustic extraction
effluents by adsorption on XAD-2 resin. The separation and measurement were
accomplished by GC analysis of the methylated materials. Gas chromatography-
mass spectrometry (GC/MS) was used for confirmation. That report included an
investigation of solvent extraction as a means of isolation of the toxicants,
but quantitative removal of all the compounds was not achieved. Further work
in this area was recommended.
A study of the efficiency of extraction with anhydrous ethyl ether in
this laboratory showed complete separation when the aqueous samples were
extracted at pH 3, as illustrated in Table 3. The extracts were analyzed by
gas chromatography using a flame ionization detector. Quantitation was
achieved by the use of an internal standard (heptadecanoic acid) and compari-
son of the areas. Detector factors were established and applied in the cal-
culations. Authentic samples of these compounds were supplied by B. C. Re-
search and NCASI. Dichlorostearic acid and trichloroguaiacol were prepared
in our laboratory according to the procedures used in the B. C. Research re-
port (k, 12). Extractability was determined by adding known quantities of
the compounds to distilled water and extracting with ethyl ether at various
acid concentrations. A bleached kraft mill effluent was spiked with known
quantities of the compounds and extracted at the optimum pH to verify re-
covery from a typical mill sample. The effluent did not contain concen-
trations of bleach plant toxicants that could be detected with a flame ion-
ization detector.
The compounds were readily separated (Fig. 2) using the following
conditions for the gas chromatography:
Column: 1.83 x 0.0032 m (6 ft x 1/8 in.) stainless steel, containing
3% OV-17 on Supelcoport 80/100
Column temp.: 150-250°C at 3°/min
Injector temp.: 225°C
Detector temp.: 275°C
Detector: flame ionization
Carrier gas: He at 30 cm3/min
The methylated extracts of the mill samples were analyzed by limited
mass reconstructed gas chromatography in an outside laboratory. A descrip-
tion of this analysis may be found in the methods section of this report.
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CHLOROFORM
The chloroform determinations were performed by the NCASI laboratory in
Corvallis, Oregon. They used an extraction procedure similar to the method
of Richard and Junk (13) for the analysis of the mill effluents. The extracts
were analyzed on a gas chromatograph equipped with an electron capture detec-
tor. A microcoulometric halide detector was used to verify the composition
of some of the peaks. The NCASI laboratory reported an average recovery of
9Q% (88-119) when spiked mill effluents were analyzed. Detection limits were
not determined, but a concentration of 1 yg/1000 cm3 could be easily measured.
STABILITY OF FATTY AND RESIN ACIDS
A preliminary study was conducted to determine the best practical con-
ditions for preserving the samples during shipment from the mill to the labo-
ratory. Losses have been observed during storage even when the samples are
adjusted to pH 11 and kept refrigerated (ll). A quantitative evaluation of
the losses was considered necessary before proceeding with any of the samp-
ling.
The samples for this study were obtained from a typical unbleached kraft
mill. Samples from two sites in the mill's sewer system were collected by a
one-time grab method. The samples represented an untreated effluent which
was taken from the pulp mill's sewer and a treated effluent which came from
the outfall of the aerated lagoon.
In the initial study, the samples were adjusted to pH 11 and stored in
the refrigerator at 3°C. The adjusted effluents were contained in 500 cm3
amber glass bottles fitted with Teflon-lined screw caps. The bottles were
filled to the top to eliminate any air. (Most of the bottles contained about
a 1 cm3 air space after standing for 4-5 days.) Duplicate analyses were made
on the unaged samples and single determinations were made after 5 and 10 days
of storage. Results in Table h indicate that losses of fatty and resin acids
were insignificant during 10 days' storage at 3°C and pH 11.
The difficulty of keeping samples refrigerated during shipment by air
freight prompted a further investigation involving the stability of the
samples when stored at ambient temperature (22°C). Another set of samples
was collected from the same sampling points. Duplicate samples were analyzed
initially and after U and 10 days' storage.
The data in Table 5 suggest that the treatment system was generating
fatty and resin acids rather than removing them. Apparently the grab sample
from the pulp mill sewer was a poor representation of this source. The out-
fall of the lagoon was not typical either due to the extremely low tempera-
ture of -29°C (-20°F) on the day the samples were taken. Nevertheless, in
spite of nonrepresentative sampling, the data in Table 5 suggest that fatty
and resin acid contents of effluents would not be significantly altered dur-
ing shipment at ambient temperature and pH 11.
Dichloromethane, considered for possible use as a preservative, was add-
ed to separate aliquots of the above samples at a concentration of 5 cm3 per
12
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100 cm3 effluent. No pH adjustment was made, although the pulp mill sewer
was at pH 10.5 and the lagoon outfall was at pH 8.3. The fatty and resin
acid concentrations decreased about 25% after 10 days' storage in a refriger-
ator. Further efforts to develop dichloromethane as a preservative were
abandoned.
STABILITY OF BLEACH PLANT TOXICANTS
The stability of certain toxic compounds from bleach plants during stor-
age was determined under the same conditions that were found to be satis-
factory for fatty and resin acids (pH 11, 22°C). Adjustment of the pH to 3
for shipping was also investigated.
A sample of the secondary effluent from a typical bleached kraft mill
was obtained for testing. The quantities of toxicants found in the initial
analysis of the secondary effluent and the bleach plant sewer were too low to
be useful in an evaluation of their stability. The use of an electron cap-
ture detector to improve the sensitivity and specificity was considered, but
the initial trials indicated the need for a significant amount of exploratory
work to make this workable. Spiking of the effluent with quantities that
could be determined with a flame ionization detector was the most practical
method of completing this study. The concentrations added were much larger
than would normally be found in effluents, but it was hoped that general
trends could be established. Samples of the secondary effluent were spiked
with known quantities of the toxicants, adjusted to pH 3 and pH 11, and
stored at room temperature (22°C) for various periods of time. The spiked
sample was analyzed in duplicate without aging, and single determinations
were made on samples aged h and 7 days.
Results shown in Table 6 demonstrate that the shipping conditions
proposed for the samples to be analyzed for fatty and resin acids were also
adequate for the bleach plant toxicants.
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SECTION 6
PROCEDURES USED IN INVESTIGATION
SAMPLING AND SAMPLE PRESERVATION
The sampling was carried out by mill personnel. Each mill was instruct-
ed as to the purpose of each sample so that a suitable sampling point could
be established. The specific sampling points for each mill are indicated
on the waste water treatment system diagrams.
To achieve the goal of the project, it was important to have the output
of a system representative of the input. Continuous sampling over an 8-12
hour period was recommended. Flow-proportional automatic samplers were used,
when available. The composites were refrigerated during sampling, if pos-
sible. The samples sent to the Institute were adjusted to pH 11 with 10%
sodium hydroxide solution and kept cool (3°C) until shipped.
Samples for determination of bleach plant toxicants and fatty and resin
acids were placed in 500-cm3 (pint) amber bottles. The bottles were filled
to within 1 cm of the top with the sample at ambient temperature (22°c)
(72°F). Screw caps fitted with Teflon-faced inserts were used to seal the
bottles.
Samples for chloroform determination, with no pH adjustment, were placed
in 125-cm3 (k-oz) bottles. The bottles were filled to the top to eliminate
any air and sealed with Teflon-lined screw caps.
The bottles were placed in polyfoam shipping cartons and shipped immedi-
ately by air freight. The samples for the chloroform determination were
shipped directly to the NCASI laboratory in Corvallis, Oregon.
Each mill was supplied with the required number of bottles, liners, and
shipping cartons to collect three sets of samples. The bottles were cleaned
by washing with a detergent, and rinsing with hot water, distilled water, and
finally, acetone. After the bottles were allowed to air dry, they were la-
beled, capped, and sent to the participating mills. Specific sampling and
shipping instructions were included.
