EPA-660/2-75-028
JUNE 1975
Environmental Protection Technology Series
Organic Compounds in Pulp Mi
Lagoon Discharges
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis, Oregon 97330
-------
RESEARCH REPORTING SERIES
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U.S. Environmental Protection Agency, have been grouped into
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technology. Elimination of traditional grouping was consciously
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2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY STUDIES series. This series describes research
performed to develop and demonstrate instrumentation, equipment
and methodology to repair or prevent environmental 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.
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EPA-660/2-75-028
JUNE 1975
ORGANIC COMPOUNDS IN PULP MILL LAGOON DISCHARGES
by
Bjorn F. Hrutfiord
Thomas S. Friberg
Donald F. Wilson
John R. Wilson
University of Washington
Seattle, Washington
ROAP/Task No. 21AZX/018
Program Element 1BB037
Grant 802084
Project Officer
Lawrence Keith
Southeast Environmental Research Laboratory
National Environmental Research Center
Athens, Georgia 30601
NATIONAL ENVIRONMENTAL RESEARCH CENTER
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CORVALLIS, OREGON 97330
For Sale by the National Technical Information Service,
U.S. Department of Commerce, Springfield, VA 22151
-------
ABSTRACT
This report presents information obtained in a study of the non-
polymeric organic compounds entering and leaving kraft pulp mill
aerated lagoons. The studies were carried out on an unbleached liner
board mill pulping mostly a mixture of *75* Douglas fir and 25* pon-
derosa pine, and on a specialty kraft mill that produces bleached
pulp from varied wood mixes including western hemlock, western red
cedar and red alder, along with Douglas fir. Both mills operate aer-
ated lagoons of 5-8 day retention time.
Compound identification and quantitative analysis were done by
classifying the compounds in three groups: terpenes and related low-
boiling water insoluble; higher molecular weight acids and neutral
compounds; and water soluble polysaccharide degradation products.
A number of monoterpenes were identified and quantitated. An
average of about 8 ppra total terpenes was found entering the lagoon,
and about 1 ppm or less was found exiting in the lagoon effluent.
o-Terplneol was the terpene in largest concentration in the influent
but camphor was the main compound in the effluent. Compounds present
are in the pulpwood or are formed in the digester and their presence
in the lagoon influent is due to a combination of physical properties.
Control in-plant by steam stripping is possible.
Resin and fatty acids were identified in both the lagoon in-
fluent and effluent. Total resin acid content in the influent was
3.2 ppm while the effluent contained 0.6 ppm. Fatty acids were lower
in concentration and were almost completely eliminated in the lagoon.
Water soluble organic compounds identified were mostly acids
from formic up to C^ acids related to sugars. These compounds appear
in the lagoon influent in about 100 ppm total, and are lowered very
effectively by the lagoon treatment, except for the acids like ace-
tic which are metabolic products in the lagoon. There is no need
for in-plant control of these compounds.
This report was submitted in fulfillment of EPA Grant Mo. 80208*1
by the University of Washington, Seattle, under the sponsorship of the
Environmental Protection Agency. Work was completed as of February 1973.
ii
-------
CONTENTS
Page
SECTIONS
I Conclusions 1
II Recommendations 2
III Introduction 3
IV Objectives 5
V Description of the Springfield Mill and
Sampling Sites at this Mill 6
VI Separation and Analysis Schemes 10
VII Neutral Compounds 13
VIII Acidic Compounds 33
IX Polar Water Soluble Compounds 42
X Control of Organic Compounds in Mill Effluent 55
XI References 57
XII Publications and Patents 60
XIII Glossary 61
11,3.
-------
FIGURES
No. Page
1 Schematic of the Unbleached Kraft Mill Wastewater
Treatment System Showing Sampling Sites 7
2 Lagoon Sample Separation Scheme 11
3 Gas Chromatograms of Neutral Compounds - Springfield 14
4 Temperature, BOD Removal and Turpentine Concentration
for the Springfield Aerated Lagoon, 1973 21
5 Chromatograms of Neutral Compounds from Douglas fir,
Everett 23
6 Chromatograms of Neutral Compounds from Western Bed
Cedar , Everett 24
7 Chromatograms of Neutral Compounds from Red Alder,
Everett 25
8 Gas Chromatograms of Acidic Compounds - Springfield 34
9 Recovery Efficiency of Acidic Compounds 38
10 Polar Compound Analysis and Identification 44
11 Gas Chromatograms of Trimethylsilyl Derivatives of
Some Polar Acids 45
12 Trimethylsilyl Derivatives of Some Saccharinic Acids 46
13 Liquid Chromatogram of Polar Acids - Lagoon Influent
2/14/73 48
14 Mass Spectra Fragmentation? - TMS Derivative of Glucometa-
saccharinic Acid 49
-------
TABLES
No. Page
1 General Data on the Springfield Lagoon 8
2 Springfield Aerated Lagoon Percentage BOD Reduction
and Lagoon Temperature for 1973 9
3 Mass Spectral Data on Neutral Compounds in the
Springfield Lagoon 16
4 Concentration of Neutral Compounds Entering and Leaving
the Springfield Aerated Lagoon 18
5 Seasonal Efficiency of the Springfield Aerated Lagoon
on Neutral Compounds 20
6 Neutral Compounds from the Everett Lagoon - Douglas fir 26
7 Neutral Compounds from the Everett Lagoon - Western
Red Cedar 28
8 Neutral Compounds from the Everett Lagoon , Red Alder 29
9 Concentration of Neutral Compounds Entering and
Leaving the Everett Aerated Lagoon , Douglas fir 30
10 Concentration of Neutral Compounds Entering and Leaving
the Everett Aerated Lagoon, Alder and Cedar 31
11 Identifications of Acids 36
12 Concentration of Acids Entering and Leaving the
Springfield Aerated Lagoon 39
13 Identification Methods for Polar Compounds 47
14 Fragmentation of the TMS Derivatives of Glucometa-
saccharinic Acid 50
15 Concentration of Polar Organic Acids in Aerated Lagoons 51
16 Treatment Efficiency for Polar Organic Acids 52
-------
ACKNOWLEDGMENTS
The work reported here was carried out by a group of graduate students
and others at the University of Washington including Juanita Collins,
Thomas Friberg, Michael Karnofski, Gary Stone, John Warlick, Donald
Wilson and John Wilson.
The assistance and cooperation of the Weyerhaeuser Company has been
invaluable to this project. Mr. James Leonard of the Springfield
Kraft Mill was especially helpful.
Useful discussions on this study have been held with Dr. I. H. Rogers
of the Vancouver Forest Products Laboratory; Dr. Larry Keith of the
Southeast Environmental Research Laboratory, Athens, GA. has also
been especially helpful in technical discussions of the work.
The support of the project by the Environmental Protection Agency,
and the help provided by Mr. George R. Webster, Dr. H. Kirk Williard,
Mr. William Donaldson, the Grant Project Officer, and Dr. Larry Keith
is acknowledged with sincere thanks.
VI
-------
SECTION I
CONCLUSIONS
Organic compounds entering and leaving kraft pulp mill aerated
lagoons have been identified and determined quantitatively. The com-
pounds found were terpenes and related low B.P. materials, resin and
fatty acids, phenols and sugar acids. The terpenes, resin and fatty
acids are similar to those present in the wood specie being pulped.
Some terpenes, phenols and sugar acids are produced during the pulping
reactions. About 8 ppm total terpenes were found in the lagoon influ-
ent and 1 ppm or less were in the effluent. ct-Terpineol was the major-
compound entering the lagoon and camphor the main terpene in the efflu-
ent. The total resin acid concentration entering the lagoon averaged
3.2 ppm with 0.6 ppm leaving. Fatty acids averaged 1.5 ppm entering
the lagoon and 0.3 ppm leaving. Saccharinic acids were the main com-
pounds found in lagoon influent - these averaged 124 ppm and 4 ppm
was found leaving. Other small acids such as acetic and formic
entered the lagoon in about 70 ppm total, the average leaving was
about 56 ppm. These values remained high because sometimes a net
production of formic acid occurred and several of these acids are nor-
mal metabolic products produced in this kind of wastewater treatment.
-------
SECTION II
RECOMMENDATIONS
Further studies of this type are needed to define the nature of
the organic materials being discharged from other parts of the pulp
and paper industry.
The methods used here are useful in determining how any waste-
water treatment facility is performing, in particular how the systems
being utilized for treatment of mixed industrial and domestic sewage
are performing. Determining % BOD reduction and other general para-
meters is no longer an adequate definition of performance.
This study and related ones have fairly well defined how the
secondary treatment systems used by pulp mills operate. Any further
improvements in effluent water quality should be brought about by in-
plant control procedures rather than additional external treatment
facilities.
-------
SECTION III
INTRODUCTION
The nature of effluent from pulp mills, particularly sul-
fite mills, has been studied by numerous workers. The nature
of kraft pulp mill effluent is not as well known, mainly be-
cause these mills have always practiced chemical recovery and
consequently have had less discharge. With recent emphasis on
the overall nature of organic contaminants in waters of the
United States, the question of what is being discharged by pulp
mills using accepted waste water treatment needs to be answered.
The size of the pulp and paper industry is very large -
about 120 million tons of pulp are now produced annually in the
U.S. and at present about 36,000 gallons of water is used per
ton of pulp produced. The pollution load carried by this water
discharged from unbleached kraft mills is 43 Ibs BOD5 and 37
Ibs suspended solids per ton of product (1).
Most of these kraft mills practice primary and secondary
treatment that removes 55 to 95% of the suspended solids and
about 40 to 50% of the BOD5 from the discharged water.
Aerated lagoons in use in the Pacific Northwest today
usually remove about 85 to 90% of the BOD5. Although this is
a satisfactory accomplishment, BOD is concerned only with
readily metabolized material and there are several kinds of
organic compounds present in kraft mill effluents that are
resistant to decomposition by microorganisms.
