EPA-905/3-78-004
Do not WEED. This document
should be retained in the EPA
Region 5 Library Collection.
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-292 818
Investigation of Chlorinated and
Nonchlorinated Compounds in the
Lower Fox River Watershed
Wisconsin Dept of Natural Resources,
Prepared for
Environmentoi Protection Agency, Chicago, II Great Lakes Nationai Program
Sep 78
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United States,
Enwonmerrtai'?rotection
Agency
Great Lakes
National Program Office
230 South Dearborn
Chicago, IL 60604
EPA-9Q5/3-78-OQ4
September 1978
vvEPA Investigation of Chlorinated
And Nonchlorinated
Compounds in the Lower
Bwt River Watershed1 ,
Wisconsin Department of Natural Resources
U.S, Environmental Protection Agencv
Region 5, library
t . "REPROOUCEO BF^ "~^~ ~
i NATIONAL TECHNICAL
1 INFORMATION SERVICE
j U.S. DEPARTMENT OF COMMERCE
j SPRINGFIELD, VA. Z2I61
*
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PB 292818
INVESTIGATION OF CHLORINATED AND NONCHLORINATED COMPOUNDS
IN THE LOWER FOX RIVER WATERSHED
by
WISCONSIN DEPARTMENT OF NATURAL RESOURCES
WATER QUALITY EVALUATION SECTION
In fulfillment of
EPA Contract No. 68-01-4186
for the
U.S. ENVIRONMENTAL PROTECTION AGENCY
REGION V
Chicago, Illinois 60604
EPA Project Officer: Howard Zar
Great Lakes National Program Office
Report No. EPA 905/3-78-004
September 1978
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
U.S. DEPARTMENT Of COMMERCE
SPRINGFIELD, VA. 22161
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THIS FORM IS PRINTED AS THE FINAL PAGE IN THE ATTACHED. REPORT '
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 905/3-78-004
REOl
r
4. TITLE AND SUBTITLE
Investigation of Chlorinated and Nonchlorinated
Compounds in the Lower Fox River Watershed
S. REPORT DATE
September 1978
6. PER'FORMING ORGANIZATION CODE
'.AUTHORS)
Joseph Ball, Francis Priznar, Paul Peterman
Compilers
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Wisconsin Department of Natural Resources
Water Quality Evaluation Section
Box 7921
Madison, Wisconsin 53707
10. PROGRAM ELEMENT NO.
ii.cb'NTRAct /GRANT NO.
EPA Contract No.
68-01-4186
s
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
230 S. Dearborn Street
Chicago, Illinois 60604
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
IS. SUPPLEMENTARY NOTES
EPA Project Officer: Howard Zar (312-353-2117)
Ti
16. ABSTRACT
This report concerns the existence, source and fate of chlorinated and non-
chlorinated organic compounds in the Lower Fox River of Wisconsin. Raw and
treated wastewaters, surface water, seston, snowmen, sediment, fish and clams
were sampled. A total of 105 compounds were identified and an additional 20
compounds were characterized by GC/MS. Twenty identified compounds are on the
U.S. EPA Consent Decree Priority Pollutant List. Tha-study shows PCBs and some
other chloro-organics in effluents are reduced by efficient suspended solids
removal. It is possible, but not proven, that some chloro-organics are formed
by process or effluent chlorination. Clams were found to rapidly bioaccumulate
PCBs. Fish fillet samples contained PCB concentrations up to 90 mg/kg. Sediments
throughout most of the river were found to be contaminated with PCBs. An ex-
tensive bibliography is included.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS c. COSATI FieW/Group
Chlorinated Organic Compounds
Organic Compounds
Toxic Compounds
PCBs
Pulp and Paper Mills
Sewage Treatment Plants
IB. DISTRIBUTION STATEMENT
IS. SECURITY CLASS (This Report)
21
SO. SECURITY CLASS (Thupage)
22. PRICE
EPA Form 2220-1 (R«v* 4-77) PREVIOUS EDITION is OBSOLETE
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This report has been developed under auspices of the Great Lakes
National Program Office. The purpose of the Office is to provide
a national focus for implementation of U.S. Environmental Protection
Agency programs on the Great Lakes.
This report has been reviewed by the U.S. Environmental Protection
Agency and approved for publication. Approval does not signify that
the contents necessarily reflect the views of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
RECYCLE NOTICE: If the report is not needed, please return to EPA,
Great Lakes National Program Office, 230 S. Dearborn,
Chicago, Illinois 60604 for further distribution.
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JW^Hk.
ACKNOWLEDGMENTS
The following people were major contributors to this report:
Joseph Ball, Thomas Gibson, Francis Priznar
Wisconsin Department of Natural Resources
Dr. Joseph Delfino, Douglas Dube, Paul Peterman
Wisconsin State Laboratory of Hygiene
We wish to thank the following people who assisted us during this study:
Furnished standards:
Dr. D. Easty9 Institute of Paper Chemistry,,Appleton, Wisconsin,
Dr. J. M. Leach, B. C. Research, Vancouver, B.C. Canada
Dr. K. Lindstorm, Swedish Forest Products Research Lab,
Stockholm Sweden
Dr. I. H. Rogers, Pacific Environment Institute, W. Vancouver,
B. C.s Canada
Dr. D. Zinkel, Forest Products Lab, Madison, Wisconsin
Mass Spectra Interpretation:
Dr. K. Shimada, Government Forest Experiment Station, Tokyo,
Japan
Dr. Bo Trost, University of Wisconsin-Madison
GC-MS Collaborative Analyses:
Drs. A. Alford and A. W. Garrison, U.S. EPA, Athens, Georgia
i
M I
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ABSTRACT
This study was developed because of the increasing concern over potentially
toxic chlorinated and nonchlorinated organic compounds entering the environ-
ment. The Lower Fox River was studied because of the large number of
industrial and municipal wastewater treatment systems discharging to this
64-kilometer stretch of river. Effluents, surface water, seston, snowmelt,
sediment, fish, and clams were sampled.
A total of 105 compounds were identified by gas chromatography/mass
spectrometry. An additional 20 compounds were characterized but not
conclusively identified. Twenty identified compounds are on the U.S.
EPA Consent Decree Priority Pollutant List. The study indicates that
PCBs and some other chloro-organic compounds are associated with efflu-
ent suspended solids and that solids removal reduces effluent contaminant
concentrations.
Effluent concentration ranges in ug/L for compounds quantified by GC/MS
were: benzothiazole 10-30, hydroxybenzothiazole 10-30, methyl thiobenzothiazole
10-40, trichloroquaiacols 10-60, tetrachloroguaiacol 10-50, dichlorophenol
15-40, Trichlorophenol 5-100, Tetrachlorophenol 2-20, Pentachlorophenol 5-40,
dehydroabietic acid 100-8500, and PCBs 0.4-68.0. It is possible, but not
proven, that some compounds were formed by process or effluent chlorination.