DETERMINATION OF FATTY AND RESIN ACIDS
Solvent Extraction
The entire sample (500 cm3) was transferred to an Erlenmeyer flask. A
250-cm3 aliquot was removed for analysis. The sample was thoroughly mixed
IT
-------
during the removal of the aliquot to ensure even distribution of any solids.
A measured amount (100 cm3) of anhydrous ethyl ether was used to rinse the
sample bottle and a proportional amount (50 cm3) was combined with the ether
used for the extraction.
The sample was acidified to pH 3.0 with 10$ sulfuric acid. A pH meter
was used for this adjustment. The acidified sample was transferred to a
separatory funnel (500-cm3) and 2.0 cm3 of a heptadecanoic acid solution was
added as an internal standard. The internal standard solution was prepared
by dissolving a weighed amount of acid in a quantity of methanol to produce a
concentration of one milligram per cubic centimeter. This standard was fresh-
ly prepared each day.
The aqueous sample was extracted by shaking vigorously with 70 cm3 of
ethyl ether for about 20 seconds. The ether layer was transferred to a sec-
ond separatory funnel (250-cm3) containing 10 cm3 of acidified water. The
extraction was repeated with two 50-cm3 portions of ether. All the ether
extracts and any emulsified materials (which frequently formed at the inter-
face) were transferred to the second funnel. When the emulsion persisted in
the second funnel, the combined extracts were centrifuged to separate the
layers.
The clear ether layer was transferred to an Erlenmeyer flask, and a few
grains of anhydrous sodium sulfate were added to remove the water. The ether
was removed on a rotary evaporator at 30°C. The evaporation was carried on
until the sample just reached dryness. The residue was immediately dissolv-
ed in 8 to 10 cm3 of ether-methanol (9:1).
Preparation of Methyl Esters
The methyl esters of the acids were formed by the addition of a fresh
ether solution of diazomethane. The diazomethane was generated from a mix-
ture of 3-5 cm3 of Carbitol, 1.2 cm3 of 37-5$ potassium hydroxide and 2.2
grams of Diazald (Aldrich Chemical Co.). The Carbitol, potassium hydroxide,
and one cm3 of ether were placed in a 50-cm3 distilling flask having a long
side arm which terminated below the surface of 15 cm3 of ether in an Erlen-
meyer flask (50-cm3). The receiving flask was placed in an ice bath and the
distilling flask in a water bath at 60-70°C. A solution containing 2.2 grams
of Diazald in 15 cm of ether was introduced into the generator via a drop-
ping funnel attached to the top of the distilling flask. The Diazald solu-
tion was added at a uniform rate over a two-minute period. The dropping
funnel was finally rinsed with 5 cm3 of ether.
The extracts were methylated immediately by adding the diazomethane
dropwise until a definite yellow color persisted. (When the extract was
colored so that the endpoint could not be distinguished, a weighed amount of
heptadecanoic acid equal to the weight of the extract was titrated with
diazomethane to give a rough estimate of the volume required for complete
methylation.) After 10-15 minutes, the diazomethane and solvent were removed
on a rotary evaporator at 30°C. The extract was taken to near dryness and
redissolved in 1 cm3 of n-hexane.
18
-------
Separation of Methyl Esters from Neutrals
The presence of certain non-acidic compounds in some of the samples made
the gas chromatographic analysis difficult due to the large number of peaks
which inhibited good resolution of the acids to be measured. In such cases
the methyl esters were separated from the neutrals by column chromatography.
A glass column 200 mm long with an inside diameter of 6 mm was packed
with a UO-mm layer of silica gel plus a 10-mm layer of anhydrous sodium sul-
fate. The silica gel was a product of Davison Chemical, Baltimore, Maryland,
grade 950, 60-200 mesh, Wo. 950-08-08-226. The silica gel was activated at
130°C and stored along with the sodium sulfate at 130°C. Columns were packed
hot to avoid deactivation at room temperature.
One cm3 of hexane was passed through the column followed by 0.3 cm3 of
the hexane solution of the methyl esters. Azulene (50 yl of a hexane solu-
tion containing 1 yg/yl) and Sudan I (10 yl of a hexane solution containing
10 yg/yl) were added to the methyl ester aliquot to serve as indicators in
the separation. The esters were loaded onto the column when the level of the
hexane (l cm3) reached the top of the sodium sulfate. A solvent composed of
hexane and ethyl ether (95+5) was used to separate the methyl esters which
were contained in the fraction between the start of the elution of the
azulene and the start of the elution of Sudan I.
The fraction containing the methyl esters was concentrated on a rotary
evaporator (30°C) to about 0.3 cm3.
Gas Chromatographic Analysis
A Becker Model ^17 gas chromatograph was used for the separation of the
methyl esters (Fig. l). The area measurements were made with a Disc integra-
tor on a Honeywell Electronik 16 recorder. The use of this type of integra-
tor made it necessary to buck out the increased background after programming.
(Note break in curve, Pig. 1.)
The following conditions were used for the GC separation:
Column: 1.83 x 0.0032 m (6 ft x 1/8 in.) stainless steel containing
10$ EGSS-X on Gas Chrom P, 100/120
Column temperature: 170°C for 22 minutes, Program 10°C/min to 200°C
Injector temperature: 200°C
Detector temperature: 235°C
Detector: flame ionization
Carrier gas: He at 30 cm3/min
Volume injected: 3-^ yl
Calculations
Area of acid x mg of internal std. x 1000 _ ,
Area of internal std. x ml of sample ~ mg/ °r Ppm
19
-------
DETERMINATION OF BLEACH PLANT TOXICANTS
Solvent Extraction
The sample was extracted according to the procedure used for fatty and
resin acids except for the quantity of heptadecanoic acid added as an inter-
nal standard. A solution containing 20 yg/cm3 of heptadecanoic acid was pre-
n O
pared, and exactly 2.0 cm was added to each 250 cm sample.
Preparation of Methyl Esters and Ethers
The method reported for fatty and resin acids was followed. The time
allowed for the reaction with diazomethane was increased from 10-15 minutes
to 30 minutes.
The methyl esters and ethers were dissolved in one cm3 of hexane and
stored in a sealed ampule.
GC/MS Analysis
The toxicants in the methylated extracts were identified and measured by
limited mass reconstructed gas chromatography. The analyses were performed
by the Calgon Corporation, Water Management Division, Box 13^6, Pittsburgh,
Pa.
The samples and standards were analyzed using the GC/MS conditions list-
ed below:
Column: 1.52 m x 2.0 mm ID glass, packed with 3% OV-17 on 100/120
mesh Gas Chrom Q
Column temperature: 135°C to 230°C at 2°C/minute
Injector temperature: 2.kO°C
MS inlet temperature: 2^0° C
MS analyzer pressure: 5 x 10~5 Torr
Mass range: 20 to ^50 atomic mass units (less air)
Scan rate: 7 m sec/atomic mass unit
Multiplier voltage: l800 volts
Electron energy: 70 electronvolts
Emission current: 0.5 milliamps
Preamp sensitivity: 10~7 amps/volt
Quantitation was by area comparison with the internal standard, hepta-
decanoic acid, using response factors based on standard solutions. The
specific ions used for quantitative measurements were:
Heptadecanoic acid — 7^ We
Trichloroguaiacol — l62
Tetrachloroguaiacol — 276
Dichlorostearic acid — 7^
Epoxystearic acid — 155
Monochlorodehydroabietic acid — h3
Dichlorodehydroabietic acid — ^3
20
-------
DETERMINATION OF CHLOROFORM
Five to ten cm3 of effluent were extracted with 2.0 to U.O cm3 of puri-
fied hexane. The hexane was purified "by distillation, followed by passage
through a column packed with activated alumina (MCB 929^ heated to ^00°C).