Review of the literature indicates that kraft mill
effluents may contain a very wide variety of compounds; alcohols
such as methanol, acids including formic, metasaccharinic, as
well as fatty and resin acids, terpenes like a-terpineol and
phenolic compounds such as guaiacol. Many others are un-
doubtedly present. Of these, at least the terpenoid compounds
are resistant to microbial action and also they may be toxic
to marine organisms. There is very little information of the
fate of such compounds in aerated lagoons.
3
-------
Keith, in several reports(2-5)has shown that sane monoterpenes
pass through aerated lagoons with partial structural changes. Anderson
has shown that sugars present in sulfite liquor are significantly
reduced in concentration in an aerated lagoon (6).
With this general background, study of the organic compounds in
kraft mill effluent has been initiated.
-------
SECTION IV
OBJECTIVES
The project objectives have been defines as follows:
a) To qualitatively identify and quantitatively determine
the organic compounds entering the receiving water from
kraft pulp mills using aerated lagoons. The organic
compounds are understood as lower molecular weight
compounds such as extractives and simple phenols, as
well as chlorinated, sulfur bearing and toxic com-
pounds. Other compounds which are of low molecular
weight but are polar and water soluble will be in-
cluded. Higher molecular weight phenolic or lignin
type compounds are not to be considered in this
study.
b) To determine the effect of the aerated lagoon treat-
ment on the organic compounds by applying the sampling
and testing of wastewater both before and after the
aerated lagoon. These results would be supplemented
by alternate pollutant measurements such as total
organic carbon.
c) To provide information on the origin of these compounds
in the process with the aim of defining possible control
points within the process.
The study was organized into three general areas in order to meet
the above objectives. Each area was the responsibility of one
graduate student. The areas of study consist of neutral compounds,
acidic compounds and polar compounds.
-------
SECTION V
DESCRIPTION OF THE SPRINGFIELD MILL AND SAMPLING SITES AT THIS MILL
A study of the influence of an areated lagoon on the organic com-
pounds in kraft mill effluent was initiated with samples from the
Weyerhaeuser Company kraft mill located at Springfield, Oregon. This
mill typifies an unbleached kraft mill. The mill produces 1250 air
dry tons of pulp per day of unbleached linerboard from a wood mix of
about 80% Douglas fir and 20% Ponderosa Pine. Both batch and continuous
digesters are used along with a variety of other processing units
typical of a modern kraft mill.
The effluent treatment system consists of two settling ponds
used for primary treatment, and a larger aerated lagoon with a reten-
tion time of seven to eight days. A schematic of the mill effluent
system is shown in Figure 1. Waste water from the pulp mill, includ-
ing any water from the causticizing, cooking, washing, recovery and
screening areas, is fed to the settling pond at a rate of about 3500
GPM. During the first part of the study, hydraulic barker and plywood
plant waste water streams were routed to the outfall via the log pond,
which also received aeration. One of these streams,hydraulic barker, waste-
water, was rerouted into the settling pond about midway through the
study. Water from the settling pond is fed to the retention basin and
about 3200 GPM of wastewater from the paper mill is also added to this
basin. This includes water from the machine room, evaporators, deckers,
various spills and floor drains. After a settling period, the water
flows to the aerated lagoon for a seven to eight day secondary treatment.
The waste water is then discharged into the McKenzie River.
The main emphasis in this study was on lagoon influent and efflu-
ent. Influent samples were collected from a sampling system located
between the retention basin and the aerated lagoon, and effluent samples
were collected from the lagoon outfall pipeline. The sampling sites
are indicated in Figure 1 as (in) and (out). The samples were all
-------
KRAFT LINERBOARD MILL
PULP
MILL
PAPER
MILL
#1
SETTLING
POND
SETTLING
SUMP
POND
in
O O O
0 0
0 0
000
21 ACRE LAGOON
750 AERATOR H.P
7 DAY RETENTION
out]
1
IOMG.PD.
Figure 1. Schematic of the unbleached kraft mill wastewater
treatment system showing sampling sites.
-------
grab-samples and during a test sequence were taken on seven day inter-
vals. The initial sample would be a single influent sample, followed a
week later by an effluent sample and a second influent sample. This was
continued for three to four weeks. The samples were shipped immediately
by air to Seattle and processed, or stored at 2°C until processed.
Similar samples were collected from the Weyerhaeuser Company
bleached kraft mill at Everett, Washington. This is a 500 ton mill
which pulps several wood mixes, including hardwood, high percent red
Cedar and western hemlock-Douglas fir mixtures.
Generally, in this report, the influent and effluent data is
treated in pairs, i.e. an effluent sample taken 7 days later than an
influent sample is considered to represent the same material as the
influent. The average retention time in the lagoon is seven days but
the sample sets are not as directly related as this since the lagoon de-
sign is not a plug flow type. This should be kept in mind when making
comparison of in and out concentration values.
Average data on several general water quality parameters is summar-
ized in Table 1. The solids, BOD and COD data was provided by Weyer-
haeuser and TOC determinations were made at the University of Washington.
The flow rate through the lagoon during the sampling period was between
500 and 700 GPM. More detailed BOD and temperature data is presented in
Table 2.
TABLE 1
GENERAL DATA ON THE SPRINGFIELD LAGOON
(ppm)
Influent Effluent
Solids 110-180 110-140
BOD 250-350 10-25
COD 700-900 350-500
TOC 130-140 80-100
8
-------
TABLE 2
SPRINGFIELD AERATED LAGOON PERCENTAGE BOD REDUCTION
AND LAGOON TEMPERATURE FOR 1973
Date
Jan.
Feb.
March
April
May
June
Days % BOD5
No. Reduction
4
11
18
25
32
39
46
53
60
67
74
81
88
95
102
109
116
123
130
137
144
151
158
165
172
179
82.0
81.5
82.4
82.5
82.1
77.6
83.4
90.5
88.0
89.1
89.8
89.0
83.3
83.3
82.4
83.6
91.0
90.2
89.1
90.0
87.3
88.1
87.3
86.1
83.4
90.6
Temperature Days % BOD5
(°F) Date No. Reduction
81.3
73.8
83.4
73.8
73.4
75.0
77.0
76.7
75.4
79.0
75.2
73.4
77.0
79.3
83.1
79.0
78.9
72.4
80.7
88.2
84.0
82.8
84.0
81.4
82.9
86.0
July 186
193
200
207
Aug. 214
221
228
235
242
Sept. 249
256
263
270
Oct. 277
284
291
298
Nov. 305
312
319
326
333
Dec. 340
347
354
363
84.9
81.9
89.5
89.1
88.2
90.6
82.6
80.6
87.3
82.1
89.4
87.8
90.6
87.4
90.5
95.7
94.4
93.5
93.9
94.9
92.9
85.2
85.7
86.4
88.7
89.2
Temperature
(°F)
84.5
84.0
85.0
84.0
84.2
84.0
84.5
82.0
79.3
82.0
83.2
83.2
82.1
82.1
76.7
82.3
82.1
82.2
73.0
75.7
71.7
73.0
73.1
73.5
74.5
70.5
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SECTION VI
SEPARATION AND ANALYSIS SCHEMES
A large variety of organic compounds with widely differing prop-
erties are present in kraft mill effluent. These compounds are pre-
sent in low concentrations, mostly in the few ppm range or less.
Thus, their detection and isolation requires processing of adequate
size samples and the use of proper equipment. In this work the aim has
been to use the gas chromatograph/mass spectrometer (GC/MS) combination
for identification work and to use gas or liquid chromatography for
quantitative determination.
Initially a considerable amount of time and effort was spent in
working out analysis schemes in which all compounds isolated were
determined on the same sample by sequential separations. This proved
to be impractable in terras of time involved and in particular in
developing reliable quantitative data. The scheme finally used involved
dividing a sample into two parts and processing these individually.
The overall separation and analysis scheme used is outlined in
Figure 2. This system results in fractionating the sample into three
parts which are designated as neutral compounds, acidic compounds and
polar compounds, according to their chemical and physical properties.
The neutral fraction was isolated by adjusting the sample to pH 11
and extracting with hexane. The extraction conditions were studied
extensively and the final version recovers greater than 90* of the
compounds in this class. Quantitative determination was done by gas
chromatography analysis using a polyethylene glycol column. Identifica-
tions were done by GC/MS matching with known compounds, and in a few
cases by matching published spectra.
Polar and acidic compounds were isolated from the samples by pass-
ing the neutralized sample over an XAD-2 resin column, which retains
the higher molecular weight non-polar acids, and collecting the column
eluate, which contains the polar compounds. The polar compounds were
10
-------
a) adjust pH Lagoon adjust pH
to 11 sample to 7.0
b) ex1
he:
i
Neutral
compounds
tract with Mf,.
so!
eluate
1 concentrate
GC/MS
Polar
compounds
1 concentrate
1
jtralized
nple
Pass over
XAD-2 resin
1
Compounds
absorbed
in resin
elute with
methanol
Acidic
compounds
GC and MS
a) concentrate
b) methylate with
diazomethane
GC/MS
Figure 2. Lagoon sample separation scheme
-------
determined by making the eluate alkaline, concentrating on the rotary
evaporator, then buffering the sample to pH ^9.3 with 0.03 M sodium
tetraborate and passing it over an anion exchange column in a liquid
chromatograph equipped with a refractive index detector. Compound
identifications were made by comparison with knowns, and where necessary,
by collection of elution peaks, silation and determination of mass
spectra using the solid probe technique. Compound identifications were
made by running knowns and by comparisons with published spectra in some
cases.
Acids were eluted from the resin column with methanol, taken to
dryness and dissolved in ether, methylated exhaustively with diazo-
methane and separated by GC using a polyethylene glycol-TPA column.
Identity was verified by GC/MS comparison with known compounds.
12
-------
SECTION VII
NEUTRAL COMPOUNDS
Compounds discussed in this section are neutral molecules
with boiling points up to about 250°C. The majority of the
compounds identified in this fraction are mono- and sesquiter-
pene hydrocarbons and monoterpene alcohols and ketones similar
to the compounds found in wood and sulfate turpentine.