Clams were found to rapidly bioaccumulate PCBs. After a 27-28 day expo-
sure, PCB concentrations in clams ranged from 255 to 740 ug/kg. Fish fillet
samples contained PCB concentrations up to 90 mg/kg. Sediments throughout
most of the river were found to be contaminated with PCBs. Toxicity data
are lacking on many of the identified compounds and additional data are
needed.
rV
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CONTENTS
I. SUMMARY ....... ....... . 1
II. INTRODUCTION . 5
III. MATERIALS AND METHODS: SAMPLE COLLECTION ..... 11
Effluent .- . . . 11
Surface Water . 11
Sediment 12
Clams 13
Fish 14
Snowmel t . 16
Seston . ...... . ..... 16
IV. MATERIALS AND METHODS - Laboratory ....... 19
Extraction Procedures 19
Cleanup Column Chromatography ...... . 23
Methylation 25
Analysis by Gas Chromatography ......... 25
Gas Chromatography/Mass Spectrometry . 27
GC/MS Interpretive Analysis 30
V. WASTE TREATMENT FACILITY DESCRIPTIONS 53
Pulp and Paper Mills 53
Sewage Treatment Plants .... .... 79
VI. RESULTS AND DISCUSSION 93
Pulp/Paper Mill and Sewage Treatment Plant Effluents 93
Surface Water and Seston ..... 107
Sediment ....... '. . 116
Clams '..... o 120
Fish 124*
Snowmel t 129
REFERENCES 137
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APPENDICES
A. Compounds Identified by Gas Chromatography/Mass
Spectrometry A-1
B. Unidentified Compounds Characterized by
Gas Chromatography/Mass Spectrometry B-l
C. Relative Retention Time Index of
Compounds/Derivatives In Acid Extracts C-l
D. Mass Spectra of Samples Compared
with Standards D-1
E. Mass Spectra of Compounds Identified
by Literature Comparisons . . E-l
F. Mass Spectra of Compounds Not Identified F-l
Vt
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LIST OF FIGURES
1. Municipal and Industrial Wastewater Discharges
to the Lower Fox River 9
2. Water and Wastewater Extraction Procedure 21
3. Total Ion Chromatogram: Acid Extract of a Paper
Mill Effluent (Nonmethylated) ..... . 31
4. Total Ion, Chromatogram: Methylated Acid Extract
of a Paper Mill Effluent . 32
5. Total Ion Chromatogram: Methylated Acid Extract
of a Paper Mill Effluent 33
6. Mass Spectrum of 2, 4, 6, Trichloroanisole 35
7. Limited Mass Reconstructed Gas Chromatogram (LMRGC)
of 2, 4, 6, Trichloroanisole 36
8. Mass Spectrum of Dichloroanisole 37
9. LMRGC of Dichloroanisole ....... . 38
10. Mass Spectrum of Ber.zothiazole ......-, 40
11. LMRGC of Benzothiazole ..... 41
12. Mass Spectrum of Pentachloroanisole ... 42
13. LMRGC of Pentachloroanisole 43
14. Mass Spectrum of Tetrachloroveratrole 44
15. LMRGC of Tetrachloroveratrole V '. ."".'."". 45
16. Mass Spectrum of Methyl Dehydroabietate . 47
17. LMRGC of Methyl Dehydroabietate 48
18, Mass Spectrum of Methyl Chlorodehydroabietate 49
19. LMRGC of Methyl Chlorodehydroabietate 50
20. Kimberly-Clark Badger Globe and Neenah Paper
Waste Treatment System 54
21. Bergstrom Paper Mill Waste Treatment System 56
22. Wisconsin Tissue Mill Waste Treatment System 60
23. Midtec Paper Corporation Waste Treatment System 63
\Ju
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FIGURES - CONTINUED
24. NCR, Appleton Paper Division Waste Treatment System 65
25. Thilmany Pulp and Paper Waste Treatment System
(before May 16, 1977) ' 67
26. Thilmany Pulp and Paper Waste Treatment System
(after May 16, 1977) 69
27. Nicolet Paper Company Waste Treatment System 71
28. Fort Howard Paper Company Waste Treatment System 74
29. Green Bay Packaging Waste Treatment System 78
30. Neenah-Menasha Sewage Treatment Plant 80
31. Appleton Sewage Treatment Plant .. 83
32. DePere Sewage Treatment Plant 87
33. Green Bay Metropolitan Sewage District 90
34. Riverwater Sampling Locations 108
35. Sestpn Sampling Locations 114
36. Sediment Sampling Locations 117
37. PCB Bioaccumulation in Clam Tissue 122
38. Correlation of PCB Concentration to Fat Content in Fish ... 128
39. Snow Sampling Locations 131
40. Snow Sampling Locations . 132
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LIST OF TABLES
1. Fish Collected and Their Feeding Habit 15
2. Average Flow, BOD and Suspended Solids
Discharged to the Fox River 91
3. Pulp and Paper Mill and Sewage Treatment
Plant Effluents - Quantified Results 94
4. Relationship Between PCB Concentration and
Suspended Solids in Paper Mills and Sewage Treatment Plants . . 100
5. Effect of Filtration on PCB Concentration in Final
Effluent from Fort Howard Paper Company 102
6. Effect of Centrifugation on Selected Chloro-
organics in Final Effluents .... 102
7. Chlorinated and Nonchlorinated Organic Compounds
Identified in Samples from the Lower Fox River Watershed . . . : 104
8. Concentration of Chloro-organics (ug/L) Found in
Unfiltered Fox River Water 'in Downstream Order 109
9. Solubility of Chlorobiphenyls in Water 110
10. Chloro-organic Concentrations (ug/L) Associated
with Fox River Seston 113
11. PCB Concentration in River Water and Seston 115
12. PCB Concentrations in Sediment 118
13. Location of Sediment with PCB Concentration Greater
Than 10 mg/kg 119
14. PCB Analysis of Clams Placed in the Fox River 121
15. Lower Fox River Fish Sampling and Analysis Results 125
16. Results of PCB Analysis on Snowmelt Samples from the
Fox-Wolf River Drainage Basin . .* 133
17. PCB Levels in Snowmelt Water, 1975 135
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!. Summary
A total of 105 compounds were identified by gas chromatography/mass
spectometry (GC/MS) in selected extracts of wastewater, surface water,
sediment, snow,and biological samples. An additional 20 compounds were
characterized but not conclusively identified. Twenty of the 105 compounds
are on the EPA Consent Decree Priority Pollutant List. Other compounds
identified, including chloro-guaiacols, chloro-phenols, resin acids and
chloro-resin acids have been reported to be toxic to fish by other
investigators of pulp and paper mill wastewaters. Also identified are
other wood extractive and ligm'n-related compounds such as acetovanillone,
fatty acids, guaiacol, syri ngal dehyde, and vanillin.. Several identified
compounds commonly used in industry are benzothiazole, bisphenol A, and
nonyl phenol. Several compounds apparently not previously reported in
wastewater are chloroindole, chl orosyringaldehyde,and,tentatively, chloro-
bisphenol A's.
Concentrations of the various compounds ranged from 0.5 to 100 ug/L. An
exception was dehydroabietic acid (DHA), a toxic resin acid not found on
the Priority Pollutant List. It was frequently found in pulp and paper
mill effluents in concentrations ranging from 100 to S500 ug/L.
Sampling data and laboratory experiments show PCBs and some other chloro-
organics associated with suspended solids. Suspended solids reduction
reduces the chloro-organic concentration from raw to final effluents of both
pulp and paper mills and municipal sewage treatment plants receiving
pulp and paper mill wastes.
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Polychlorinated biphenyls (PCBs) were found in every type of environmental
sample collected during this investigation in the Fox River watershed.
Two hundred and fifty samples of pulp and paper mill wastewaters, sewage
treatment plant wastewaters, river and lake sediment, river water,
seston, snowmelt, clams,and fish were examined.