A 15-cm3 graduated glass-stoppered centrifuge tube was used for the
extraction. The sample and hexane were shaken vigorously for 15 seconds and
allowed to stand for a few minutes. The hexane layer was removed with a dis-
posable pipet and stored in a small screw cap vial.
The extract was analyzed by injecting directly onto the GC column.
Conditions for the gas chromatographic analysis are as follows:
Column: U.6 x 0.003 m (15 ft x 1/8 in.) stainless steel containing
10$ Carbowax 20 M on Gas Chrom Q, 100/120.
Column temperature: TO°C for 8 minutes, then programmed to 1^0°C
at 6°C/min. A constant temperature of 95°C was used for
samples that contained only chloroform.
Carrier gas: Nitrogen at 20 cm3/min with detector make-up flow
at 30 cm3/min.
Detector: (l) Electron capture, Model lljOA, Analog Technology Corp.,
constant current type.
(2) Microcoulometric halide detector.
Standards for gas chromatographic analyses were prepared by volumetrical-
ly adding chloroform to hexane.
21
-------
SECTION 7
RESULTS OF ANALYSES
MILL 1
Mill 1, located in the northern midwest, produces about 272 metric
tons/day (300 tons/day) of corrugating medium. About l8l metric tons/day
(200 tons/day) of neutral sulfite semichemical pulp are produced from mixed
hardwoods, primarily red oak, elm, and hard and soft maple. An additional
91 metric tons/day (100 tons/day) of pulp are produced by repulping kraft
clippings.
The mill operates with an essentially closed white water system. Excess
water is removed from the system by a commercial size reverse osmosis (RO)
plant. Weak wastes from the white water system are fed to the RO unit and
separated into uncontaminated water (permeate) and a concentrate of white
water solubles which is returned to the countercurrent washing system in the
pulp mill. Feed to the RO plant contains h-6% dissolved solids consisting of
wood extractives and sodium lignosulfonates; it also contains about 300 ppm
suspended solids. This feed is supplied to the RO plant at a pH of 5.6-6.0,
a pressure of 7.03 kg/cm2 (100 psi) and a temperature of 60-65°C (l^O-150°F).
Prior to entry into the RO equipment the feed is cooled to 38°C (lOO°F).
The RO system is comprised of 288 modules divided equally among six
racks. Each module contains 18 porous tubes which are fiberglass, filament-
wound, and resin bonded. The membrane, formed from cellulose acetate, is on
the inner surface of the fiberglass tubes and provides 1.55 m2 (l6.7 ft2) of
membrane surface per l8-tube module.
Clarified process water feed flow, under conditions of full plant
operation, is 0.3^1 m3/min (90 gpm). Two feed pumps pressurize this to 31.6
kg/cm2 (U50 psi) before it combines with the recycled concentrate. The com-
bined flows, 0.9^6 mVmin (250 gpm) are boosted by the six recycle pumps to
^2.2 kg/cm2 (600 psi). This feed is supplied to the six module rack assem-
blies in parallel. After passage through the modules, a portion of the con-
centrate, 0.255 m3/min (67.5 gpm), is returned to the pulp mill, and the re-
mainder is recycled for combining with fresh feed. Permeate goes into the
mill discharge to the river. Although the design flux of the system was
0.011 m3/m2-hr (6.65 gal/day-ft2), the present flux is about 0.0085 m3/m2-hr
(5 gal/day-ft2).
For this investigation, samples were taken of reverse osmosis feed, per-
meate, and total mill effluent, as indicated in Fig. 3. RO feed and permeate
22
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were sampled by taking a 200-ml grab every half hour for eight hours. Sam-
pling of total mill effluent was done with a chain-driven bucket sampler
which emptied into a container inside a refrigerator. This device took a
constant volume, timed sample every 3-75 minutes over a 2l|-hour period.
Analytical data from Mill 1 are shown in Table 7.
MILL 2
Mill 2 is a bleached kraft mill located in the southeast. It produces
1206 metric tons/day (1330 tons/day) of pulp from about 60% softwood and kd%
hardwood. Of particular interest in this investigation was the treatment of
a portion of the mill's pine caustic extraction filtrate in a pilot ultra-
filtration unit.
The ultraf iltration unit is sketched in Fig. k. From the feed tank the
caustic extract passed through a Kisco filter containing 0.76 m (30 in.) of
Filter AG granular anhydrous aluminum silicate. Final prefiltration in a
Broughton basket type filter removed suspended solids greater than 10 um.
Only one spiral wound module was used in this study. Area of the Abcor WRP
No. 1 membrane was 3.72 m2 (kO ft2). This is a proprietary synthetic polymer
membrane which permits the feed to have higher temperature and pH than allow-
ed by cellulose acetate membranes. Concentrate was not recycled in this in-
vestigation.
Samples taken for this study included feed, prefiltered feed, concen-
trate, and permeate.
Analytical data for these samples are reported in Table 8.
MILL 3
This mill, located in the south, produces about 5^ metric tons/day (600
tons/day) of bleached kraft pulp. Its bleaching sequence is CEHD. Of in-
terest at this location is a pilot ultrafiltration unit operating on the
mill's caustic extract.
The feed tank for the ultrafiltration (UF) unit is supplied with caustic
extract from the bleaching of hardwood, softwood (pine), or a combination of
both. This valving arrangement in the mill bleach plant is necessary in
order to ensure a continuous flow of caustic extract in the event that one
of the bleaching operations goes down. Concentrate from the UF unit is re-
cycled back to the feed tank during the course of a run, and new caustic ex-
tract is added to the tank at the same rate as permeate leaves the system.
This flow is diagrammed in Fig. 5. Fibers are removed from the feed with a
5 ym woven polypropylene fabric filter.
The ultrafiltration unit employs dynamic membranes formed on a ceramic
tubular support. The membranes consist of a hydrous zirconium oxide bottom
layer and a hydrous silicon oxide overlayer. Each tube has a diameter of
0.58 cm (0.23 in.). There are 19 tubes in a bundle having a filtration area
of 0.11-0.13 m2/bundle (1.2-1.^3 ft2/bundle). The UF unit has a total surface
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temperature of U6°C (115°F). Velocity of the feed across the membrane was
^57 cm/sec (15 ft/sec) with a flow rate of 0.12 m3/min (3.3 gpm). Permeate
flow rate was 1.02 m3/day (270 gal/day). Flux was 0.91 m3/m2-day (22.3 gal/
day-ft2). Pressures were 15.5 kg/cm2 (220 psi) inlet and 7.03 kg/cm2 (100
psi) outlet.
Samples of feed and permeate from the UF system were grab samples which
were not composited over a time period. This was justified because the sys-
tem was operating at close to steady state.
Analytical data for these samples are given in Table 9-
MILL 1*
Mill k is an integrated kraft pulp and paper mill located on the east
coast. Total production averages 860 metric tons/day (950 tons/day) of un-
bleached softwood kraft paper, corrugated medium, and linerboard and 230
metric tons/day (250 tons/day) of bleached hardwood market pulp. The bleach-
ing sequence is D/COD.
Principal components of the waste treatment system include a primary
clarifier, an oxygen-activated sludge treatment facility, and two secondary
clarifiers, as indicated in Fig. 6. The center feed peripheral overflow
primary clarifier is 38 m (125 ft) in diameter with a side water depth of 3 m
(10 ft). It was designed for 55%_jemoval of total suspended solids at a max-
imum flow of 6l,700 m3/day (l6.3 M gpd). In the cooling tower, the tempera-
ture of the primary clarifier effluent is reduced to 35°C (95°F). The
oxygen-activated sludge basin is 30 m (100 ft) wide by 60 m (200 ft) long
with a liquid depth of 3.2 m (10.5 ft) and a gas space of l.h m (H.5 ft).