The analysis system used required that the unknown com-
pounds be separated from water and concentrated. After study-
ing several systems, hexane extraction was adopted. Using ci-
te rpineol in water as a model, it was demonstrated that quan-
titative recovery of ppm quantities could be extracted from pH
12 samples using 100 ml of redistilled hexane with a 3500 ml
sample. The mixture was mechanically stirred for an hour and
the extraction repeated 3 times. Combined extracts were dried
and concentrated to 1 ml by careful evaporation using a Kuderna-
Danish evaporator-concentrator heated on a steam bath.
Analysis was done by gas chromatography using a 100 foot
Carbowax 20M support coated open tubular column in a Perkin
Elmer 990 gas chromatograph. This instrument is connected with
a Biemann-Watson separator to a Hitachi RMS-4 mass spectrometer.
Gas chromatographic analyses were done by injecting 0.3yl
samples and programming from 90 to 150°C at 2°/minute. Results
were recorded on a Hitachi Model 56 recorder and integrated
with a Infotronics electronic integrator. Typical gas chromato-
grams from lagoon influent and effluent (for weeks 5-10 and
5-17) are shown in Figure 3. Peaks on which qualitative and
quantitative data were obtained were numbered 1 through 46, as
indicated on the curve.
Qualitative identifications were done by determining
the mass spectra of the compounds, and wherever possible
running pure knowns through the same system for verification.
Literature spectra were also
13
-------
21
EFFLUENT
27
23 £9 32 36 39
31, ^37 44
WOUL
0
10 15 20 35
TIME (minutes)
Figure 3. Gas chromatograms of neutral compounds-Springfield
14
-------
used extensively. Pertinent information establishing identity of the
neutral compounds is summarized in Table 3.
Quantitative data on the individual compounds was obtained from the
peak areas of the gas chromatograms of the extracts. These peak areas
were corrected for flame detector response by the use of compound class
factors relative to limonene as 1.0. The factors used were for hydro-
carbons 0.98; ketones 0.84; and alcohols 0.80. The individual quanti-
ties were then calculated from the weight of the extract (corrected
for non-volatile residues) and the corrected peak areas. Finally the
concentrations were calculated in ppm from the individual quantities
and the sample size.
Quantitative data obtained on the Springfield lagoon is summarized
in Table *». In general, the major terpene entering the lagoon is
a-terpineol accompanied by lesser amounts of other terpene alcohols,
including terpinene-4-ol, and fenchyl alcohol. Trace amounts of terpene
hydrocarbons and ketones are also present. The major terpene leaving
the lagoon is camphor, accompanied by other hydrocarbons, alcohols and
ketones with the alcohol fraction being greatly reduced. In some in-
stances both camphor and fenchone increased in concentration in the
lagoon.
The efficiency of removal of the neutral compounds by the aerated
lagoon treatment is generally quite good. The average influent concen-
tration of terpenes etc. is about 7-5 ppm and the average effluent
concentration is about 0.9 ppm, giving a reduction of 88%. A summary
of the % removal data is presented in Table 5. Information on BOD
removal efficiency, lagoon temperature, and neutral compound concen-
trations in Influent and effluent is summarized in Fig. 4. The trend of
terpene removal showed increasing efficiency throughout the sampling per-
iod. The mill operating data showed the same trend for BOD^ removal and
these trends have a correlation coefficient of 0.75. None of the lagoon
operating data explained the increasing BOD removal efficiency, in fact
the lagoon temperature which normally directed influences BOD^ removal
15
-------
TABLE 3
MASS SPECTRAL DATA ON NEUTRAL COMPOUNDS IN THE SPRINGFIELD LAGOON
Peak
NO.
1A
IB
1C
ID
2
3
4
5
6
7A
7B
8
9A
9B
10A
10B
11
12
13
14
15
16
17
18
19
20
21
22
Compound
Identity
Solvent
Unknown
Unknown
Chloroform
a-Pinene
Santene
Camphene
Sabinene
B-Pinene
Myrcene
ot-Phe llandrene
1-4 Cineole
Limonene
Die thy 1 dissulfide
1-8 Cineole
B-Phellandrene
X
A Carene
p-Cymene
Terpinolene
Unknown
Unknown
Dimethyl trisulfide
Fenchone
Unknown
Unknown
Guaiacol
Camphor
Linalool
Molecular
Weight
84
118
136
122
136
136
136
136
136
136
122
136
136
134
136
152
152
126
152
124
152
154
M.S. Major Fragments and Comments
57 43 41 71 85 56 (Hexane isomer)
correlated with M.S. of known
/ / / / and published M.S.
correlated with published M.S.
correlated with M.S. of known and published M.S.
il / / /
/ / / /
/ / / /
correlated with published M.S.
correlated with M.S. of known
correlated with M.S. of known and published M.S.
correlated with M.S. of known
/ / / /
/ / / /
correlated with M.S. of known and published M.S.
/ / / / /
/ / / / /
79 43 41 93 55 67
67 95 41 82 110 57
correlated with M.S. of known
correlated with M.S. of known and published M.S.
10.9 81 124 50 41 55
50 41 81 120 57 55
correlated with M.S. of known
correlated with M.S. of known and published M.S.
/ / / / / M.S.
Lit.
Ref.
(7)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(9)
(9)
(10)
-------
TABLE 3 (Continued)
MASS SPECTRAL DATA ON NEUTRAL COMPOUNDS IN THE SPRINGFIELD LAGOON
Peak
No.
23
24A
24B
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
Compound
Identity
Unknown
Unknown
Unknown
Fenchyl alcohol
Unknown
Te rpinene- 4- ol
Sesquiterpene
Sesquiterpene
Unknown
Sesquitexpene
Borneol
a-Terpineol
Unknown
Sesquiterpene
Unknown
Sesquitezpene
Unknown
Sesquitexpene
Unknown
Anethole
Unknown
Unknown
Unknown
Unknown
Unknown
Molecular
Height
138
154
154
154
204
204
204
154
154
204
204
204
162
148
163
220
220
218
M.S. Major Fragments and Comments
57 43 41 71 85 56
95 43 138 123 79 55 (camphene)
95 93 91 43 41 67
correlated with known and published M.S.
Lit.
Ref.
(11)
(ID
121 93 136 107 105 91 (trans-B-terpineol)
correlated with M.S. of known and published
93 121 136 41 43 91
93 71 43 41 121 69
93 121 41 95 91 81
correlated with known and published M.S.
/ / /
93 161 119 137 204 105
93 41 43 91 121 105 (longifolene
93 68 41 136 121 43
119 91 43 68 39 121
(11)
(11)
(11)
(7)
correlated with M.S. of reference standard (p-propenyl
132 117 91 111 115 92
205 41 43 138 93 95 (cedranone)
205 57 41 43 55 71
41 59 91 55 93 119
anisole)
(7)
-------
TABLE 4
CONCENTRATION OF NEUTRAL COMPOUNDS ENTERING AND LEAVING
THE SPRINGFIELD AERATED LAGOON (ppm)
GC (eg
peak* ^
1A
IB
1C
2
4
6
7A
7B
8
9A
10A
10B
11
12
13
17
18
21
23
25
27
29
32
33
35
37
39
42
Compound
Identification
*
*
*
o-Pinene
Camphene
B-Pinene
Myrcene
a-Phe 11 andrene
1-4-Cineole
Limonene
1-8-Cineole
3 -Phe llandrene
A -carene
p-Cymene
Terpinolene
Fenchone
*
Camphor
*
Fenchyl alcohol
Terpinene-4-ol
Sesquiterpene
Borneol
a-Terpineol
Sesquiterpene
Se squi te rpene
Se squi terpene
*
TOTAL
(a) Order of Elution on
*BI™
1-31 (C)
tr
-------
TABLE 4 (Continued)
CONCENTRATION OF NEUTRAL COMPOUNDS ENTERING AND LEAVING
THE SPRINGFIELD AERATED LAGOON (ppm)
GC
Peak
1C
ID
2
4
5
6
7A
8
9A
9B
10A
12
13
15
16
17
18
19
20
21
23
24A
24B
25
26
27
28
29
31
32
33
34
35
37
38
39
40
41
42
43
45
46
Compound
Identification
Chloroform
o-Pinene
Camphene
Sabinene
g-Pinene
Myrcene
1-4-Cineole
Limonene
Diethyl dissulfide
1-8-Cineole
p-Cymene
Terpinolene
*
ABI
5-10
.01
.53
.03
.05
.22
.11
tr
.08
.04
ABE
5-17
.05
.13
.01
.04
Dimethyl trisulfide.02
Fen ch one
*
*
Guaiacol
Camphor
*
*
*
Fenchyl alcohol
*
Terpinene-4-ol
Sesqui terpene
Sesqui terpene
Sesqui terpene
Borneol
a-Terpineol 5
*
Sesqui te rpene
Sesqui terpene
*
Sesqui te rpene
*
Anethole
*
*
*
*
TOTAL 8
.06
.04
.23
.08
.48
.45
.04
.13
.02
.12
.01
.01
.03
.04
.11
.06
tr
.12
.10
.03
.01
tr
.02
.06
.97
ABI
8-10
.01
.06
tr
.01
.09
.01
tr
.02
.02
.01
.04
.04
.04
.01
.03
.19
.12
.01
.20
.59
.04
.01
3.72
1.05
.11
.02
.01
.01
.05
6.53
ABE
8-17
.01
.07
tr
.02
.10
tr
tr
.03
.02
tr
.01
.02
.04
.01
.35
.05
.02
.02
tr
.03
.03
.01
.02
.04
tr
.01
.03
.06
.07
1.06
ABI
10-9
.01
.06
tr
.01
.06
.01
.02
.01
.03
tr
.01
.05
.05
.01
.07
.17
.14
.20
.52
.04
.06
.01
.01
2.95
.47
.44
.02
tr
.03
.04
.03
.02
.04
5.96
ABE
10-16
.02
.01
tr
tr
.04
.01
.01
tr
tr
.02
.02
.01
.02
.01
tr
.04
tr
.01
.01
tr
.01
.23
19
-------
TABIE 5
SEASONAL EFFICIENCY OF THE SPRINGFIELD AERATED LAGOON ON NEUTRAL COMPOUNDS
Season/Date
Winter
1-31, 2-7
2-07, 2-14
2-14, 2-21
Average
Spring
5-10, 5-17
(Aug)
Summer
8-10, 8-17
8-20, 8-27
Average
Autumn
10-3, 10-9
10-9, 10-16
Average
Monoterpene
Concentration % Terpene
influent effluent Removal
8.26
10.92
5.02
8.06
8.04
6.53
7.02
6.86
6.48
5.96
6.22
1.19 85.6
1.23 88.7
0.71 85.9
1.03 86.7
0.97 87.9
1.06 83.7
0.31 95.6
0.68 89.6
0.40 94
0.22 96.2
0.31 95.1
% BOD
Reduction
82.2
83.4
90.5
85.4
90.0
82.6
87.3
85.0
90.5
95.7
93.1
20
-------
7.0
CL
^6.0
5
5.0
4.0
90
£80
o:
LJ
Q.