Of the 26 wastewater effluents sampled, 12 contained detectable levels
of PCBs. Concentrations of PCBs in final effluents ranged from 0.1 to
56 ug/L while raw wastewaters contained levels from 0.2 to 8200 ug/1.
Most effluents containing PCBs were related to paper mills using recycled
paper fibers in their production process. Aroclor 1242 was the predominant
mixture detected, although 1248 and 1254 were also found.
Levels of PCBs in 16 seston samples averaged 0.016 ug/L of filtered
water. The concentration of PCB associated with seston in river water
increased as the water traveled downstream and became exposed to more
discharge points.
PCBs in Fox River water were detected in 9 out of 25 samples collected.
The concentrations ranged from 0.05 to 0.85 ug/L. Samples containing
PCBs were collected near the outfalls of sewage treatment plants and
pulp and paper mills.
The concentration of PCBs in 34 river bottom sediments ranged from 0.05
to 61.0 mg/kg on a'dry weight basis. PCBs were not found in some samples
taken from Green Bay or upstream from all known PCB point sources.
Sediments with highest PCB concentrations were near known PCB discharge
points.
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Clams seeded at various locations in the Lower Fox River rapidly accumulated
PCBs. After 27-28 days exposure in the Lower Fox River,clams accumulated
PCBs from 255 to 740 ug/kg. The amount of PCB bioaccumulation in seeded
clams appears to be related to sediment concentrations.
Thirty-five fish samples from two locations contained PCBs. Concentrations
varied from 0.5 to 90 mg/kg fillet tissue. The concentration of PCB in
all of the sampled species was proportional to fat content. Aroclor
1242 was the predominant PCB mixture detected at the upstream site while
1248 was almost exclusively found downstream. Analytical masking or
selective bioaccumulation of the higher chlorinated isomers, which are
more lipid soluble, may be responsible for this effect.
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II. INTRODUCTION -
The current concern with the fate of chlorine in the aquatic environment
arises because,for decades, chlorine has been the principal means of
disinfecting drinking water and wastewater effluents. More recently,
chlorine has achieved importance as an anti-foulant for the cooling
systems of power production facilities. Together, these uses consume 3
to 4 percent of the nation's chlorine production (1). Increased understanding
of the ecological problems associated with chlorinated pesticides and
polychlorinated biphenyls (PCBs) has caused increased concern that other
chloro-organics may be formed in the chlorination process and have
similar impacts.
The presence of organic compounds in the water supplies of some large
U.S. cities has been documented (2,7). The results of a study by the
U.S. Environmental Protection Agency (EPA) in 1974 indicated that the
drinking water in New Orleans contained 66 organic compounds (3). Since
then, EPA has investigated the water supplies of 80 other cities under
the National Organics Reconnaissance Survey (NORS). Th'is sampling
program indicated the presence of one or more organohalide in 79 of the
supplies (4). The occurrence of halogenated (e.g. chlorine) organics in
finished water has been demonstrated to be widespread and to be a direct
result of the chlorination practice (5).
An even greater potential for chloro-organic formation is present when
municipal wastewater is chlorinated, because of its high organic content.
When used for disinfection, chlorine was thought to be oxidizing the
organic compounds to harmless substances and thereby lowering the biochemical
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oxygen demand of the effluent. Research has now shown that although
chlorine does oxidize many substances, it can also create many organo-
chlorine compounds which were not present in the raw wastewater entering
the treatment plant (6,42,52,58). The incorporation of chlorine into an
organic molecule generally increases its lipophilic character and at the
same time increases the toxicity, persistence, and bioaccumulation prop-
erties. Measurements that illustrate the nature of chloro-organics are
of interest because such information is useful in efforts to regulate
these compounds.
Of particular interest in Wisconsin is the chlorine or chlorine-containing
compounds being used by pulp and paper mills, one of the major industries
of the state. While 3 to 4 percent of the chlorine manufactured in this
country is used for wastewater and potable water disinfection, 15-16 per-
cent is utilized by the pulp and paper industry (1). During 1976 the
pulp and paper industry in the Lower Fox Valley reported using over 34
metric tons of chlorine per day (100). If chldro-organic compounds are
formed in the disinfection of wastewaters, it is reasonable to postulate
that similar compounds are created in the pulp and paper bleach process
and can gain entry into the open environment. Indeed, several investi-
gators have reported chloro-organics in bleached pulp mill effluent
(8, 22-26, 31, 36, 46).
Because of this interest, U.S. EPA (Great Lakes National Program, Region V)
contracted with the Wisconsin Department of Natural Resources (DNR) and the
associated State Laboratory of Hygiene (SLH) to initiate an explorative study
of chloro-organics in the Lower Fox River. The major goals of the study
follow:
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1. To monitor the distribution and occurrence of PCBs and suspected
chloro-organics.
2. To identify previously undetected chloro-organic compounds in
Lower Fox River effluents, surface water, biota,and sediment.
3. To determine which methods of treatment would be best suited
for chloro-organic removal from wastewater.
4. To describe the fate of PCBs in the Lower Fox River in terms of
a mathematical model.
The Lower Fox River is 64 kilometers long and extends from the outlet of
fake Winnebago to Green Bay (Figure 1).' The Lower Fox is one of the
major drainage streams in Wisconsin and is the most industrialized. It
is controlled by 11 dams and is navigable via an extensive series of
locks. The mean flow for the water year October '76 to September'77 at
the Rapide Croche Dam was 54.35 m3/s. The average discharge for the 81-
year record is 117.7 m^/s (101). Industrial pollution has been a problem
since the early 1900s. Wisconsin DNR water pollution surveys dating
back to 1938 indicate BOD, suspended sol ids,and dissolved oxygen problems.
Numerous references to fish kills are also found in Wisconsin DNR fish
management files.
Previous investigations indicate PCBs are present in the Lower Fox River
(10). This stretch of the river is also likely to contain other chloro-
organics since it receives the treated discharge from 15 pulp and/or
paper mills, one electric power plant, and 11 municipal wastewater
treatment plants serving a population of over 250,000 people.
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The information generated by this study will be used to establish or
revise effluent discharge limitations. Under the authority of the
Federal Water Pollution Control Act Amendments of 1972, P.L. 92-500, and
the 1977 amendments to it, the EPA must establish limitations including
toxic compounds for existing sources, standards of performance for new
sources, and pretreatment standards for discharge to publicly-owned
treatment facilities. The date for promulgating the limitations and
standards for the pulp and paper industry is September 30, 1979. Thus,
the information developed in this study will be applicable to the Federal
pollution control schedule.
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Consolidated
Riverside
Green Bay STP
Green Bay Packaging
Proctor & Gamble
American Can
Fort Howard
GREEN BAY
10
DePere STP
Nicolet Paper
LAKE
WINNEBAGO
NEENAH
Heart of the Valley STP
Thilmany Paper
Applefon Paper
Midtec
Applefon STP
Menasha SO East & West
.Wisconsin Tissue
I , ^iTGeorge Whiting
\imberly-Clark
~Neenah-Menasha STP
"Bergstrom Paper
'Kimberly-Clark
Badger Globe
Figure 1. Municipal and Industrial Waste Discharges to the Lower Fox River.
.9.