Effluent from the oxygen-activated sludge system flows into two peripheral-
feed peripheral-overflow secondary clarifiers which are ^1 m (135 f"t) in
diameter with a side water depth of U.3 m (l^ ft). Calculated hydraulic
detention times of the primary clarifier, the oxygen-activated sludge basin,
and the secondary clarifiers, are 1 hr 50 min, 3 hr 10 min, and 6 hr, respec-
tively.
The oxygen-activated sludge basin mixed liquor volatile suspended solids
concentration is controlled to maintain a food to microorganism ratio of 0.7-
1.0 day"1. In the first stage of the oxygen-activated sludge basin the pH is
controlled between 6.2 and 7.5. The activated sludge recycle ratio is ap-
proximately 35%.
During the period of this study, the waste water treatment plant had the
following average operating characteristics: Solids Production, O.h3 kg
(ib) suspended solids produced/kg (ib) BOD removed; Oxygen Usage, 1.36 kg
(ib) 02 applied/kg (ib) BOD removed; Oxygen Utilization, gh.2.%.
For this investigation, samples were taken at the points shown in Fig.
6. The period of composite was eight hours, and four grab samples were taken
at each point during that period. Sampling periods were scheduled to account
for the detention times of the components of the waste treatment system.
29
-------
TABLE 9- MILL NO. 3 DATA
Mill No. 3; Location: South; Process: bleached kraft; Bleach Sequence: CEKT
Wood Species : hardwood or softwood
Waste Treatment System: ultrafiltration
Sampling date
BOD, ppm
Flow rate, m3/min
(gpm)
Production, metric tons/day
(short tons/day)
PH
Temperature , °C
(°F)
Bleach plant products, ppm
Trichloroguaiacol
Tetrachloroguaiacol
Epoxystearic acid
Dichlorostearic acid
Monochloro-
dehydroabietic acid
Dichloro-
dehydroabietic acid
Total
Chloroform, ppm
Raw caustic extract
7-12*
1*57
0.12
(33)
—
(__)
9.5-10.5
k6.0
(115)
1.06
0.696
6.87
3.17
0.356
1.2U
13.it
0.126
Permeate
7-12
111
0.0007
(0.19)
—
( — )
—
—
0.20k
0.128
1.58
0.228
0.092
0.180
2.1+
0.101
#
Samples were taken on second day of operation. Background data were available
only for the first day of operation. Some parameters could be as much as double
the numbers indicated, due to recycling of concentrate back to the feed tank.
30
-------
§
-P
W
0)
fi
0)
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-P
-------
Thus, the same portion of effluent was sampled as it passed through the fa-
cility.
Analytical data from Mill k are shown in Table 10. Daily loadings for
bleached toxicants and chloroform are based on bleached pulp production.
MILL 5
Mill 5» located in the south, is a totally unbleached operation produc-
ing about Uo8 metric tons/day (ij-50 tons/day) of kraft pulp. The mill pulps
principally loblolly pine chips plus about 15$ hardwood, which is mostly gum.
Waste treatment facilities are shown in Fig. J. They consist of a pri-
mary clarifier, three parallel oxygen-activated sludge units, and a tertiary
clarifier employing alum treatment. Each oxygen-activated sludge unit is
33.^ m (109.5 ft) in diameter and U.9 m (l6 ft) tall. Roughly half the tank
volume is a H-stage activated sludge system and the other half is a clarifier.
Effluent, oxygen, and recycled biomass enter the first stage. About 3.7 m
(12 ft) of the height is occupied by mixed liquor, leaving 1.2 m (U ft) of
space for oxygen. From the first stage, effluent and oxygen flow to the
second and so on to the fourth, and from there to the secondary clarifier.
Under Current operation the average throughput per unit is 10,670 m3/day
(2.82 M gpd), which gives an average detention time of 3-72 hours. The sys-
tem operates with a food/microorganism ratio of approximately 1 day"1 and a
mixed liquor suspended solids of about 2500 ppm.
Effluent flows to a reactor-clarifier forming the tertiary system. Alum
mud is added in the tertiary system to bring the pH to 5-0-5.3- This precip-
itates organics and suspended solids. Effluent from the tertiary clarifier
flows to a holding lagoon.
Settled solids from the tertiary clarifier, the primary clarifier, and
waste biomass are dewatered and burned. Furnace ash is conveyed to reactor
tanks, where sulfuric acid is added to convert the aluminum oxide content of
the ash to alum for reuse in the tertiary clarifier.
Because the tertiary system was not running at the time of this study,
its operation was simulated by bench-scale alum treatments. Alum was added
with stirring to two-liter samples of secondary effluent to reduce the pH to
5. One ppm of cationic polyelectrolyte was also added, and the samples were
allowed to settle for 2-2.5 hours.
Time-intervaled composite samples were taken from the mill waste treat-
ment system at the points indicated on the sketch. The samples were taken
every 30 minutes for 2^ hours and were accumulated in iced sample containers.
Analytical data for these samples are shown in Table 11.
MILL 6
Mill 6 produces unbleached kraft and semichemical pulp and is located in
the south. Kraft pulp production, 800-1200 metric tons/day (900-1300 tons/
32
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Figure 7. Mill No. 5 waste treatment system.
35
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36
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day), employs Kamyr digesters with internal "Hi-Heat" washing followed by two
conventional cylinder washers; the wood is loblolly pine. Hardwoods (10—20?
gum, the rest primarily oak) are pulped by a continuous green liquor semi-
chemical process (17-20 minutes at l80°C). Production is about 180 metric
tons/day (200 tons/day). The corrugating mediiam paper machine white water
system is closed, so that spent liquors are normally lost only from pulping
and washing leaks, spills, vacuum pump carry-over, and felt washing. Includ-
ed in the discharge from semichemical pulping is wood sap squeezed out at the
digester feed screws, 0.06-0.07 m3/min (15-20 gpm) at 16,000 ppm BOD.
Of principal interest in this project is the mill's lime treatment color
removal system. Lime slurry is prepared at about 10$ consistency and added
to raw waste at about 1000 ppm lime based on weight of effluent. As indicat-
ed in Fig. 8, the treated waste passes into the color clarifier, vfaich is kl
m (135 ft) in diameter. At a niHyinn^m rise rate of 58.7 m3/mz-day (it&O gal/
day-ft2), this provides a capacity of 68,130 m3/day {lB M gpd). From the
color clarifier, effluent passes to a 9 m (30 ft) diameter by 3-6 m (12 ft)
deep carbonation tank where lime kiln stack gas is introduced. Calcium car-
bonate formed by carbon dioxide reaction with the remaining calcium hydroxide
is settled in a second clarifier, called the carbonation clarifier, which is
essentially identical with the color clarifier. Sludge from the color clari-
fier is dewatered and sent to the lime kiln. Effluent from the color removal
process enters a lagoon system; study of the lagoon system is not included in
this project.
Sampling periods for this study were of eight hours duration. A flow-
proportional sampler was used for raw waste, and continuous, peristaltic pump
samplers were used for the other two stages. The sampling periods were off-
set for the estimated holdup time in the clarifiers. Sample receivers were
cooled in an ice bath. The process in this mill is sufficiently variable to
make samples taken only a few days apart represent a typical range of mill
operations. Consequently, intervals between the three samplings were shorter
than for most mills in this project. During the second and third samplings,
recarbonation and final clarification for the sampling were accomplished on a
pilot scale sidestream to avoid interference of solids carryover from the
color clarifier. The only deviation from normal process conditions should
have been a lower temperature, which could affect retention of soluble or
condensible gases from the kiln.