70
90
80
70
INFLUENT
TURPENTINE
B.O.D. REMOVAL
TEMPERATURE
I
1
I
1
1
60 120
180 240 300
DAYS
Figure 4. Temperature, BOD removal and turpentine concentration
for the Springfield aerated lagoon, 1973.
21
-------
showed no correlation at all (11). The influent terpene concentration,
which decreased during the latter part of the sampling year, may be
important here in the lagoon operating efficiency since terpenes have
a well known bacterial inhibiting effect.
Lagoon samples were also obtained from a bleached kraft mill at
Everett. This mill pulps several wood species including Douglas fir,
western hemlock, western red cedar and red alder. These are pulped in
varying ratios, with some Douglas fir present in most wood mixes. The
grade of pulp produced is changed frequently and as a result the lagoon
input is highly variable. Generally, sampling of lagoon influent was
done 24 hours after the beginning of pulping of a given wood mix and
the lagoon effluent was sampled a week later, which equals the average
retention time of the lagoon.
Samples from the Everett mill were treated by procedures similar
to those used for the Springfield samples.
Influent and effluent gas chromatograms from the pulping of Douglas
fir, a red cedar and red aldennixture are presented in Figures 5, 6 and
7. The GC/MS identifications are given in Tables 6, 7 and 8. Concen-
tration of the neutral compounds, in ppm, are given in Tables 9 and 10.
The GC results in Figure 5 and the compounds listed in Table 9
are from the pulping of 100% Douglas fir and can be compared to the
Springfield mill results (Figure 3 and Tables 3 and 4) since the wood
mix used there is about 80% Douglas fir and 20% Ibnderosa pine. All
sixteen mono terpenes identified at Everett were found in the Springfield
lagoon and the chromatograms from the two locations are very similar.
More compounds are detectable in the Everett lagoon. For the red alder
and western r
-------
EFFLUENT
53
10 15 20
TIME (minutes)
Figure 5. Chromatograms of neutral compounds from
Douglas fir, Everett
35
23
-------
EFFLUENT
i
i i i i i i i i i i i i i
10
15
INFLUENT
19
20
10
TIME (minutes)
15
Figure 6. Chromatograms of neutral compounds from
western red cedar, Everett
20
24
-------
EFFLUENT
45 6a 8
i ' ' i I I I I I 1 1 1 1 1 1 L
0
10
15
INFLUENT
20
18
2 4
15 16
19
17
i i i i I I 1 1 1 1 1 1 1 1 1 1 1 i 1 1 1
05 10 15 20
TIME (minutes)
Figure 7. Chromatograms of neutral compounds from
red alder, Everett
25
-------
TABLE 6
NEUTRAL COMPOUNDS FROM THE EVERETT LAGOON - DOUGLAS FIR
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Compound
Identity
Unknown
Unknown
Unknown
ct-Pinene
Santene
Camphene
Sabinene
Unknown
Unknown
3-pinene
Unknown
Myrcerte
a-Phellandrene
1-4 Cineole
Limonene
1-8-Cineole
Unknown
A3-Carene
p-cymene
Unknown
Terpinolene
Unknown
Unknown
Unknown
Unknown
Unknown
Fenchone
Unknown
Unknown
Unknown
Unknown
Molecular
Weight
146
136
122
136
136
136
154
136
136
136
136
134
136
152
190
M.S. Major Fragments
57 43 41 71
correlated with
correlated with
correlated with
/ /
correlated with
91 57 43
correlated with
/ /
/ /
/ /
/ /
correlated with
/ /
correlated with
correlated with
154 43 59
M.S.
and Comments
55 85
of known and published M.S.
published M.S.
M.S.
/
M.S.
41
M.S.
/
/
/
/
M.S.
/
M.S.
M.S.
81
of known and published M.S.
of known and published M.S.
50 71 (terpene alcohol)
of known and published M.S.
of known and published M.S.
/
of known and published M.S.
of known and published M.S.
131 111
Lit.
Ref.
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(8)
(9)
-------
TABLE 6 (Continued)
NEUTRAL COMPOUNDS FROM THE EVERETT LAGOON - DOUGLAS FIR
Peak
No.
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47A
47B
48A
48B
49
50
51
52
53
Compound Molecular
Identity Weight
Unknown
Unknown
Unknown
Camphor
Linalool
Unknown
Unknown
Fenchyl alcohol
Unknown
Unknown
Terpinene-4-ol
Unknown
Unknown
a-Terpineol
Unknown
Sesquiterpene
Sesquiterpene
Sesquiterpene
Se squi te rpene
Anethole
Unknown
Unknown
Unknown
Unknown
124
152
154
148
148
154
148
154
154
204
204
204
204
M.S.
57
104
Major
43
81
correlated
correlated
95
41
67
81
correlated
93
41
correlated
correlated
93
119
91
160
93
41
41
91
119
119
136
67
Fragments
41 71
108
with
with
43
95
with
91
with
with
91
134
93
91
91
91
109
M.S.
M.S.
138
67
M.S.
55
M.S .
M.S.
69
65
79
43
130
119
and Comments
55 85
93
of known
of known
123
55
of known
121
of known
of known
55
41
41
41
117
57
95
and published M.S.
and published M.S.
41
69
and published M.S.
39
and published M.S.
and published M.S.
43
39
55
105
77
55
Lit.
Ref .
(9)
(10)
(11)
(11)
(11)
-------
TABLE 7
NEUTRAL COMPOUNDS FROM THE EVERETT LAGOON - WESTERN RED CEDAR
10
oo
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Compound
Identity
Unknown
Unknown
a-Pinene
Camphene
B-Pinene
Myrcene
ct-Phe 1 landrene
1-4-Cineole
1-8-Cineole
Unknown
Fenchone
Unknown
Guaiacol
Camphor
Tropolone
Tropolone
Fenchyl alcohol
Tropolone
Unknown
o-Terpineol
Unknown
Molecular
Weight
136
136
136
136
136
154
154
152
153
122
152
164
164
154
164
164
154
206
M.S. Major Fragments and Comments
83 85 44 41 47
correlated with M.S. of known and published M.S.
/ / /
/ / /
/ / /
correlated with published M.S.
correlated with M.S. of known
/ / /
correlated with M.S. of known and published M.S.
43 153 71 41 81 55
correlated with M.S. of known
correlated with M.S. of known and published M.S.
123 138 41 55 67 39 (tropolone)
95 41 123 55 67 119 /
correlated with M.S. of known and published M.S.
93 77 121 79 95 107 (tropolone)
93 107 79 91 121 41 /
correlated with M.S. of known and published M.S.
119 93 41 91 76 79
Lit.
Ref.
(8)
(8)
(8)
(8)
(8)
(9)
(9)
(12)
(12)
(11)
(12)
(12)
(11)
-------
TABLE 8
NEUTRAL COMPOUNDS FROM THE EVERETT LAGOON, RED ALDER
NJ
vo
Peak
No.
1
2
3
4
5
6
7
7A
7B
8
8A
9
10
11
12
13
14
15
16
17
18
19
20
Compound
Identity
Unknown
Acyclic Terpene
Unknown
a-Pinene
Camphene
B-Pinene
Myrcene
1-4 Cineole
Lintonene
1-8-Cineole
0 -P he 1 1 andrene
Unknown
Unknown
Fenchone
Unknown
Unknown
Camphor
Fenchyl alcohol
Terpinene-4-ol
Unknown
a-Terpineol
Unknown
Unknown
Molecular
Weight
142
148
136
136
136
136
136
136
152
153
152
154
154
154
138
M.S. Major Fragments and Comments
43 57 41 71 93 85
54 43 41 71 44 55
correlated with M.S. of known and published M.S.
/ / / /
/ / / /
/ / / /
correlated with M.S. of known
correlated with M.S. of known and published M.S.
correlated with M.S. of known
correlated with M.S. of known
correlated with M.S. of known and published M.S.
43 46 153 71 81 55
correlated with M.S. of known and published M.S.
/ / /
/ / /
correlated with M.S. of known and published M.S.
94 41 43 55 44 57
Lit.
Ref.