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III. MATERIALS AND METHODS - SAMPLE COLLECTION
EFFLUENT
Sampling was restricted to municipal wastewater treatment plants and
pulp and paper mills because of their high chlorine usage. Sampling was
performed by plant personnel to facilitate a time-of-travel study. Self-
sampling was necessary because of the large number of dischargers and
limited number of DNR personnel attached to this project. Detailed
sampling instructions were sent to each discharger several weeks in
'advance, and each one was telephoned just prior to the scheduled sampling '
date. Cooperation was excellent from all but one discharger.
Twenty-four-hour flow proportional composite samples of influent to and
effluent from wastewater treatment systems were collected when possible.
If composites were riot available, grab samples were taken. Samples were
refrigerated until picked up by DNR personnel within 24 hours of collection.
They were placed in coolers and hand-delivered to the laboratory
within 48 hours of removal from the waste stream. Glass bottles (2.5 L)
washed with detergent, hot water, acid,and distilled water were supplied
by DNR. All bottle caps were lined with aluminum foil,
SURFACE WATER
River and lake water samples were collected within 0.5 meter of the
surface at all locations. When samples were taken from piers, dams,or
bridges, a metal bucket was lowered by rope to make the collection. The
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water sample was poured into the sample container,which was rinsed at
least twice with the water sample before the actual sample was collected.
When samples were taken from a boat,the sample bottle itself was dipped
into the water. Care was taken to avoid gas and oil contamination from
the boat's motor.
These samples ranged in volume from 2 to 10 liters. _In all cases they
were immediately capped with an aluminum foil-lined top and placed in
insulated chests. The samples arrived at the laboratory within 48 hours
of collection.
SEDIMENT
The bottom sediment is generally considered the ultimate "sink" for most
contaminants reaching the aquatic ecosystem. Polychlorinated biphenyls
and other chlorinated organic compounds .are associated with particulate
matter. It is assumed that most particulate matter settles out .in slow
current areas, carrying these compounds to the bottom of the river.
Compounds in sediment may be redistributed via biological activity,
oxidation reduction reactions, volatization, physical disturbance, etc.
Twenty sediment samples were collected from Lake Winnebago to Green Bay.
An additional 14 sediment samples were collected in the lower part of
Green Bay to help establish the distribution of organic contaminants.
Sampling sites were located in conjunction with point sources, obvious
sediment build-up areas, and the prevailing current in Green Bay.
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Sediment was collected with a Peterson Dredge at all sites. Upon retrieval-,
the dredge was opened upside down and the sediment was scooped out of
both sides of the dredge with a quart-sized wide-mouth mason jar. The
jars had been previously rinsed with hexane,and lids were covered with
aluminum foil. All samples were then transported to the laboratory within
48 hours. Samples that could not be processed immediately were frozen.
CLAMS
The concentration of chloro-organic compounds at any one point in a
flowing river is in a continuous state of flux due to discharge
variations. Therefore, grab samples of the water column may not result ,
in a completely accurate determination of compounds present in the
ecosystem.
Freshwater clams filter feed on plankton and organic detritus. When
clams are feeding, a continuous stream of water passes through them,
and suspended particles are directed to the mouth after being filtered by
the gills. It has been established that clams bioaccumulate chemical
compounds in solution (9), and tissue concentrations eventually reach
an equilibrium that is correlated with the concentration in the water.
Very few clams are naturally present in the Fox River; therefore clams
were "seeded" at strategic locations as a biomonitoring organism.
Clams (Anodontoides ferussacianus)* were collected from the Deerskin
River, Vilas County,Wisconsin, which is devoid of point sources of
chlorinated compounds. Three specimens were sacrificed and screened for
* Identification by Harold A. Hathiak, Horicon, Wisconsin
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chlorinated organic compounds by GO/EC analysis, and no contaminants
were detected. Immediately after collection the clams were transported
in ice chests containing water from the collection stream and were placed
in the Fox River.
The clams were secured at the sampling sites by carefully drilling a
small hole in one half of the outer margin of the shell, placing a loop
of heavy tnonofi1ament line through the hole, and tying a sufficient
length of nylon line to the monofilament loop to assure free movement.
The nylon line was then secured to various anchors at each site (tree
limbs, buoys, etc). Wire baskets were rejected because of the problem
of solids or slime accumulation on the baskets and potential smothering
of the clams. All clams were gathered from the Deerskin River on May
23, 1977 and were placed in the Fox River by May 25, 1977.
A total of 74 clams were placed at 10 locations and harvested from each
site at varying time intervals. Upon collection the clams were wrapped
in aluminum foil, placed on ice, and transported to the laboratory for
analysis. If the clam's abductor muscle:-was under tension it was assumed
that the specimen was alive and had. been filtering for the full time in
place. It was recognized that time of submersion is not necessarily
equal to clam filtering time.
FISH
The discovery of PC&s in the environment in 1966 prompted investigations
of PCB bioaccumulation in fish (10). These studies did indicate that
PCBs were bioaccumulating to high concentrations in Fox River fish.
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Other investigations have shown that PCBs and other organic compounds
may also bioaccumulate in fish (21, 58, 62, 83).
Previous testing has shown that high fat content species such as carp
and trout generally contain much higher PCB concentrations than do low
fat content fish such as walleye and northern pike (10). It is therefore
desirable to include both game and rough fish in a sampling program;
rough fish because they are more apt to contain the lipophilic -compounds
of interest and game fish because they are more likely to be consumed by
humans. The species of fish commonly found in the Fox River collected
for this study are given in Table 1, along with their predominant feeding
habit.
Table 1. Fish Collected and their Feeding Habit.
Common Name Scientific Name Feeding Habit
Carp Cyprinus Carpio Omnivore
White Sucker Catostomus Commersoni Omnivore
Yellow Perch Perca Flavescens PIanktivore/Predator
Yellow Walleye Stizostedion Vitreum Predator
Northern Pike Esox lucius Predator
A fyke net was used to collect fish from Little Lake Butte des Morts and
below the De Pere Dam in April, 1977. A total of 35 samples were retained
for analysis. A sample was composed of either a large single fish or a
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composite of two or more small fish. Immediately after collection the
fish were wrapped in individual aluminum foil packages, placed on ice,
and transported to the laboratory for freezing prior to analysis.
As laboratory time permitted, the fish were partially thawed, filleted,
chopped, and placed in glass containers. All sample bottles were thoroughly
cleaned., hexane rinsed, and fitted with aluminum foil-lined caps prior
to use.
SNOWMELT
Nineteen snowmelt samples were collected by thawing a sufficient quantity
of snow from vertical snow columns to yield 2.5 L of water. Samples
were collected by melting snow in a clean metal container,using a portable
gas stove as a heat source. Temperature measurements were made on the
slush as a precaution against excessive heating and possible chloro-
organic loss by vaporization. The sample temperature was maintained at
^ 25°C as measured at the slush surface. The water was poured into a
glass sample bottle, covered with a metal-lined cap, and placed in
insulated chests for transport to the laboratory.
SESTON
Seston includes all suspended matter in a body of water, both living and
non-living, which is capable of being removed by filtration. Seston
samples were collected because of the presumed absorptive characteristics
of suspended material, and the possible bioaccumulation of many compounds
by planktonic organisms. If chlorinated organic compounds were present
in the river, even in low concentrations, they would likely be found in
detectable concentrations in the seston.
GPO 821-«>»3
-16-
-------
Seston samples were collected from 16 stations with a small gasoline
engine powered pump. The outlet side of the pump flowed through a
calibrated meter to allow determination of the volume of filtered water.