Analytical data for this mi~n are shown in Table 12.
MILL 7
Mill 7» located in the east, uses the sulfite process and produces
bleached pulp from raized eastern hardwoods. Separate systems are used to
treat the pulp mill waste, which has high oxygen demand, and the paper mill
waste containing significant amounts of suspended solids. Only the pulp
mill waste control facility is of interest in this project. Spent liquors
collected from the multistage countereurrent brownstock washers are evaporat-
ed and burned without chemical recovery. Volatile organic material in evapo-
rator distillate, dilute spent liquors from the prebleach washers, and spent
37
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bleach wash waters are neutralized in pH and subjected to biological degrada-
tion in an activated sludge plant.
As shown in Fig. 9, variations in waste strength and flow are equalized
in a basin which has an effective detention time of 2.5 hours. The waste is
then aerated for a theoretical detention time of 2k hours. Aeration is
achieved with mechanical surface aerators. The food to microorganism ratio
for an average mixed liquor volatile suspended solids of 6000 ppm is about
0.7 day"1. Sludge production is 0.5 kg (lt>) mixed liquor total suspended
solids per kg (ib) BOD removed. Prior to release to the river, the effluent
passes through a clarifier which has a theoretical detention time of 6 hours.
Samples analyzed in this project were composites of one-hour grab sam-
ples collected over 2k hours. The samples were not proportional to flow
since the normal flow variation is only about +_10$.
Analytical data for Mill 7 are shown in Table 13- In the table, Influent
A and B and Effluent A and B refer to duplicate samples collected on the
dates indicated.
MILL 8
Mill 8, located on the west coast, produces about 875 metric tons/day
(900 tons/day) of bleached kraft pulp from sawdust and western hemlock. Its
bleaching sequence is CEHED. The mill also produces 2^9-272 metric tons/day
(275-300 tons/day) of refiner groundwood.
Principal features of the mill's waste treatment facility include a pri-
mary clarifier of 76.2 m (250 ft) diameter and an activated sludge system.
The bleach sewer bypasses the primary clarifier and goes directly to second-,
ary treatment, as indicated in Fig. 10. Also shown in the figure is the
wasting of secondary sludge back to the primary clarifier. This sludge wast-
ing occurs at a flow rate of 1.9 m3/min (500 gpm) for eight hours per day.
Nominal flows for the principal streams into the waste treatment system are
bleach sewer 57,000 m3/day (15 M gpd) and process sewer 95,000 m3/day (25 M
gpd). Consequently, the flow of wasted sludge contributes only slightly to
total effluent flow from the primary clarifier. The primary clarifier, hold-
ing pond, and aeration basin each have detention times of 8 hours. Detention
time in the secondary clarifiers is 6 hours. The activated sludge system
operates with a food/microorganism ratio of 0.12 day"1, a mixed liquor sus-
pended solids of 5983 ppm, and a sludge volume index of 99-5 ml/g. Diameter
of the secondary clarifier is 6k m (210 ft).
Samples for this investigation were taken at the points shown in Fig.
10. Grab samples from the process sewer, the bleach sewer, and the primary
clarifier effluent were taken each hour for nine hours. Secondary effluent
to the river was sampled automatically with a refrigerated sampler.
Analytical data for these samples are shown in Table lk.
ko
-------
Evaporator Condensate
Primary Sludge Centrate
Imhoff Effluent
' Sludge
Recycle
Sampling Points
[l) Activated Sludge Influent
^2) Activated Sludge Effluent
Figure 9. Mill No. 7 waste treatment system.
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MILL 9
Mill 9, located in the south, produces about 1360 metric tons (1500
tons) of paperboard per day. Typical pulp production includes about 1225
metric tons/day (1350 tons/day) unbleached pine kraft, of which up to l8l
metric tons/day (200 tons/day) are subsequently bleached, and about 91 metric
tons/day (100 tons/day) of hardwood semichemical. Because bleached pulp pro-
duction is small compared with total production, this is considered to be an
unbleached mill for the purpose of this project.
As indicated in Fig. 11, the mill's waste treatment facilities consist
of a primary clarifier and a 25.5 ha (63 acre) aerated lagoon. Twenty-seven
56-kw (75-hp) aerators are employed in the first two-thirds of the lagoon.
Detention times are 5 hours in the clarifier and 10 days in the lagoon. Typ-
ical effluent flow is lll|,000 m3/day (30 M gpd).
Raw and primary waste samples taken for this study were composites of
grab samples collected at two-hour intervals over an eight-hour period. The
sampling period for the primary effluent was delayed five hours to account
for the detention time of the clarifier. The lagoon outfall was sampled con-
tinuously with a timed sampler into a refrigerated container. Lagoon outfall
and primary effluent samples were taken during the same period.
Analytical data for Mill 9 are listed in Table 15.
MILL 10
Mill 10 is a west coast, ammonium bisulfite mill which produces bleached
pulp. Bleaching sequence is CEH, daily pulp capacity is 28l metric tons (310
tons), and primary wood species is western hemlock.
The mill's waste treatment system is sketched in Fig. 12. After leaving
the ^5.7 m (150 ft) diameter primary clarifier, effluent enters the two-cell
aerated lagoon system. The first lagoon, with a detention time of two days
and an area of 6.5 ha (l6 acres) has eleven 7^.6-kw (100-hp) aerators. The
second lagoon has a detention time of seven days, an area of 20.7 ha (51
acres), and employs six 7^.6-kw (lOO-hp) aerators. Lagoon capacity is
600,000 m3 (150 M gal). Normal waste load to the lagoons is 13,600-18,150
kg/day (30,000-^0,000 Ib/day) of BOD. Bleach effluent bypasses the primary
clarifier and joins the primary effluent prior to entry into the lagoons.
For this study, samples were taken continuously at the points shown on
the sketch, refrigerated, and submitted as 2i|-hour composites.
Analytical data are shown in Table 16. Daily loadings for bleached
toxicants and chloroform are based on bleached pulp production.
MILL 11
Nominal production at this mill amounts to 726 metric tons/day (800
tons/day) of bleached kraft pulp and 118 metric tons/day (130 tons/day)
bleached groundwood. The kraft mill production is regularly changed from
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Figure 12. Mill No. 10 waste treatment system.
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hardwood pulp to softwood pulp, with the grade change occurring at intervals
of approximately 20 to 36 hours. Mill 11 is located in the northern midwest.
The mill's effluent treatment facilities consist principally of primary
clarifiers and an aerated lagoon system, as shown in Fig. 13- Two primary
clarifiers, arranged in parallel, are 5^.9 m and 6l m (l80 and 200 ft) in
diameter and have 3 hours detention time. The first aerated lagoon is k.3 m
(ill ft) deep, holds ^5^,000 m3 (120 M gal), and has five 1^.7-kw (60-hp) and
two 55.9-kw (75-hp) aerators. The second lagoon has a controllable depth;
normally it is 2.1* m (8 ft) deep with a volume of 757,000 m3 (200 M gal). It
employs twelve UU.7-kw (60-hp) aerators. Detention times in the lagoons are
U.O and 6.7 days. Between the lagoons and the river are an 18.3 m (60 ft)
diameter flocculator and an 82.3 m (270 ft) diameter secondary clarifier with
U.5 hours detention time.