(8)
(8)
(8)
(8)
(8)
(9)
(9)
(ID
(ID
(ID
-------
TABLE 9
CONCENTRATION OF NEUTRAL COMPOUNDS ENTERING AND LEAVING THE EVEBETT
AERATED LAGOON, DOUGLAS FIR
(ppm)
GC(a)
peak
1
2
3
4
5
6
7
9
10
11
12
13
14
15
16
17
A *
18
19
20
21
22
23
24
25
27
29
30
31
32
— . —
Compound
Identi f i cation
*
*
*
a-Pinene
Santene
Camphene
Sabinene
*
*
g-Pinene
Myrcene
a-Phellandrene
1-4-Cineole
Limonene
1-8-Cineole
*
A -Carene
p-Cymene
*
Terpinolene
*
*
*
*
Fenchone
*
*
*
*
12-21 (
.02
.14
.01
tr
tr
.01
tr
tr
tr
.01
.01
.01
.01
tr
.01
tr
.01
.01
.02
.07
.01
^ABE
1.2-21
.02
.07
.02
.04
*
.03
.03
.01
.04
.02
.01
.02
.01
.01
tr
tr
.01
.01
.02
.01
.02
tr
.01
.02
T
GC
peak
34-
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
_«_ — . '
Compound
Identification
*
Camphor
Linalool
*
*
Fenchyl alcohol
*
*
Terpinene-4-ol
*
*
a-Terpineol
*
Sesquiterpene
Sesquiterpene
Ane thole
*
*
*
*
TOTAL
ABI
12-12
.04
.06
.02
.02
.10
.03
.12
.39
.33
.01
.02
.02
tr
.06
.06
.03
1.85
ABE
12-21
.03
tr
tr
tr
tr
tr
s\ i
.01
.01
.01
.01
tr
.03
.04
.03
.65
(a) Keyed to Figure 5
(b) Aeration Basin Influent and Effluent
(c) Sanple date
(*) Unknown
30
-------
TABLE 10
CONCENTRATION OF NEUTRAL COMPOUNDS ENTERING AND LEAVING THE EVERETT
AERATED LAGOON, ALDER AND CEDAR
( PPm)
peak
2
3
4
5
6
7
7A
7B
8
8A
9
10
11
12
13
14
15
16
16A
17
18 &
Alder
Compound
Identification
Acyclic terpene
a-P inene
Camphene
B-P inene
Myrcene
1-4-Cineole
Limonene
l-8-cineole
3- phellandrene
Fenchone
Camphor
Fenchyl alcohol
Terpinene-4-ol
19 a-Terpineol
TOTAL
ABI
2-26
.05
.03
.08
.02
.02
.03
.tr
tr
.02
tr
.01
.01
tr
.02
.01
.05
.11
.08
.01
.65
1.20
ABE
3-5
.04
.02
tr
tr
tr
.01
tr
.01
tr
.03
tr
tr
.23
.03
.06
tr
.42
GC
peak
1
2
3
4
5
6
7
8
9
10
11
12
13
14
14A
15
16
17
18
19
20
Cedar
Compound
Identification
a-P- inene
Camphene
8 -P inene
Myrcene
a-Phe llandrene
1-4-Cineole
1-8-Cineole
Fenchone
Guaiacol
Tropolone &
.Camphor
Camphor
Tropolone
Fenchyl alcohol
Tropolone
a-Terpineol
TOTAL
ABI
2-28
.05
.01
.01
tr
tr
.03
.02
.02
.01
.05
tr
.69
.13
.23
.39
.26
.02
1.92
ABE
3-7
.03
.01
.06
tr
.02
.02
.01
tr
.01
.04
tr
tr
.31
tr
.08
.02
tr
.03
.61
(a) Keyed to Figures 6 and 7
31
-------
a different GC column and at different sensitivity. These results are
not surprising since Douglas fir is the only one of these species that
contains any terpenes. The results point out that some mixing of wood
species probably occurs, and certainly water reuse and recirculation is
occurring to a great extent so that species changes for a few days has
little influence on the mill effluent organics.
The concentration of terpenes entering the Everett lagoon is only
15-20% of that found in the Springfield lagoon. This is mainly due to
simple dilution because of the bleach plant effluent and also partially
due to differences in the type of processing equipment, i.e., the use of
batch digesters at Everett and of a continuous digester at Springfield.
The treatment efficiency of the Everett lagoon averages about 65% removal
of these compounds while Springfield removes 88%.
32
-------
SECTION VIII
ACIDIC COMPOUNDS
The acidic compounds isolated in this fraction are a variety of
resin and fatty acids, neutral terpenes and some phenolics. Most of
these occur as such in the wood being pulped, although some composi-
tion changes take place in the resin acids, and the phenols are formed
in the digester. The fraction is very complex because the method of
isolation tends to collect all acidic and neutral compounds of low
solubility in water, including neutral terpenes as found in the pre-
ceding section. These compounds find their way to the mill effluent
in weak wash water, liquor spills and a variety of other streams.
The organic material was isolated from the lagoon samples by
adsorption on Amberlite XAD-2 resinR. Typically, sample pH was
adjusted to 7.0 and 5 gallons were passed through a ItoO ml bed volume
column (5 cm x 80 cm) of resin at a flow rate of three bed volumes/hr.
The column was washed with four bed volumes of distilled water and the
organic material was eluted with five liters of methanol. The methanol
and residual water was removed by vacuum rotary evaporation at 30°
and the residue taken up in 100 ml of water. This was acidified to
pH 3.0 with HC1 and extracted with ether (3 x 200 ml). The ether was
dried over Na2SO. and concentrated with a Kuderna-Danish evaporator.
The compounds were derivatized by forming their respective methyl
derivatives by reaction with diazomethane.
Analysis of the derivatized samples was done with a Perkin-Elmer
990 gas chroraatograph using a 50 ft. Carbowax 20M-TPA S.C.O.T. column,
which was temperature programmed 100-200° at Wmon. The injector and
manifold temperatures were maintained at 250°C. Column flow was about
6 cc/mm.
Typical gas chromatograws of the compounds isolated from samples of
lagoon influent and effluent are shown in Figure 8 and the compounds
detected, on which qualitative and quantitative information was sought,
are numbered 1 through 38.
RRegistered Trademark - Rohm and Haas Company
33
-------
AERATION BASIN
EFFLUENT
40
30
20
10
Figure 8. Gas chroma to grams of acidic compounds-Springfield
-------
Qualitative identifications were done by determining the mass spec-
tras of the compounds and wherever possible by comparison with spectra
obtained from known compounds. Reference was made to spectra reported
in the literature also. The data on compound identification is summar-
ized in Table 11. Several resin acids were identified and a number of
others were detected but not identified. These are components of the
wood resin and are expected in the mill effluent. Also several of the
usual fatty acids are found, here perhaps the relatively greater abun-
dance of the saturated acids than unsaturated is surprising. Another
acid tentatively identified is p-tolyl-valeric acid, which has recently
been reported as a major extractive in Douglas fir. The hydrocarbon
abietane also is found and is from this source. Very few phenols were
identified, and this was found to be due to extremely poor retention
of this class of compounds by the XAD-resin. This was discovered too
late to correct for in this study.
Quantitative data was obtained from the GC curves by use of an
internal standard technique, a known amount of margaric acid (17:0) was
added prior to reaction with diazomethane. Quantitative analysis was
facilitated by use of an electronic integrator. Relative response
factors for a number of knowns were determined and found to range between
0.96 and 1.02, these were not used in calculations. Quantitation of
unidentified peaks was done using a response factor of 1.0.
The recovery efficiency was determined by processing known quan-
tities of individual compounds through the analysis system, and the
efficiency was found to be concentration dependent. At concentrations
above 1 ppm recovery was about 95% while below this level the efficiency
dropped to around 85%, Figure 9.
The quantitative data is summarized in Table 1 2. The p-tolyl-
valeric acid is the magor component, sometimes as high as 25 ppm in
mill wastewater, and this compound is completely eliminated in the
lagoon. The largest concentration of compounds found are the resin
35
-------
TABLE 11
IDENTIFICATION OP ACIDS
Peak Compound Molecular
No. Identity Weight
1
2
3
4
5
6
7
8
9
10 p-Tolyl valeric acid
11
12
13
14 Abietane
15 Methyl palmitate
16
17
18
19 Veratraldehyda
152
154
136
178
192
146
136
206
220
220
272
95
93
93
119
119
131
93
119
119
119
119
M« S •
81
121
68
91
91
119
68
132
132
132
93
Major Factors
109
95
121
178
132
146
121
133
145
133
105
108
91
67
120
117
91
91
91
91
91
83
121
136
117
135
117
206
117
175
229
152
107
79
77
192
115
117
220
117
272
correlated with known
correlated with known
Comments
(p-Hy droxybenz aldehyde )
Hydrocarbon
Palmitic acid
Vanillin
-------
TABLE 11 (Continued)
IDENTIFICATION OF ACIDS
OJ
vl
Peak Compound Molecular
No. Identity Weight M.S. Major Factors
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
Methyl stearate correlated with known
Methyl oleate " " "
Methyl linoleate " " "
316
316
Methyl pimarate correlated with known
Methyl sandaracopimarate correlated with known
316 242 301 316
316
Methyl isopimarate correlated with known
Methyl abietate correlated with known
Methyl dehydroabietate " " "
Methyl neoabietate " "
Comments
Stearic acid
Oleic acid
Linoleic acid
(Resin acid)
(Resin acid)
Pimaric acid
Sandaracopimaric acid
(Resin acid)
(Resin acid)
Isopimaric acid
Abietic acid
Dehydroabietic acid
Neoabietic acid
-------
100
UJ
>
o
o
LJ
O
(C
UJ
Q.
90
80
70
RESIN
ACIDS
10 100 IOOO 10000
CONCENTRATION 1/xQ/Nttr)
Figure 9. Recovery efficiency
acidic compounds
of
38
-------
w
TABLE 12
CONCENTRATION OF ACIDS ENTERING AND LEAVING THE SPRINGFIELD AERATED LAGOON
fepb)
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
ABI
1-31-73
tr
tr
720
tr
tr
240
520
2520
240
480
780
tr
600
tr
190
180
200
ABE
2-7-73
35
100
25
50
tr
70
20
100
40
30
tr
60
tr
ABI
2-7-73
45
tr
110
30
130
160
170
170
50
tr
340
180
50
170
60
170
ABE
2-14-73
tx
40
50
40
tr
180
60
tr
60
tr
ABI
2-14-73
tr
560
tr
220
440
1660
320
220
1280
1050
740
280
300
ABE
2-21-73
tr
tr
20
tr
tr
40
tr
tr
40
tr
ABI
5-5-72
260
1300
80
220
80
740
tr
320
140
100
180
80
ABE
5-5-72
tr
60
30
tr
60
50
40
tr
60
ABI
9-13-72
50
tr
40
100
30
80
80
180
tr
200
40
50
tr
50
60
ABE
9-21-72
20
tr
tr
120
60
20
20
-------
TABLE 12 (Continued)
CONCENTRATION OF ACIDS ENTERING AND LEAVING THE
SPRINGFIELD AERATED LABOON
Peak
No.