The metered flow was directed through a #20 mesh (80 urn) plankton net
with a #20 mesh cup attached. The body of the net was submerged in
water at all times to decrease pressure on the net and loss of material.
It was recognized that many small particles, including some of the
smaller phytoplankton, may pass through the net. It was standard procedure
to pump until a visible amount of material was present in the net. All
samples were collected from a depth of one meter. After pumping* the
samples were concentrated in the attached cup and transferred to glass "--..
bottles. Samples were stored in a styrofoam container and transported
within 48 hours to the laboratory for analysis.
-17-
-------
IV. MATERIALS AND METHODS - LABORATORY
EXTRACTION PROCEDURES
A. Water and Wastewater Samples (Figure 2)
Reagents
1. Chloroform, ACS, redistilled in glass.
2. Hexane (Skelly Solve B) b.p. 60-68°C,
redistilled in glass.
3. Sodium sulfate, ACS, granular, anhydrous. Stored at 130°C.
4. Methylene chloride, ACS, redistilled in glass.
5. Ethyl ether, AR, anhydrous.
6. Acetone, ACS, redistilled in glass.
7. Potassium Hydroxide, ACS, pellets.
Depending upon the amount of suspended material present,! or 2 liters of
sample were placed in a glass separatory funnel fitted with a Teflon
stopcock. The pH was adjusted to >11 with potassium hydroxide, and 100
ml of 15% methylene chloride in hexane was added. The funnel was shaken
for at least 1 minute. The aqueous phase was transferred to a second
separatory funnel and shaken with another 100 ml of the same solvent.
The aqueous phase was transferred to a third separatory funnel and
extracted with 100 ml of hexane. All three extracts were dried with a 2-
inch anhydrous sodium sulfate column and drained into a 400 mL beaker.
The aqueous phase was retained for acid extraction. The solvent was
evaporated to ca. 5 ml by passing a gentle stream of filtered air over
the beaker at room temperature,and the remaining solution was cleaned-up
by column chromatography. The aqueous layer from the previous extraction
was adjusted to pH less than 3 with 50% hydrochloric acid, and extracted
-19- Preceding page blank
-------
with two 100 ml aliquots of chloroform. The chloroform extracts were
combined and evaporated to dryness under a gentle stream of filtered
air. The residue was redissolved in acetone and adjusted to an appropriate
volume for injection into the gas chromatograph. Some acid extracts
were methylated to verify compound identification and to facilitate
analysis of more polar compounds.
B. Fish.
Reagents
1. Dry Ice.
Ap_p_aratus_
1. Laboratory blender and stainless steel blender jar.
2. Glass chromatography column, 350 mm by 20 mm id. with a 300
ml reservoir on top, a fritted glass disk at the bottom, and
a Teflon stopcock to control the flow.
Fish tissue was blended with dry ice at high speed to produce a free-
flowing powder. The dry ice was sublimed in a freezer for ca. 15 hours
at -20°C. Ten grams of frozen fish were mixed with 60 grams of anhydrous
sodium sulfate and allowed to stand for ca. 30 minutes with occasional
stirring.
One-half inch of sodium sulfate was added to a chromatography column and
the fish mixture was poured on top. The stopcock was opened and 200 ml
of 10% ethyl ether in hexane was added. When the solvent had filled the
column, the stopcock was closed slightly and the solvent eluted at ca. 5
mL/min.
Most of the solvent was evaporated and the extract quantitatively
transferred to a tared beaker. The remaining solvent was evaporated and
-20-
-------
1X3
-_^
I
1.5L WATER OR WASTEWATER :
w
pH £ 11 w KOH
- I
EXTRACT 2 x w 100 ml 15% CH2Cl2 in Hexane
1 x w 100 ml Hexane
SOLVENT PHASE
FLORISIL COLUMN CHROMAT06RAPHY
ELUTE w Hexane or ELUTE w 20% Ether
6% Ether in Hexane in Hexane
ANALYZE by GC/EC and GC/MS
AQUEOUS PHASE
pH 4 3 w 50% HCl
EXTRACT 2 x w 100 mL CHC13
CONC. & REDISSOLVE IN ACETONE
5 mL Aliquot
ADD 0.2 mL 5% K2C03
METHYLATE w 1 ml CH3I for 30 min.
EXTRACT W Hexane
ANALYZE by GC/EC and GC/MS
Figure 2. Water and Wastewater Extraction Procedure
-------
the residue weighed to determine the fat content. The fat was redissolved
in hexane and transferred to a Fieri si 1 column for clean-up by column
chromatography.
C. Sediment
Apparatus
1. Extraction assembly, Soxhlet.
2. Paper extraction thimbles.
3. Hot plate or steam bath.
The water layer over the sediment was discarded. The sediment was
allowed to partially air dry at ambient temperature in an evaporating
dish. The sample was thoroughly mixed; stones, sticks, and leaves were
discarded. The moisture content was determined by drying a separate
portion in a tared container at 103°C. Twenty to 50 grams of air-dried
sediment were mixed with an equal amount of granular anhydrous sodium
su If ate and allowed to stand for c_a_. 30 minutes with occasional stirring.
The sediment was placed in an extraction thimble and extracted for at
least 8 hours with 300 ml of 1:1 acetone-hexane in a Soxhlet apparatus.
The extract was dried by passage through a column of sodium sulfate.
The solvent was evaporated to 10 ml and the extract cleaned-up by column
chromatography.
D. Sestori^
Reagents
1. Hydrochloric acid, ACS, 1:1.
2. Chloroform, ACS, redistilled in glass.
3. Methylene chloride, ACS, redistilled in glass.
4. Sodium hydroxide, AR, 0.1 N.
5. Benzene, ACS, redistilled in glass.
.22-
-------
The entire sample was acidified with 10 ml of 1:1 hydrochloric acid and
diluted to 1 liter. The sample was extracted with two 100 ml aliquots
of chloroform except methylene chloride was used for the last series of
samples.
The resulting emulsion was mixed with two 100 ml aliquots of acetone and
the extract filtered through Whatman No. 42 filter paper. The filtered
acetone extract was combined with 500 ml of 0.1 N sodium hydroxide and
extracted with 100 ml of hexane. This extract was retained for clean-up
by column chromatography.
Twenty ml of 1:1 hydrochloric acid was added to the aqueous layer. The
layer was then extracted with 100-rat" of b&niene and evaporated to an ap-
propriate volume for' injection Into the g'as chromatograph;
E. Suspended Solids
Ten to fifty ml of wastewater were vacuum filtered through Reeve Angel
glass fiber filters (Grade 934 AH). The oven-drying techniques and
calculations followed Standard Methods (84).
F. Centrifugation
Two 800 ml samples were centrifuged at 2000 RPM for 30 minutes to demonstrate
PCS reduction by removal of solids. Both samples demonstrated ca_. 50%
reduction in PCS concentration.
CLEANUP COLUMN CHROMATOGRAPHY
-23-
-------
Reagents
1. Rorisil, pesticide reagent grade, 60-100 mesh, activated at
55QQC for 15 hours stored at 160°C.
2. 94% hexane (Skelly solve B b.p. 60-68°C redistilled in glass)/
6% ethyl ether, ACS
3. 80% hexane (skelly solve B b.p. 60-68°C redistilled in glass)/
20% ethyl ether, ACS
Equipment
1. Glass chromatography column, 350 mm by 20 mm id. with a 300
ml reservoir on top, a fritted glass disk at the bottom, and a
Teflon stopcock to control the flow.