An additional component of the mill's environmental control system is a
steam stripping column used to reduce odor and BOD in condensates produced in
the kraft process. Waste waters collected for steam stripping include hot
water accumulator overflows from digester blows, turpentine decanter under-
flow, evaporator hot-well condensates, water seal tank purge water, and con-
densates from odorous gas conveyance pipelines. The stripper column is l6 m
(53 ft) high, 2.2 m (7.3 ft) in diameter, and consists of a 2^-tray column
with U6 bubble caps per tray. Feed enters near the top of the fourth plate
down in the column and 4.22 kg/cm2 (60 psi) steam enters at the bottom. Con-
centrated odorous gases removed at the top of the column go to the lime kiln
or incinerator for combustion. Stripper effluent ultimately goes to the mill
process sewer.
Samples were taken over US-hour periods in order to contain effluents
from both hardwood and softwood pulp production. There was no attempt made
to account for effluent treatment system delays in scheduling the sampling,
so effluent samples would tend to favor the pulp being run at the start of
sampling. Sample set 1 began with hardwood and ended with softwood; set 2
was the reverse. Set 3 covered two grade changes beginning with a softwood
run.
Individual grab samples, approximately proportional to flow, were re-
frigerated and then blended to produce a composite sample at the end of the
sampling period. Sampling points are shown in Fig. 13. Steam stripper in-
fluent and effluent samples were also taken.
Analytical data are shown in Table 17. Daily loadings for bleached
toxicants and chloroform are based on bleached pulp production.
MILL 12
This mill, located in the east, produces approximately k^k metric tons/
day (500 tons/day) of bleached pulp. Separate lines for mixed hardwoods
(basically oak) and mixed softwoods (mostly pine) yield about 272 metric
tons/day (300 tons/day) and l8l metric tons/day (200 tons/day), respectively.
The bleaching sequence on each of the two lines is CHHD.
53
-------
Raw Mill Effluent
Nutrients
Aerated
Basin
Aerated
Basin
_ Recjrclgd Sludge.
Sampling Points
l) Raw Effluent (Composite)
y Primary Effluent (Composite)
3 Final Effluent
Figure 13. Mill No. 11 waste treatment system.
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Principal features of the mill's waste treatment facilities, shown in
Fig. l4, include primary clarification and a contact-stabilization activated
sludge system. Three primary clarifiers [two 22.8 m (75 ft) in diameter and
the other 32.3 m (106 ft) in_ diameter] provide 3.2 to 2_/f hours retention
time for 45,000 m3/day (12 M gpd) to 53,000 m3/day (lit M gpd) mill effluent
flow. Clarifier overflow rates range from 27.9 m3/m2-day (684 gal/day-ft2)
to 32.3 m3/m2-day (792 gal/day-ft2).
The secondary treatment plant consists of three aeration basins in
series. One basin is a stabilization tank for reaeration of return sludge,
while the other two are contact aerators for aeration of the mixed liquor.
For the 45,000 m3/day (12 M gpd) to 53,000 m3/day (l4 M gpd) average mill ef-
fluent flows and a 40-55% recycle of activated sludge, the stabilization tank
provides 3.7 to 2.3 hours retention for return sludge aeration, and the two
aeration basins allow for 3.8 to 2.9 hours mixed liquor aeration. Operating
characteristics of the plant include a mixed liquor suspended solids of 2500
ppm, a food/microorganism ratio of 0.3-0.35 day"1, and a sludge volume index
of 275 ml/g. Four secondary clarifiers in parallel have overflow rates of
24.9 m3/m2-day (6l2 gal/day-ft2) to 32.3 m3/m2-day (792 gal/day-ft2) and de-
tention times of 3.3-2.5 hours.
Samples taken at the points shown in Fig. Ik- included mill raw waste,
primary effluent, and secondary effluent. In addition, samples of sludge
lagoon supernatant containing primary sludge thickener overflow were also
taken. Flow-proportional samples were used on raw mill waste and secondary
effluent. Time-intervaled composite samples were taken from the primary ef-
fluent, and grab samples of sludge lagoon supernatant were taken at 2-hour
intervals. Duration of a sampling period was 8 hours.
Analytical data for samples from Mill 12 are given in Table 18. Daily
loadings for bleached toxicants and chloroform are based on bleached pulp
production.
MILL 13
Mill 13 is located on the west coast. It produces about 163 metric
tons/day (l80 tons/day) of pulp from a mixture of pine, Douglas-fir, white
fir, and cedar. The bleaching sequence is CEHKD. Paper production is about
363 metric tons/day (400 tons/day).
As shown in Fig. 15, the mill's waste treatment system consists of pri-
mary clarification followed by biological treatment in lagoons. Prior to
clarification, mill wastes enter either the North Holding Basin (NHB), with
a capacity of 7570 m3 (2.0_F gal), the Primary Control Basin (PCB), with a
capacity of 2950 m3 (0.78_M gal), or the South Holding Basin (SHB), with a
capacity of 7570 m3 (2.0 M gal). Primary clarifier No. 1 treats paper mill
waste, for the most part. It has a diameter of 25 m (82 ft), theoretical
detention time of 2.6 hours, and rise rate of 29.9 m3/m2-day (734 gal/day-
ft2). Primary clarifier No. 2 receives most of the pulp mill effluent. Its
diameter is 42.7 m (l4o ft), detention time 4.5 hours, and rise rate 23-7
m3/m2-day (582 gal/day-ft2).
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The first lagoon's area is 1.6U ha (U.I acres), its depth is 3-36 m
(11.0 ft), and its theoretical detention time is 1 day. It has six 56-kw
(75-hp) aerators. The second lagoon's area is 10.9 ha (27 acres), its depth
is 3.20 m (10.5 ft), and its theoretical detention time is 6 days. This
lagoon is divided into two sections, one-third devoted to aeration and two-
thirds to settling. The aeration section contains nine 22.U-kw (30-hp)
aerators.
Samples for this investigation were taken at the points indicated in
Fig. 15. Points 1, 2, and 3 were sampled by hand every 30 minutes for a
period of 12 hours. Amounts of sample taken at each Point 1 were weighted
in proportion to flow. Point k was sampled for 2k hours using a flow pro-
portional automatic sampler. All samples received immediate refrigeration.
Analytical data for these samples are given in Table 19. Daily loadings
for bleached toxicants and chloroform are based on bleached pulp production.
MILL Ik
Mill lU is a kraft mill without bleaching located on the west coast. It
produces about 1088 metric tons/day (1200 tons/day) of unbleached linerboard
from a pulpwood mix of about 80-85% Douglas-fir and 15-20% ponderosa pine.
Waste water treatment facilities, shown in Fig. l6, consist of primary
clarification and a completely mixed aerated lagoon. Effluent from the pulp
mill, including water from causticizing, cooking, washing, recovery, screen-
ing, and hydraulic barker, is fed into a 39-6 m (130 ft) diameter primary
clarifier at a rate of about 12.5 m3/min (3300 gpm). Paper mill effluent,
after clarification in a dissolved air flotation system, is added to the pulp
mill effluent at about 9.5 m3/min (2500 gpm). Combined effluents receive
final treatment in a lagoon with an area of 8.5 ha (21 acres) and 4.5-5*5
days detention time. The lagoon contains 11 aerators with a total of 6l5 kw
(825 hp).
Samples for this study were taken at the points shown in Fig. l6. Ex-
cept for the secondary effluent, samples were composites of k grabs taken at
2-hour intervals. Secondary effluent was sampled automatically over 2h hours
to yield a time-intervaled composite.
Analytical data are shown in Table 20.
MILL 15
This mill is located in the south and produces about h^h metric tons/day
(500 tons/day) of bleached kraft pulp and about ^hk metric tons/day (600
tons/day) of coated board. The bleaching sequence is CEDED. Wood species
used are pine, oak, and gum.