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
ABI
1-31-73
tr
200
120
120
170
130
180
170
160
340
tr
160
300
330
240
950
tr
ABE
2-7-73
20
10
160
tr
60
25
20
tr
60
70
150
tr
tr
80
100
50
120
ABI
2-7-73
90
290
100
140
120
130
160
150
120
440
100
170
580
380
470
1030
tr
ABE
2-14-73
40
30
50
80
50
70
35
90
60
180
tr
tr
110
50
80
150
ABI
2-14-73
tr
tr
90
360
240
340
190
300
300
320
1000
tr
440
490
720
140
1440
tr
ABE
2-21-73
50
tr
100
30
50
140
30
60
140
50
70
80
tr
150
ABI
5-5-72
tr
tr
150
tr
150
300
120
80
90
120
220
tr
370
300
340
290
880
120
ABE
5-5-72
30
tr
40
40
70
tr
50
60
90
40
70
tr
60
110
tr
ABI
9-13-72
20
30
50
300
70
90
30
50
tr
140
300
240
tr
170
380
300
200
560
tr
ABE
9-21-72
20
20
20
20
40
20
80
60
40
60
70
30
120
20
-------
acids which were found ranging from 4.8 to 2.3 ppm entering the lagoon,
averaging 3.2 ppm. The levels in the lagoon discharge were considerably
lower, ranging from 0.7 to 0.5 ppm and averaging 0.6 ppm. This is a
reduction in concentration of about 80%, fairly comparable to the over-
all lagoon BOD efficiency which is in the 85 to 87% range usually.
The fatty acids are the next major class of compound found, these
ranged from 3.1 to 0.7 ppm entering the lagoon with an average of
1.5 ppm. Again the levels in the lagoon effluent were much lower,
ranging from 0.6 to 0.1 ppm and averaging 0.3 ppm, about 80% removal.
The saturated fatty acids palmitic and especially stearic seem to be
more difficult to remove than the unsaturated acids, this is in agree-
ment with other observations on sewage treatment plant performance.
The information on phenols is disappointing. Early in this
study a number of phenols were detected and identified, including
guaiacol and syringbl, however a change in analysis methods to the
resin isolation rather than solvent extraction effectively eliminated
the phenols from the recovered compounds and the quantitative data
reported in Table 32 on phenols is not reliable.
41
-------
SECTION IX
POLAR WATER SOLUBLE COMPOUNDS
Polar compounds as used in this report is defined as those organic
compounds that cannot be extracted from aqueous solutions by organic
solvents. The types of compounds of this class found in kraft pulp
mill effluent are mostly polysaccharide degradation products such as
sugar acids and their fragmentation products. In the lagoon effluent
many products of bacterial metabolism also appear. Most sugar acids
remain in the black liquor and are burned in the recovery furnace, how-
ever, there is an appreciable amount of these compounds that reaches the
lagoon via weak wash water, black liquor spills and other miscellaneous
sources, so it was necessary to include this class of compounds in this
study.
Lagoon influent and effluent samples were prepared for analysis by
filtering, adjusting pH to 7.0, and passing one liter of the sample over
a 50 ml column bed of XAD-2 resin at a 2 ml/min flow rate for removal of
most of the low solubility neutral and acidic organic materials. The
column eluate was then adjusted to pH 8.5 and concentrated 60 fold using
a heated rotary evaporator. The pH was raised to 9.2 and sodium tetra-
borate and methanol added to adjust their concentration to 0.03 M and 2%
respectively. This solution was then analyzed by liquid chromatography.
The liquid chromatograph used a 2 liter solvent reservoir, a Waters
3000 pvunp, a septum injector, a 2.4 mm ID x 50 cm stainless steel column
j^
packed with 35-37 micron Bio-Rad AGI-X10 anion resin, and a Waters Differ-
ential refractometer detector. Data was recorded with a Varian A-25
recorder. Elution was done with a 0.03 M sodium tetraborate 2% methanol
solvent.
Compound identifications were made by collecting eluted portions
corresponding to detector peaks, preparing trimethylsilyl (TMS) deriva-
42
-------
tives, checking these for purity by gas chromatography and then obtain-
ing their mass spectra via the liquid sample inlet system in the mass
spectrometer. The scheme of analysis and identification is illustrated
in Figure 10.
Individual detector peaks were collected as fractions from the
liquid ch romatog raph, freeze dried and converted directly to the TMS
derivatives. Five mg of the acid salt fraction were mixed with O.^t ml
pyridine, 0.2 ml N,0-bis-trimethylsilyl-acetamide and 0.1 ml trimethyl-
chlorosi lane. After reaction at room temperature for 4 hours the
mixture was rotary evaporated to dryness at 35°C and the residue
dissolved in hexane. Compound purity was checked by gas chromatography
using a 3% QF-1, 1/8 in. OD by 6 ft. packed column. A temperature
program of 70 to 180°C was used so that solvent and any remaining rea-
gents were well separated from the derivatized acid. Examples of the
gas chromatographs of several of the TMS derivatives of these acids are
shown in Figure 11. If the compound was sufficiently pure, the sample
was evaporated to dryness and introduced into the mass spectrometer
through either the solid probe or the liquid inlet.
Typical mass spectra obtained by these methods are shown in Figure
12. Examination of these examples shows that there are not large
differences in the spectra of the sugar acids, and consequently identi-
fication had to be made by running knowns through the same procedure
on our mass spectrometer. The methods of identifications are summarized
In Table 12, and a typical liquid chromatogram from a lagoon sample
with the identified compounds indicated is shown in Figure 13.
The sugar acids are not as well known as most of the other organic
compounds encountered in this study and therefore an illustration of
the mass spectra of the TMS derivative of glucometasaccharinic acid,
including a schematic showing the fragmentation pattern is shown in
Figure 14 and the fragment losses resulting in the observed mass spectra
-------
SAMPLE
CLEAN-UP
(XAD-2)
CONCENTRATION
(ROTO EVAP)
H P LIQUID CHROMATOGRAPH
(ANION EXCHANGE)
FRACTIONS.
DERIVATIZATION
(TMS)
GC
MS LIQUID INLET SYSTEM
MS
I.. L .1. i I ..
Figure 10. Polar compound analysis and identification
44
-------
LU
(/)
z
o
Q.
(T)
LU
o:
\-
o
LU
I-
LU
a
10 15
TIME (minutes)
3-DEOXY-PENTONIC
(ERYTHRO ••- THREO)
L
GLUCO "ISO" SACCHARINIC
GALACTO "META" SACCHARINIC
GLUCO "META" SACCHARINIC
20
Figure II. Gas chromatograms of trimethylsilyl derivatives of some polar acids
-------
100
80
60
40
20
100
80
uj 60
o
^40
§ 20
13
03
UJ
UJ100
60
40
20
100
80
60
40
2C
3-
*
^
6
K
f-
h
6
K
N
r
f
-
-
-DEOXY-ERY
A
r)
f
J
O
ALACTO "M
>
h
5
, ' \
THRO-PENTONIC 205! 321
CID i
r CH2-i-CH— {-CH2 — CH— r-C*
OTMS OTMSJ OTMS OTMS
335 ! „
IO
3 s i
k(M "J (\|
T , , , , , T*f T i "I i i i i | i i nr^ | i i i i , , . . . | i i i i
ETA" SACCHARINIC 205| 423
ACID !
OTMS!
« CH2-UCH— J-CH CH2— CH — !-Cf
8 I ! l 1 nru«
C ^ OTMS | OTMS OTMS °™5
437 J335
1CM 10 ,0 K
!o ^ ^
423!
LUCO"lSO" SACCHARINIC ACID 1 205|437\ OTMSJ
! x> H r '
1 1 \ M2l« | n
'• CH2-j-CH— j-CHz— ~C }cf'
OTMS; OTMS! OTMS! OTMS
10 1437 ! !
N S ^^
1 Ixio
111 • .^1 . i li J !__•
2 GLUCO"MI
f
<
ro
O
l"
; 205i 423 i
ETA" SACCHARINIC ACID ^-j-CH-r CH— CH2-CH-^ cf
? OTMSI OTMS OTMS OTMSi OTMS
« 1437 335 '
O m
S fxro «
t 10
«» 1 to
2! f-
1 S J5
J j f M J_i
100 200 300 400
m/e
Figure 12. Trimethylsilyl derivatives of some saccharinic acids
46
-------
TABLE 13
IDENTIFICATION METHODS FOR POLAR COMPOUNDS
Peak
NO.