The column was rinsed with acetone to dry the fritted disk and then
rinsed with hexane. After the stopcock was closed, the column was
filled to the base of the reservoir with hexane. One-half inch of
granular anhydrous sodium sulfate was then added followed by 25 grams of
florisil. Entrainment of air bubbles was avoided. One inch of sodium
sulfate was added to the top. Next, the concentrated sample extract
(ca_. 5 ml) was added. The stopcock was opened and the column eluted at
ca_. 5 mL/min. The sample container was rinsed twice with a small
amount of hexane and the rinses added to the column. When the solvent
reached the top sulfate layer, 200 ml of hexane was added. The solvent
was eluted again at a rate of ca. 5 mL/min. A solution of 94% hexane:
6% ether was later substituted for hexane in this method to elute more
.polar compounds in the first fraction. When the hexane (94% hexane/6%
ethyl ether) portion reached the top sulfate layer, 200 ml of 80%
-24-
-------
hexan«/20% ethyl ether was added and the collection beaker changed. The
column was then allowed to drain. When each aliquot of solvent had
passed through the column, the solvent was reduced to a suitable volume
by evaporation and analyzed by gas chromatography/electron capture
(GC/EC) and gas chromatography/mass spectrometry (GC/MS).
METHYLATION
Reagents
1. Acetone, ACS, redistilled in glass,
2. Potassium carbonate, AR.
3. Methyl iodide, Aldrich, 99%.
The acid extract was dissolved in 5 ml of acetone in a 50 ml screw-top
centrifuge tube, and 0.2 ml of 5% potassium carbonate and 0.5 ml of
methyl iodide were added. The mixture was allowed to react at room
temperature for ca_. 30 minutes. The acetone and methyl iodide were
evaporated to ca. 0.5 ml with a gentle stream of clean, dry air. One
gram of anhydrous sodium sulfate was added to remove water. The solution
containing the methylated derivatives was quantitatively transferred to
a graduated centrifuge tube and diluted with hexane to an appropriate
volume for injection into the gas chromatograph.
ANALYSIS BY GAS CHROMATOGRAPHY
Equipment
1. Gas chromatograph (Perkin Elmer model 3920 or Hewlett Packard
model 402) with electron capture dector (63^)
-25-
-------
Conditions:
Injectors: 250°C.
Columns: 200°C.
Detectors: 230° to 300°C.
2. GLC columns, glass, 1.8 m by 4 mm i.d. Packings:
6% SP-2401/4% SE 30 on Supelcoport 100/120 mesh.
10% SP-lOQQ/1% Phosphoric acid on Supelcoport 80/100 mesh.
3. Strip chart (Perkin Elmer model 690) or integrating recorder
(Hewlett Packard model 3380A)
4. Ten uL syringe.
Twenty-five to 50 mg of an Aroclor PCB mixture was dissolved in hexane
and diluted in a volumetric flask to give a concentration of 2.0 ug/mL.
Four to 8 uL of.standard was injected into the gas chromatograph to
determine the linear range of the detector. Samples were diluted as
necessary to ensure that they were in the same order of magnitude as the
standard (s).
Four to 8 uL of the sample was injected and PCB or chloro-organic
compounds were identified by retention times and/or fingerprint patterns.
Peak heights were measured and matched to the standards. The concentration
of each compound was calculated using the peak height method (strip
charts) or peak area method (integrating recorder).
Extraction and analysis methods were adapted from Hesse!berg and Johnson
(85), Thompson (86) and the U.S. EPA (87).
-26-
-------
GAS CHROMATOGRAPHY/MASS SPECTtQMETRY
GC/MS System
The identification and confirmation of compounds in this project were
accomplished using a Finnigan gas chromatograph (model 9500)/mass spec-
trometer (model STOOD) with an on-line computer data system (model 6000)
and a Zeta X-Y plotter. Electron impact mass spectra ranging from m/z
35-500 were acquired at an emission current of 0.35 mi Hiamps, electron
energy of 70 eV., amplification of 10"7 amp./Volt, and electron multiplier
setting of 2.10 kV. The GC/MS was calibrated with perf1uorotertiarybutylamine
(PC-43) whenever ions of known samples of aldrin, chloro-phenols, chloro-
anisoles,or polychlorinated biphenyls (PCBs) were not well resolved or
exhibited shifted m/z ratios as evidenced by abnormal ion abundances for
the number of chlorines present in the standards. The resolution of FC-
43 was adjusted to agree with specifications given by Carter (74).
Known compounds were analyzed daily as part of a quality assurance
program to document column efficiency and overall GC/MS system performance.
Experimental Approach
Several months were spent exploring different GC/MS conditions and
evaluating column packings that were best suited to suspected compounds
in the sample fractions. A retention index relative to aldrin was
employed to help identify and locate compounds detected by a gas chromatograph
with an EC detector (GC/EC). (See Appendix C for a relative retention
index of acid fraction compounds that were chromatographed either directly
or as methylated derivatives on Ultra-Bond 20M).
-27-
-------
GC/MS Column Selection
Glass columns were packed with 3% SE-30 on 80/100 mesh Gas Chrom 9-3%
SP-2100 on Supelcoport 100/120 mesh or physically bonded Ultra-Bond 20M
on 100/120 mesh Chromosorb W (loading ca_. 0.2% Carbowax 20M). Column
lengths were either 1.8 or 3 m x 2 mm i.d. The SE-30 and SP-2100
columns were temperature programmed from 100 to 220°C at 4°/min when
neutral extracts (hexane, 94% hexane/6% ethyl ether and 80% hexane/20%
ethyl ether) were analyzed. The Ultra-Bond 20M columns were programmed
either from 90 to 210°C (1.8 m column) or 110 to 250°C (3 m column) at
4°/min. to analyze both methylated and nonmethylated acid fractions as
well as for general purpose analyses. All column packings were obtained
from commercial sources. The injector and glass jet separator heaters
were set at cju 250°C. Helium carrier gas flow varied between 20 to 30
mL/min based on the optimum separator efficiency with a vacuum not
exceeding 6 x 10 Torr.
GC/MS Operation
The GC/MS was programmed to integrate spectra at the following times:
4 millisec (ms) from m/z 35 to 150, 8 ms from m/z 151 to 300, and 12 ms
from m/z 301 to 500, resulting in 4 second scans. Occasionally integration
times were changed to 4 ms from m/z 35 to 150, 9 ms from m/z 151 to 300
and 12 ms from m/z 301 to 350 or 400, resulting in 3-second scans. The
sample run time ranged from 10 to 35 minutes depending on the number of
peaks detected by GC/EC. The GC/MS data system displayed a Total Ion
Chromatogram (TIC) that resembled a gas chromatogram.
-28-
-------
The ions of compounds eluting at various retention times were detected
as peaks on the TIC. These peaks were investigated with the data system
to search the entire mass spectra for a specific ion or ion cluster of
each compound. The Limited Mass Reconstructed Gas Chromatogram (LMRGC)
and/or TIC were used to choose an appropriate background spectrum and to
determine isomers, closely related compounds, and compounds with similar
(.interfering) retention .times. Compounds in sample extracts were identified
by various means as described in Appendix A. One way was to compare the
retention time and mass spectrum of a suspected constituent with those
of a standard of that compound. Another way was to compare the full or
partial mass spectrum (8 most abundant ions) of a constituent with
published spectra, e^. The Eight Peak Index of Mass Spectra (78). For
several unknown compounds, mass spectra were compared with the Finnigan
GC/MS data system library of about IjOOO abbreviated spectra of pesticides,
drugs,and industrial chemicals. A mass spectrum remaining unidentified
after these processes was interpreted by the abundance or lack of an
apparent molecular ion, known fragmentation patterns, and isotopic abundances.