For waste treatment, this mill uses a primary clarifier, an aerated
lagoon, and polishing ponds, as shown in Fig. 17. In this project the mill's
final effluent was also subjected to a tertiary treatment, a bench-scale alum
precipitation.
62
-------
TABLE 19. MILL NO. 13 DATA
Mill No. 13, Location West Coast, Process: "bleached
Wood Species: 30-35^ pine; 30-3^^ Douglas- fir , 20-25% win
Waste Treatment System, primary clarifier and aerated lag
Sampling date
BOD, ppm
Flow rate, ra3/min
(gPm)
Production, metric tons/day
(short tons/day)
PH
Temperature , °C
(°F)
Fatty and resin acids, ppm
Oleic
Linoleic
Linolenic
Pimaric
Isopimanc
Abietic
Dehydroabietic
Total
Daily loading
kg/day
(Ib/day)
kg/ton
(Ib/ton)
Bleach plant products, ppm
Tricnloroguaiacol
Tetrachloroguaiacol
Epoxystearic acid
Dichlorostearic acid
Monochloro-
dehydroabietic acid
Dichlorodehydro-
abietic acid
Total
Dally loading
kg/day
(Ib/day)
kg/ton
(Ib/ton)
Chloroform, ppm
kg/day
(Ib/day)
kg/ton
(Ib/ton)
Saw
4-18
159
30.3
(8000)
165
(182)
9.4
33.9
(93)
0.29
0.14
<0.02
0.08
0.33
0.36
0.55
1.75
76.2
(168)
0.46
(0.92)
-------
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Landfill
Flotator
Recovered Fiber
Sampling Points
(l) Pulp Mill Effluent
(2) Paper Mill Effluent
(3) Primary Effluent
Ck) Final Effluent
Aerated
Lagoon
Figure 16. Mill No. Ik waste treatment system.
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Strong waste, indicated in Fig. 17, consists of waste occurring around
the digester, and from washing and screening. Process waste comes from the
board machine, the bleach plant, and from treatment of fresh intake water
from the river. These wastes pass into the primary clarifier, which has a
diameter of 83.8 m (275 ft). Effluent from the clarifier enters the aerated
lagoon, which has an area of 19«8 ha (^9 acres), a depth of k.6 m (15 ft), a
capacity of 999,000 m3 (26k M gal), and a detention time of 15 days. Aera-
tion is achieved by three blowers driven by 298-kw (UOO-hp) motors which con-
vey 696 m3 (2*1,600 ft3) of air per minute to 1120 static aerators in the
lagoon. From the aerated lagoon, effluent flows to a quiescent stabilization
lagoon (polishing pond) which has an area of 12.1 ha (30 acres), a depth of
_k.6 m (15 ft), a capacity of 1*50,000 m3 (119 M gal), and a detention time of
7 days. A second, identical, stabilization lagoon is kept empty for emergency
use.
Samples were taken from the mill's waste treatment system at the points
indicated in Fig. 17. Hourly grab samples were taken for 2k hours from the
clarifier effluent and the aerated lagoon effluent. They were stored as a
composite at i*.i*°C (^0°F). Effluent from the stabilization lagoon was sampl-
ed continuously into an iced sample container.
Bench-scale alum precipitations were conducted on 1-liter samples of ef-
fluent from the stabilization lagoon. About 4.5 cm3 (l tsp) of alum sludge
ash were added, and pH was adjusted to pH k.5-5-0 with water plant alum.
Four drops of anionic polymer were added and the sample was allowed to settle.
Analytical data are given in Table 21. Daily loadings for bleached
toxicants and chloroform are based on bleached pulp production.
67
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SECTION 8
DISCUSSION OF RESULTS*
GENERAL OBSERVATIONS
Data showing removal of fatty and resin acids, bleach toxicants (bleach
plant products), chloroform, BOD, and suspended solids for each of the mills
studied are summarized in Table 22. Immediately evident and of greatest
significance is the indication that nearly all of the systems studied removed
essentially all of the materials of interest quite effectively. Consequently,
the discussions in the following sections of this report will deal with
subtle differences between mills and processes rather than the gross ability
or inability to remove a specific toxicant. Mills in Table 22 that achieved
90 or more percent removal of each of the parameters studied include Mills 1,
5 (when alum treatment was used), 12, and 13• Mills 8 and 1^ dropped below
90% removal only on suspended solids.
Chloroform was removed effectively in nearly all of the mill-scale waste
treatment systems. Volatilization is one suspected removal mechanism.
Amounts of chloroform in final mill effluents (8-75 PP^>) are in the range
that has been reported for some municipal drinking waters (2-152 ppb) (ll|).
Average levels of total fatty and resin acids in mill effluents shown
in Table 22 ranged from a few ppb to 9.0 ppm. The detection limit for an
individual compound was 20 ppb. Bleach plant toxicant concentrations were
lower than the concentrations of fatty and resin acids; the highest average
was O.hh ppm. The detection limit for the bleach plant toxicants was ho ppb.
The mills' individual data tables indicate that very little removal of
fatty and resin acids or bleach toxicants occurred during primary clarifica-
tion. This suggests that these compounds were not associated with the sus-
pended solids removed during that treatment. Mill 12 was an exception, with
significant removal (63%) of fatty and resin acids but not bleach toxicants
occurring in the clarifier.
BIOLOGICAL PROCESSES
Sulfite Mills
Raw effluents from the two sulfite mills in the program, Mill 7 and Mill
10, were characterized by their low concentrations of fatty and resin acids.
*Pulping process, location, and waste treatment process of each of the par-
ticipating mills (listed by code number) are shown in Table 1, p. 5.
70
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These concentrations, which were less than those exhibited by most of the
kraft mills, were further reduced in secondary treatment. Mill 10's two-cell
lagoon facility achieved a greater removal of these compounds (91%} than did
Mill T's activated sludge plant (83%). The apparent removal of fatty and
resin acids in Mill 10's primary clarifier was only a dilution by bleach ef-
fluent. Raw effluents from these mills contained little or no bleach toxi-
cants; levels in the final effluents were below the detection limit.
Kraft Mills
Included in this investigation were kraft mills which used oxygen-
activated sludge, air-activated sludge (usually called simply activated
sludge), and aerated lagoons. Some of the data obtained on these systems are
summarized in Table 23 and are plotted in Figs. 18 and 19- Data in both fig-
ures suggest a trend toward less complete removal of fatty and resin acids in
those systems which received heavier resin and fatty acid loading. Based
upon the limited number of mills sampled, the air-activated sludge systems
performed as well as or better than the lagoons, while the two oxygen-
activated sludge systems achieved somewhat lower percentage removal of fatty
and resin acids. As illustrated in Fig. 18, the performance of the oxygen-
activated sludge systems might be explained by their receiving a heavier
daily loading of fatty and resin acids per kg MLSS than did the air-activated
sludge systems. Under the conditions of operation at the time of this study,
the oxygen-activated sludge systems demonstrated a higher percentage removal
of BOD than of the toxic compounds.
Data in Table 22 show that only three of the kraft mills with biological
waste treatment had measurable amounts of the bleach toxicants in their sec-
ondary treatment plant effluents (Mills kt 11, and 15). The relative ability
of these mills to remove the bleach toxicants paralleled their relative
ability to remove fatty and resin acids. In each case, the percentage re-
moval of the bleach toxicants was less than the percentage removal of the
unchlorinated fatty and resin acids. This behavior is consistent with the
reported biodegradability of these compounds (7).
PRECIPITATION PROCESSES
Precipitation processes yielded substantial reductions in concentration
of the compounds of interest in each of the three mills studied. In Mill 6,
lime treatment removed 78% of the fatty and resin acids from waste streams
containing an average of over 30 ppm of those compounds. BOD removal, aver-
aging 32%, is typical of what has been reported previously for that instal-
lation. Because the lime treatment system was designed for removal of color
rather than BOD, its ability to remove these toxic compounds might be con-
sidered an unexpected benefit.