1
2
3
4
5
6
7
8 & 9
10
11
12
13
Compound Identity
Formic
Acetic
Gly colic
2-Hydroxybutyric
Lactic
3 -Deoxy- D-thre o-pentoni c
3-Deoxy-D-erythro-pen tonic
a& 3-D-Gluco"iso"saccharinic
3-D-G luco "me ta "a accharini c
a-D-G luco"me t a"saccharinic
Unknown
-D-Galacto"meta"saccharinic
Identification Method Reference
LC retention correlated with purchased - two different
same
same
same
same
LC retention correlated with synthesized
GC retention correlated with published value
LC retention correlated with synthesized
GC retention correlated with published value
Mass spectra correlated with published spectra
LC retention correlated with synthesized
GC retention correlated with published value
Mass spectra correlated with published spectra
LC retention correlated with published value
GC retention correlated with published value
Mass spectra correlated with published spectra
LC retention correlated with published value
GC retention correlated with published value
Mass spectra correlated with published spectra
GC retention correlated with published value
Mass spectra correlated with published spectra
buffers
(13,14)
(13,15)
(16)
(14 ,15)
(16)
(17,18)
(13,15)
(16)
(J8)
(13,15)
(16)
(13)
(16)
-------
1 FORMIC ACID
2 ACETIC
3 GLYCQLIC
5 LACTIC
6 3-DEOXY-D-THREO-PENTONIC
7 3-OEOXY-D-ERYTHRO-PENTONIC
8 -D-GLUCO "ISO" SACCHARINIC ACID
9 -0-GLUCO "ISO" SACCHARINIC
10
I-GLUCO "META" SACCHARINIC
it a - GLUCO "META" SACCHARINIC
I2 UNKNOWN
13 -D-GALACTO "META" SACCHARINIC
CO
LU
cn
o
a.
c/)
UJ
or
o
o
h-
LL)
O
3 5
6 7 8 9 10II 12 13
0
50 100 150
ELUTION VOLUME (ml)
200
Figure 13. Liquid chromatogrom of polar acids- lagoon influent 2/14/73
-------
vc
LU
100
-co a
-HOTMS
435
PARENT m/e
540
-CH2OTMS
437
-o*
"OTMS
423
OTMS OTMS
\
147 DECOMPOSITION
PRODUCT
335
§100
m 80
< ~~
LU
p 40
3 20
LU
or
n
t*
-
"
T
if
o
-.1
L
It 1
i i i i i i i i \
in
-HOTMS
0 10 OAR
CJ ^- t.*Tj
I
J
K " Sxio &
CM
J
1 ™ "
i 'O
1 1
ro
! 1 ou^
! 1 5?
, ! J J ^,L
1 1 1 1 1 1 1 1 1 I 1 1 ! 1 1 1 1 1 1 1
1 I 1 I I I 1 l 1 1 l 1 I
200 300 400
m/e
Figure 14. Mass spectra fragmentations-IMS derivative of
glucometasaccharine acid
-------
are summarized in Table 14 . The primary fragmentations are carbon chain
cleavage.
TABLE 14
FRAGMENTATION OF THE TMS DERIVATIVE
OF GLUCOMETASACCHARINIC ACID
m/e(T) RATIONAL
437 (1) Loss of C-6 from in/e 540 parent
435 (1) Loss of carbon monoxide and trimethylsilanol from m/e
540 parent
423 (2) Loss of C-l from m/e 540 parent
335 (4) Loss of C-5 and -6 from m/e 540 parent
245(45) Loss of trimethylsilanol from m/e 335
217(17) Loss of carbon monoxide from m/e 245
205(55) C-5 and -6 TMS fragment
147(80) Decomposition from m/e 205
103(55) C-6 TMS fragment Also a rearrangement product
73(100) Trimethylsilyl ion (base peak)
The polar compounds identified in lagoon samples are essentially the
saccharinic acids and further degradation products expected from alkaline
treatment of polysaccharides. A number of small molecule organic acids
such as acetic are observed which may also arise as a result of metabolic
processes occurring in the lagoon.
Quantitative data was obtained from the liquid chromatograph by
calibration with purchased or synthesized known compounds. Unavailable
saccharinic acids (galacto) were quantitatively correlated by dichro-
mate oxidation of individual fractions with the other knowns. Data ob-
tained on the Springfield and Everett lagoons is summarized in Table 15
which shows concentrations of the individual acids in ppm, and Table 16
50
-------
TABLE 15
CONCENTRATION OF POLAR ORGANIC ACIDS IN AERATED LAGOONS
in
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Compound
Identity
Formic
Acetic
Glycolic
2-Hydroxy butyric
Lactic
3 -Deoxy -D- threo-
pentoni c
3-Deoxy-D-ery thro-
pent onic ,.
a or B-D-Glucoiso >
saccharinic
a or 8-D-Glucoiso
saccharinic
8-D-Glucometa
saccharinic
a-D-G lucometa
saccharinic J
Unknown
D-G alactoraeta
saccharinic
Other Acids
TOTAL
ABI ABE
7/17/72 7/25
15.6
35.2
2.4
1.2
3.3
0.8
0.6
\
\
I 1
I
> 14.4
/
J
8.8
2.8
11.8
96
35.2
29.2
1.0
0.8
0.9
0.4
->.
'
1
> 2.0
1
0.8
0.4
13.7
84 ]
ABI
9/13
11.2
13.5
2.0
2.0
2.0
4.5
6.5
\
\
79.5
J
22.0
21.0
9.0
L73
Springfield
ABE ABI
9/21 2/14/73
77.5
7.2
1.5
Cl.O
tr
3.5
7.0
97
36.0
56.0
2.5
5.0
32.5
3.0
37.0
58.0
60.0
53.0
32.0
29.0
30.0
436
ABE
2/21
6.5
3.0
tr
tr
tr
nd
nd
nd
nd
nd
nd
nd
nd
18.0
27
ABI
5/10
9.6
10.2
2.1
2.8
1.3
nd
nd
nd
nd
nd
nd
nd
nd
16.7
43
ABE
5/17
5.5
6.0
0.7
0.4
0.5
nd
nd
nd
nd
nd
nd
nd
nd
10.0
23
Everett
ABI
2/28/73
17.2
9.6
3.8
2.0
4.0
8.8
1.3
1.4
3.8
4.4
5.2
5.7
2.8
41.8
112
-------
TABLE 16
TREATMENT EFFICIENCY FOR POLAR ORGANIC ACIDS
TOTAL IN PPM TOTAL IN PPM
PEAKS 1-13 ALL PEAKS
SUMMER
07-18-72 IN 84.6 96.4
07-25-72 OUT 70.7 84.4
QUANTITY REMOVED 13.9 12.0
PERCENT REMOVED 16.6% 12.4%
AUTUMN
09-13-72 IN
90-21-72 OUT
QUANTITY REMOVED
PERCENT REMOVED
WINTER
02-14-73 IN
02-21-73 OUT
QUANTITY REMOVED
PERCENT REMOVED
SPRING
05-10-73 IN 26.0 42.7
05-17-73 OUT 13.1 23.1
QUANTITY REMOVED 12.9 19.6
PERCENT REMOVED 49.6% 45.9%
52
-------
which presents a summary of the seasonal treatment efficiency of these
compounds.
It seems appropriate to discuss these acids in two categories;
the sugar acids which arise from the pulp mill only/ and the small
molecule acids such as acetic and formic, which are also metabolic
products formed in the lagoon.
The lagoon is very effective at all times in eliminating the
sugar acids from the wastewater stream. The case with formic and
acetic acid is much different. Acetic acid is lowered in concentra-
tion across the lagoon an average of 60%, and in the best case (Winter
1973) over 94%. Formic acid, however, is actually produced by the
lagoon. This effect is thought to be a function of the operating
pH, since metabolism of formic acid is known to be retarded at pH
7.4 and above (19 )• Strained oxygen conditions within the lagoon
also interfere with formic metabolism.
Reviewing one years lagoon performance, during the summer 1972
the saccharinic acids are effectively metabolized (80%+), while the
acetate and other small molecule acids remains high and formate more
than doubles in concentration. The fall 1972 samples showed better
overall performance with the saccharinic acids being over 96% removed.
Again acetate and other small molecules remain somewhat high, and
formate .increased seven fold across the lagoon. The winter 1973 samples
were taken during a heavier loading period, probably some liquor spill
was involved here as indicated by the unusually large amount of
saccharinic acids being fed. The effluent sample corresponding to this
influent was exceptionally clean, showing only traces of acetate and
other small molecule acids. The spring 1973 sample, in contrast to the
winter sample, shows almost no evidence of liquor in the input, and low
output levels.
These results illustrate several things. First, the input levels
53
-------
to the aerated lagoon vary widely. Even in the limited number of sam-
ples taken in this study a 10 fold range can be seen. Secondly, regard-
less of whatever else is occurring, the sugar derived saccharinic acids
are essentially completely removed from the wastewater. Thirdly/ acetate,
formate and other small molecule acids which are metabolic products in
the lagoon are often not significantly lowered in concentration by the
lagoon treatment.
54
-------
SECTION X
CONTROL OF ORGANIC COMPOUNDS IN HILL EFFLUENT
This study has identified simple organic acids, saccharinic acids
and related products, resin acids, fatty acids, phenols and various
terpenes in the effluent from kraft pulp mills. It has also shown that
the aerated lagoon is quite effective in lowering the amounts of these
materials so that the treated water discharged from the lagoon contains
less than 1 ppm of each class of compound except the simple organic
acids, which may be near the 100 ppm range, depending on lagoon opera-
tion.
Based on review of the literature, these discharge levels do not
seem to be of importance environmentally, with the possible exception
of the resin and fatty acids where a wider safety margin would be
desirable (20,21). There are recent reports of a variety of bacteria
which readily metabolize resin acids (22). At present there does not
seem to be much effort to optimize lagoon performance by utilization of
specific bacteria or other means and in-plant control has therefore been
examined. These acids are non-volatile and can only enter the mill waste-
water in an aqueous stream. Some sources of loss are liquor spills,
entrainment in the evaporators, weak wash water and bleach plant efflu-
ent which is not reused etc. A special and important case is foaming
over of equipment. It is known that these acids are associated with
foam stabilization and they can be recovered from black liquor by
foam fractional ion. Any process unit which foams over, resulting in
a spill, is selectively transferring these acids out of the recovery
process and into the wastewater discharge stream. Control of foaming
is therefore an essential part of in-process control of discharge of
the resin acids. Probably the best way to protect against loss of
this type is to provide a system for spill containment which will allow
return for recovery of the material. Controlled release to the treat-
ment system is an alternative.