For instance, if the compound was chlorinated (e.g. trichlorophenol
Appendix D-19), the number of chlorines on the molecule could be noted
according to isotopic abundances. An abundant molecular ion usually
implies an aromatic compound (e.g. phenol). A small or absent molecular
ion implies at least some substitution (e.g. ethyl phenol Appendix E-
14). A compound with a strong molecular ion showing a loss of 1 m/z
suggests a labile hydrogen as seen in the spectra of vanillin (Appendix
D-23) and syringaldehyde (Appendix D-22).
-29-
-------
GC/MS/ INTERPRETIVE ANALYSIS
The sample selected for a detailed interpretive analysis here was an
acid extract of the Bergstrom Paper Company final effluent* which is
discharged into Little Lake Butte des Morts. The sample was extracted
according to the procedure outlined on page 21. This extract was first
analyzed by GC/EC and then GC/MS to determine the presence of methylated
compounds (e_.£. chloro-anisoles, chloro-veratroles, and resin acid
esters) prior to any further sample treatment. A TIC for this sample is
shown in Figure 3, No methylated compounds were found in this extract.
The extract contained small quantities of chloro-phenols and chloro-
guaiacols, along with dehydroabietic acid. However, in order to facilitate
improved gas chromatographic analysis and to detect more polar compounds
that do not elute well off a GC column, methylated derivaties were
prepared according to the procedure outlined on page 25. The TIC of
this extract after methylation is shown in Figure 4. Figure 5 shows
an expanded amplitude scale with peak identification. Upon methylation,
chloro-phenols are converted to chloro-anisoles, chloro-guaiacols become
chloro-veratroles, and dehydroabietic acid becomes methyl dehydroabietate.
The mass spectra of the various compounds identified in this sample were
compared with mass spectra obtained by injecting pure compounds into the
GC/MS system under identical operating conditions as well as mass spectra
in the literature and data system library. Mass spectra of compounds
found in this sample compared with standard spectra are included in
Appendix D in alphabetical order. Mass spectra of compounds compared
with published mass spectra are presented in Appendix E. Mass spectra
of compounds unidentified or tentatively identified are presented in
Appendix F.
-30-
-------
AMPLITUDE
U)
t-3
O
rt-
H
O
ct-
O
>
O
o .
o
o
vn
o
ro
o
o
ro
ui
o
U)
o
o
U)
v/i
o
-------
COMPOUNDS
Unidenliliod Fallv Acid Milhvl Ester
SPECTRUM NUMBER
Figure U. Total Ion Chroraatogram: Methylated Acid Extract Of A Paper Mill Effluent
1. Chioroanisole
2. 2, 4, 8 - TricWoroanisole
3. Oichloroanisole
4. Benzotniazole
5. TetraeMoroanisole
5. Nonylanisole
7. Pentachloroanisofe
8. Tetrachloroveratrole
9. Methyl thiobenzothiazote
10. Trichloroverairole
11. Trichloro-trimethoxybenzene
12. Tributyl phosphate
13. Methoxybenzothiazole
14. Methyl palmitate
15. Aldrin External standard
16. Methyl heptadecanoate
17. Methyl oleate
18. Methyl stearate
19. Methyl 8,15 - isopimardien-18-oate
20. Methyl pimarate
21. Methyl sandaracopimarate
21 a. Bisphenol a dimethyl ether
22. Unidentified R A M E* (MW 318)
23. Unidentilied R A M E (MW 316}
24. Unidentified R A M E (MW 328)
25. Methyl dehydroabietate
26. MethylS, 8,11,13-abietatetraen-18-oate
27. Unidentilied R A M E f MW 328)
28. Dichloro-bisphenol a dimethyl ether
29. Chloro-bisphenol a dimethyl ether
30. ChloroRAME(MW362)
31. Chloro-methyl dehydroabietate (A)
32. Chloro-methyl dehydroabietate (B)
33. Tetrachloro-bisphenol a dimethyl ether
34. Dioctyl phthalate
35. Trichloro-bisphenol a dimethyl ether
36. Dichloro-bisphenol a dimethyl ether
37. Dichioro-methyl dehydroabietate (MW 382)
38. Methyl oxo-dehydroabietate (MW 328)
*R A M E = Resin Acid Methyl Ester
-------
100
j
CJ
(-0
M
30 -
Column Conditions: Ultra-Bond 20M, 3m x 2mm,
temperature programmed 110-250°C @ 4°C/min. lor 35 minutes
I rr»'l i I
100 ISO 200 250
I I'!'!} i'| II I "i I r '] "i I »'l 'I'
350 4OT
SPECTRUM NUMBER
Figure 5. Total Ion Chromatogram: Methylated Acid Extract of a Paper Mill Effluent
-------
Mass spectra and LMRGCs of some of the compounds found in this methylated
extract are presented here as Figures 6 through 19. Mass spectra indicate
how molecules fragment when ionized by electrons. The LMRGC is a data
system function that helps identify a specific compound by searching for
one or more distinguishing ions in the mass spectra of a sample. These
ions could be the base peak, molecular ion and/or isotopic molecular
ions.
Peak 2 in Figure 5 is 2,4,6-trichloroanisole. Five other trichloro-
anisole isomers are also possible. This isomer is the least polar
trichloroanisole and elutes early on the Ultra-Bond 20M column. Trichloro-
anisole has a molecular weight of 210 (35C1 isotope) and with isotopic
molecular ions unique for three chlorine ions on a molecule (M+' =
100%, M+1 + 2 = 98%, M+' + 4 = 31%, M+> + 6 = 3%) as seen in Figure 6.
The LMRGC for 2,4,6-trichloroanisole is given in Figure 7. The isotope
m/z 210 was used to draw the LMRGC. Scan Number 37 (peak 2) in Figure
5 is 2,4,6-trichloroanisole. The peaks at later elution times contain
the ion m/z 210, but they have higher molecular weights.
Peak 3 in Figure 5 is an isomer of dichloroanisole. Dichloroanisole has
a molecular weight of 176 with isotopic molecular ions equivalent to two
chlorine ions on a molecule (M+- = 100%, M+- + 2 = 65%, M+> + 4 = 11%)
as seen in Figure 8.
The LMRGC in Figure 9 represents the isotope (m/z 176) of dichloro-
anisole. Scan Number 47 (peak 3) on Figure 5 is dichloroanisole.
Several other compounds also have m/z 176 in them, as noted by the later
eluting peaks, but they have much larger molecular weights.
-34-
-------
PERCENTAGE OF BASE PEAK
ON
ro
"ON
V
n
H-
n
o
o
n
H-
03
O
TO
05
ro
o
Q j?-
cnl
Q 1
cni
Q i
ro,__
QT5"
Q 1.
3
cn~1
S J
^.
N
Q
Q
o
H
cn
PERCENTAGE OF TOTAL
-------
AMPLITUDE
I
Ot)
t
-------
Q i'
cn : =
Q i =
cm-
roj
Q !-
rc !
cn~i
Q i
PERCENTAGE OF BASE PEAK
...i,,.