When used as a tertiary treatment, as in Mills 5 and 15, alum precipita-
tion reduced fatty and resin acids and bleach toxicants to near or below
limits of detection. In these mills, the streams entering the treatment con-
tained rather light loadings of the compounds of interest (in contrast with
Mill 6, above). It must be noted, however, that because the mill-scale alum
72
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treatment system at Mill 5 was not operating, the alum precipitations for
both Mill 5 and Mill 15 vere conducted in the laboratory.
MEMBRANE PROCESSES
Three mills studied in this investigation employ membrane processes.
Using a commercial size reverse osmosis system, Mill 1 achieved ^100% removal
of BOD and fatty and resin acids. This result is consistent with the recog-
nized ability of RO membranes to retain low as well as high molecular weight
solutes.
The two pilot ultrafiltration units (Mills 2 and 3) operated on caustic
extraction filtrate. Concentrations of the bleach toxicants in the feed (be-
fore prefiltration) to each of the units were quite similar, yet the UF unit
in Mill 3 achieved a higher percentage removal of these compounds than was
achieved in Mill 2. The membranes on the two UF units were quite dissimilar.
Mill 2 used a synthetic polymer membrane, and Mill 3 used a membrane formed
from hydrous zirconium and silicon oxides. Apparently the characteristics of
the membrane used in Mill 3 were such that it tended to retain compounds
whose molecular size was that of the bleach toxicants.
The chloroform content of the caustic extraction filtrate was much high-
er in Mill 2 than in Mill 3. In both cases, the chloroform passed through
the UF membranes virtually unimpeded.
-------
REFERENCES
1. Leach, J. M., and A. N. Thakore. Identification of the Constituents of
Kraft Pulping Effluent That are Toxic to Juvenile Coho Salmon (Oncorhyn-
chus kisutch). J. Fish. Res. Board Can. 30:^79-^84, 1973.
2. Rogers, I. H. Isolation and Chemical Identification of Toxic Components
of Kraft Mill Wastes. Pulp Paper Mag. Can. 7M9) :T303-T308, 1973.
3. Rogers, I. H., and L. H. Keith. Organochlorine Compounds in Kraft
Bleaching Wastes. Identification of Two Chlorinated Guaiacols. Tech.
Rep. 465, Environment Canada, Fisheries and Marine Service, Ottawa,
Ont., 1974.
h. Leach, J. M., and A. N. Thakore. Identification of the Toxic Constitu-
ents in Kraft Mill Bleach Plant Effluents. CPAR Rep. No. 2^5-2, Can.
Forestry Service, Ottawa, Ont., 1975*
5. Walden, C. C., and T. E. Howard. Toxicity of Pulp and Paper Mill Ef-
fluents. A Review of Regulations and Research. Tappi 6o(l) Q22-125,
1977.
6. Leach, J. M., and A. N. Thakore. Compounds Toxic to Fish in Pulp Mill
Waste Streams. Prog. Wat. Tech. 9:787-798, 1977.
7. Leach, J. M., J. C. Mueller, and H. P. Meier. Biodegradability of
Various Toxic Compounds in Pulp and Paper Effluents. CPAR Rep. No.
408-1, Can. Forestry Service, Ottawa, Ont., 1976.
8. Mueller, J. C., J. M. Leach, and C. C. Walden. Detoxification of Bleach-
ed Kraft Mill Effluents — A Manageable Problem. In: TAPPI Conference
Papers — 1977 Environmental, pp. 77-81.
9. Rogers, I. H., and H..W. Mahood. Removal of Fish-Toxic Organic Solutes
from Whole Kraft Effluent by Biological Oxidation and the Role of Wood
Furnish Extractives. Tech. Rep. 43^, Fisheries Research Board of Canada,
Pacific Environment Institute, West Vancouver, B.C., 197^-.
10. National Council of the Paper Industry for Air and Stream Improvement,
Inc. Evaluation of Analytical Procedures for the Analysis of Selected
Organic Compounds in Kraft Effluents. NCASI Technical Bulletin No. 258.
New York, 1972.
11. Claeys, R. R., E. L. Owens, and K. Carter. Improved Procedures for the
Gas Chromatographic Analysis of Resin and Fatty Acids in Kraft Mill
77
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Effluents. RCASI Technical Bulletin No. 28l. National Council of the
Paper Industry for Air and Stream Improvement, Inc. New York, 1975.
37 PP.
12. Pihlaja, K., and M. Ketola. Chlorinated Long-Chain Fatty Acids. Their
Properties and Reactions. I. The Synthesis and Purification of Chlori-
nated Octadecanoic Acids. Suomen Kern. B. k3-21-27, 1970.
13- Richard, J. R., and G. A. Junk. Liquid Extraction for the Rapid Deter-
mination of Halomethanes in Water. J. Am. Water Works Assoc. 69(1):62-
6U, 1977.
14. Bellar, T. A., J. J. Lichtenberg, and R. C. Kroner. The Occurrence of
Organohalides in Chlorinated Drinking Waters. J. Am. Water Works Assoc.
66:703-706, 197!*.
78
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-78-031
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Removal of Wood-Derived Toxics from Pulping and
Bleaching Wastes
5. REPORT DATE
February 1978 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Dwight B. Easty, LeRoy G. Borchardt, Bette A. Wabers
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Institute
1043 East
Appleton,
of Paper Chemistry
South River Street
WI 54911
1BB610
1T7TCONTRACT/GRANT NO.
R803525-04
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab.
Office of Research & Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
- Cin., OH
13. TYPE OF REPORT AND PERIOD COVERED
Final 8/76 - 11/77
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Wood-derived compounds known to possess toxicity toward fish and to be present in pulp
nill effluents include resin and unsaturated fatty acids, their chlorinated analogs,
chlorinated guaiacols, and epoxystearic acid. The objective of this investigation has
been to assess the extent to which these compounds are removed from pulp mill effluents
different waste treatment systems in use in several locations in the United States.
Effluents before and after treatment were collected and submitted for determination of
the compounds of interest. Nearly all of the waste treatment processes studied removed
the toxic compounds effectively. Although primary clarification had little effect on
these materials, aerated lagoons and air-activated sludge systems normally removed from
80 to 100% of the resin and fatty acids and their chlorinated analogs from kraft and
sulfite mill effluents. Biological treatment facilities which exhibited poorer fatty
and resin acid removal were those which received high loadings of fatty and resin acids
and BOD. High loadings were apparently reflected also in the lower percentage removal
of the toxic compounds in the two oxygen-activated sludge systems studied. Large reduc-
tions in concentrations of the toxicants were observed following precipitation proces-
ses. Systems studied included lime precipitation and tertiary treatments employing
alum. Reverse osmosis demonstrated essentially complete rejection of fatty and resin
acids. Performance of pilot ultrafiltration units was either good or marginal, appar-
ently depending upon the type of membrane used. Although chloroform contents of the
amples were affected minimally by ultrafiltration, they underwent reduction of from
85 to 97% in all of the other treatment systems studied.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Paper and Pulps,
Waste Treatment,
Industrial Wastes,
Toxicity,
Fatty Acids
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Resin Acids,
Chlorinated Organics,
Dulp & Paper Toxics,
Membrane Processes,
Secondary Treatment
'oxicity Control >
Toxicity Reduction,
Blasts Purification
68D
3. DISTRIBUTION STATEMENT
Release to Public,
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
89
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
79
&US GOVERNMENT PRINTING OFFICE 1978— 757-140/6637
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