55
-------
This study shows that the major terpene in the discharged wastewater
is ot-terpineol. The monoterpenes in the wastewater are about 90% oxy-
genated compounds and most of this is a-terpineol. This turpentine
content is very different from the crude sulfate turpentine from the
same mill, which is about 15% oxygenated terpenes. The main reason for
this difference is that most of the hydrocarbons are removed in the
turpentine collection system, and only the less volatile more water solu-
ble terpenes remain in process water to enter the wastewater streams (23).
The main sources are the turpentine decanter underflow, 4500 ppm turpen-
tine and hot water accumulates water, 650 ppm turpentine (24). If further
in-plant control is desired, steam stripping of these two streams would
lower the turpentine in mill effluent by about one-half and this should
help lower the overall terpene discharge.
56
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SECTION XI
REFERENCES
1) Kleppe, P.J. and C.N. Rogers. Survey of water utilization and
waste control practices in the Southern pulp and paper industry.
Water Resources Research Institute, University of North Carolina.
Chapel Hill. Report No. 35. Water Resources Research Institute.
March, 1970. 60 p.
2) Keith, L.H. Identification of organic contaminants remaining
in a treated kraft pulp mill effluent. Presented at: ACS
Meeting. Minneapolis, April 14-18, 1969. 6 p.
3) Keith, L.H., A.W. Garrison, M.M. Walker, A.L. Alford and A.D.
Thruston. The role of nuclear magnetic resonance spectroscopy
and mass spectrometry in water pollution analysis. Presented
at: ACS Meeting. New York, September 8-12, 19&9- 4 P-
4) Garrison, A.W., L.H. Keith and M.M. Walker. The use of mass
spectrometry in the identification of organic contaminants in
water from the kraft mill industry. Presented at: Eighteenth
Annual Conference on Mass Spectrometry and Allied Topics.
San Francisco, June 14-19, 1970. 9 p.
5) Keith, L.H. and S.H. Hercules. Environmental applications of
advanced instrumental analyses. Assistance Projects. FY 69-71.
Washington, D.C. Report No. EPA-R2-73-115. Environmental
Protection Agency. May, 1974. p. 50-63.
6) Anderson, A.W. and G.A. Beierwaltes. Slime growth evolution of
treated pulp mill wastes. Report No. 12040-DLQ. Environmental
Protection Agency. August, 1971. 54 p.
7) Cornu, A. and R. Mossat. Compilation of mass spectral data.
London, Heyden and Sons, Ltd., 1964.
8) Ryhage, L. and E. vonSyndow. Mass spectrometry of terpenes - I.
Monoterpenes and Hydrocarbons. Acta Chem. Scand. _[8_:2025-2035,
1963.
9) VonSyndow, E. Mass spectrometry of terpenes -III. Monoterpene
aldehydes and ketones. Acta Chem. Scand. U[: 1099-1104, 1964.
10) Willhalm, B., A.F. Thomas and M. Stull. Mass spectra and organic
analysis - IV. Some comments on the mass spectra of monoterpenes
alcohols. Acta Chem. Scand. UJ: 1573-1576, 1964.
57
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11) Carpenter, W.L., J.G. Vamakias and i. Gellman. Temperature
relationships in aerobic treatment and disposal of pulp and
paper wastes. J. WPCF. 40_:733-740, 1968.
12) Stenhagen, E., S. Abrahamsson and F.W. McLafferty. Atlas
of mass spectral data. New York, Interscience, 1969.
13) Samuelson, 0. and L. Thede. Influence of oxygen upon glucose
and cellobiose in strongly alkaline medium. Acta Chem. Scand.
22^:1913-1923, 1968.
14) Petersson, G.H. Riedl and 0. Samuelson. Gas chromatographic
separation of aldonic acids as trimethyIsilyl derivatives.
Svensk Papperstidn, 70^:371-375, 1967.
15) Petersson, G., 0. Samuel son, K. Anjou and E. vonSyndow.
Hass spectrometric identification of aldonolactones as tri-
methylsilyl ethers. Acta Chem. Scand. 21_: 1251-1256, 19&7.
16) Petersson, G., A. McLafferty. Type rearrangement of a tri-
methylsilyl group in silycated hydroxyl carbonyl compounds.
Org. Mass Spec., 7.:575-591, 1972.
17) Alfredsson, R., L. Gedda and 0. Samuel son. A comparison
between alkali cooking of cellulose and hot alkali treatment
of hydrocellulose. Svensk Papperstidn, 6_J_:684-698, 1961.
18) Samuelson, 0. and L. Thede. Identification of carbonyl groups
in cellulose after aging as alkali cellulose. TAPPI, 52;
99-104, 1969.
19) Tikka, J. The mechanisms of glucose metabolism in E. Col i
(German). BiochimZ, 2_79_:264-288, 1935-
20) Rogers, I.H. Secondary treatment of kraft mill effluents:
Isolation and identification of fish-toxic compounds and their
sublethal effects. Pulp Paper Mag. of Can., 74_:T303-T308, 1973.
21) Leach, J.M. and A.N. Thakore. Identification of the constituents
of kraft pulping effluents that are toxic to juvenile coho salmon.
J. Fisheries Res. Brd. Can., 30_:479-484, 1973-
22) Hemingway, R.W. and H. Greaves. Biodegradation of resin acid
sodium salts. TAPPI , 56:189-192, 1973.
58
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23) Hrutfiord, B.F. and D.F. Wilson. Turpentine in kraft mill
process streams. To be presented at: 1975 Environmental
Improvement Conference, Vancouver, October 15-17, 1975, 4 p.
24) Hrutfiord, B.F. and D. F. Wilson. Turpentine concentrations
in kraft mill condensate streams. Pulp Paper Mag. of Can..
7i:T217-T219, 1973.
59
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SECTION XII
PUBLICATIONS AND PATENTS
The following publications have been produced or are antici-
pated to be produced as a result of this project:
1) Wilson, Donald F. and Bjorn F. Hrutfiord, "The Fate of
Turpentine in Kraft Mill Aerated Lagoons," presented at
the 1974 CPPA Environmental Conference, Toronto. In
press. Pulp and Paper Magazine of Canada.
2) Hrutfiord, B. F., T. S. Friberg, D. F. Wilson and J. R.
Wilson, "Organic Compounds in Pulp Mill Lagoon Discharge,"
presented at the 1975 TAPPI Environmental Conference,
Denver. Submitted to TAPPI for publication.
3) Hrutfiord, Bjorn F. and Donald F. Wilson, "Turpentine in
Kraft Mill Wastewater" presented at the 1975 CPPA regional
Environmental Conference, Jasper.
4) Dissertation: "Monoterpenes: Their Fate and Analysis in
Kraft Mill Aerated Lagoons and Kraft Processing" Donald
Frederick Wilson. University of Washington, 1974.
60
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SECTION XIII
Aerated Lagoon
Lagoon Influent
GC/MS
XAD Resin
Neutral Compounds
Acidic Compounds
Polar Compounds
Terpenes
Fatty Acids
Resin Acids
Extraction
GLOSSARY
A pond used for BOD removal in which mill efflu-
ent is intensively aerated for seven days or so.
Waste water from the entire mill complex in-
cluding both the pulp mill and paper mill.
A coupled gas chromatograph-mass spectrometer
used for organic compound separation and
identifi cation.
A resin capable of removing organic compounds
from water which operates by adsorption by
weak interactions.
Organic compounds soluble in organic solvents
which do not contain acidic or basis func-
tional groups.
Organic acids, including phenols, resin acids
and fatty acids present in kraft effluent.
Water soluble organic solvent insoluble com-
pounds, mostly derived from polysaccharide de-
gradation.
C _ hydrocarbons, ketones and alcohols which
are related to isoprene.
C,^ and C, _ long chain aliphatic acids.
16 lo
C acids from wood rosins.
Immiscible solvent pair partition to selectively
remove dissolved materials from one liquid
into a second.
61
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-660/2-75-028
3. RECIPIENT'S ACCESSION-NO.
TITLE AND SUBTITLE
5. REPORT DATE
Organic Compounds in Pulp Mill Lagoon Discharge
6. PERFORMING ORGANIZATION CODE
AUTHOR(S)
Bjorn F. Hrutfiord, Thomas S. Friberg, Donald F.
Wilson, John R. Wilson
8. PERFORMING ORGANIZATION REPORT NO.
PERFORMING ORG\NIZATION NAME AND ADDRESS
College of Forest Resources
University of Washington AR-10
Seattle, WA 98195
10. PROGRAM ELEMENT NO.
IBB037
11. CONTRACT/GRANT NO.
2. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
5. SUPPLEMENTARY NOTES
16. ABSTRACT
Organic compounds entering and leaving kraft mills aerated lagoons have been
identified and determined quantitatively. The compounds found were terpenes
and related low B.P. materials, resin and fatty acids, phenols and sugar acids.
The terpenes, resin and fatty acids are similar to those present in the wood
specie being pulped. Some terpenes, phenols and sugar acids are produced during
the pulping reactions. About 8 ppm total terpenes were found in the lagoon influent
and 1 ppm or less were in the effluent. a-Terpineol was the major compound entering
the lagoon and camphor the main terpene in the effluent. The total resin acid
concentration entering the lagoon was 3.2 ppm with 0.6 ppm leaving. Fatty acids
were lower both entering and leaving the lagoon. Sugar acids were found at about
100 ppm total entering, these were usually completely eliminated in the lagoon.
Control of terpenes can be done by in-process steam stripping and the other com-
pounds can be partially controlled by in-plant spill containment.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
aerated lagoon, kraft pulping, terpenes,
resin acids, fatty acids, sugar acids,
identification organics, mass spectro-
meter
Kraft mill effluent
characterization,
aerated lagoon effluent,
chemical composition
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport/
21. NO. OF PAGES
20. SECURITY CLASS (Thispage}
22. PRICE
EPA Form 2220-1 (9-73)
* U.S. GOVERNMENT PRINTING OFFICE: 1975—699-182 /3I REGION 10
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