Q
Q
3
ON
cn
PERCENTAGE OF TOTAL
-------
AMPLITUDE
i i
**)
h*
05
(V
VO
o
§
H-
m
O
H
H
J
OS
-------
Benzothiazole is peak 1 in Figure 3 and peak 4 in Figure 5. The benzothiazole
molecule was not methylated under the conditions given. The mass spectrum
(Figure 10) for benzothiazole indicates ?.n odd-numbered molecular ion
(135). This suggests a compound with an odd number of nitrogen atoms.
The mass spectrum does not show a methyl loss (M - 15)+.
The LMR6C for the molecular ion (m/z 135) and the second most abundant
ion (m/z 108) of benzothiazole is found in Figure 11. Scan Number 50 in
Figure 11 is benzothiazole. The later eluting peaks all have higher
molecular weights.
The mass spectrum of pentachloroanisole is shown in Figure 12. The
spectrum shows the definite isotopic molecular ions for five chlorine
atoms on a molecule (M+> = 51%, M+' + 2 = 100%, M+1 + 4 = 65%, M+> + 6
= 21%, M+- + 8 = 37%). Peak Number 7 in Figure 5 is pentachloroanisole. <
The LMR6C for pentachloroanisole is provided in Figure 13. The two
most abundant isotopic molecular ions for pentachloroanisole, m/z 280
and 282, were used.
Peak 8 in Figure 5 is tetrachloroveratrole. Its mass spectrum is found
in Figure 14. The spectrum has the typical ion cluster for four chlorine
ions on a molecule (M+> = 77%, M+I + 2 = 100%, M+- + 4 = 49%, M+- + 5 =
10%) at m/z 274.-
The isotopic molecular ion m/z 274 of tetrachloroveratrole indicates
that scan Number 132 in Figures 5 and 15 is its retention time. The
later eluting peaks have higher molecular weights.
-39-
-------
N
o
PERCENTAGE OF BASE PEAK
i , . i i iii 11
Q
a
a
<8
H
O
cn"
Q
(B
N
O
CD
a
CO
o
d-
Q
o
CD
i
tn~
a
04
ff
Q
en
Q
CO
Q
PERCENTAGE OF TOTAL
-------
AMPLITUDE
1
o
oo
H
U)
-------
3
ct-
o
§
l-fc
to
o
H
ro
ta
to
ca
t3
(B
O
ci-
O
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ft
-)
§
Q
or
rc_
Q-a
Q
cn
Q
PERCENTAGE OF BASE PEAK
i i i i . iii U
a
a
o
ro
CD
ru
PERCENTAGE OF TOTAL
-------
AMPLITUDE
, i .
J*-1*
Q
Q
-------
-nn-
PERCENTAGE OF BASE PEAK
H-
OQ
-er
«
t-3
o
D*
M
O
>1
O
o
o
>-*)
TJ
(9
ft
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4
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Qt)
Q"
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Q
NJ
Q"
Q
en ]
Q !-.
s j
C3
C3
n
-------
-sn-
AMPLITUDE
-------
Peak Number 25 in Figure 5 is methyl dehydroabietate. Its mass spectrum
is illustrated in Figure 16. The spectrum shows the molecular ion, M+-,
at m/z 314. Principal fragment ions are (M - 15) + at m/z 299 and the
most abundant ion or base peak (M - 75)+ at m/z 239 corresponding to
losses of methyl (CH3) and (CH3 + HCQOCHs), respectively. The LMRGC of
its molecular ion m/z 314, in Figure 17, shows only one peak at scan
Number 299 and corresponds to peak 25 in Figure 5.
The mass spectrum of one of two isomers of methyl chlorodehydroabietate
can be seen in Figure 18. The spectrum is very similar to that of
methyl dehydroabietate except for an upward shift of m/z 34 (314 + 34 =
348). The isotopic molecular ions m/z 348 (100%) and 350 (33%) are
consistent for one chlorine atom on a molecule. Principal fragment ions
are (M - 15)+ at m/z 333 and the base peak (M - 75)+ at m/z 273 corresponding
to the same losses described for methyl dehydroabietate. The exact
positions of the chlorine atom in the molecule for the two isomers were
not easily determined. Since both spectra exhibited the same fragmentation
as methyl dehydroabietate without any discernible loss of an HC1 molecule,
Trost (80) proposed that the chlorine atom was on the aromatic ring.
These probable positions marked X on Figure 18 were those verified by
^c and ^H NMR in Thakore and Oehlschlager (63). The mass spectra and
relative retention times of these isomers were consistent with synthesized
standards furnished by Leach and Thakore (BC Research, Vancouver, British
Columbia) and previously published data (26, 63).
The LMRGC for methyl chlorodehydroabietate, using the most abundant ion
(m/z 273) in the spectrum, is found in Figure 19. The two peaks at scan
Numbers 243 and 253 both have the same molecular weight but elute at
different retention times.
-46-
-------
-in-
s
n
I
m
01
CO
tf
01
O
cf
H
t\3
I
OQ
XI 1:
Q i"
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Q 1
Q ;
Q 1
.cn i
Q
PERCENTAGE OF BASE PEAK
t | j . I I 1 ... 1
Q
Q
ro
ro
cn
PERCENTAGE OF TOTAL
-------
100
w .
H
H
^
50
100
150 200 250
SPECTRUM NUMBER
1 I f ' | 1
300
350
400
Figure 17. L^^RGC of Methyl Dehydroabietate M/Z 3lU
-------
PERCENTAGE OF BASE PEAK
I
H
CD
I
o
o>
e
o
H-
8-
01
01
tl
ro
R-
w
ro
§
H-
09
ro !
cnl-
O i-
Q
U)
u>
w
U)
Q
C3
X
U)
. *-
c»
PERCENTAGE OF TOTAL
-------
-os-
<9
H
i?
sff-
o
p
o
4
o
p^
I
PO
Q -
C3
a
en'
a
CO
T!
W
O
H
1°
1
en
C3
_
C3 .-
C3 -
AMPLITUDE
'. .-' L - i
a
a
-------
These two peaks locate the two isomers of methyl chlorodehydroabietate
present in the sample.
A base-neutral extract of another sample from the Bergstrom Paper Company
was sent to the U.S.EPA Environmental Research Laboratory in Athens,
Georgia for additional identification and confirmation. The sample was
analyzed on a 1.8 m column packed with OV-1 installed in a Varian MAT-44
&C/MS system equipped with the electron impact mode. The column was
programmed from 50° to 250°C at 8°/min. The EPA laboratory confirmed
about 15 compounds in the sample which we previously identified as aliphatic
and aromatic hydrocarbons. Two of the compounds had a molecular ion of
m/z 230. The mass spectra of these two compounds had isotopic molecular
ions for one chlorine. One compound had a molecular ion of m/z 196. It..
apparently is the precursor of the aDove compounds (Appendix F). Future
analysis by high resolution mass spectrometry at the EPA laboratory
will help in its identification.
-51-
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V. WASTE TREATMENT FACILITY DESCRIPTIONS
This section describes the pulp and paper mill and municipal waste
treatment systems discharging to the Fox River. Dischargers are listed
in downstream order. Table 2 following the treatment system descriptions
gives mean BOD, suspended solids and flow data for 1977, taken from
Wisconsin DNR NR 101 discharge reporting files.
PULP AND PAPER MILLS
Kimberly - Clark Corporation
Badger Globe and Neenah Paper Mill Divisions
Neenah, Wisconsin
The Badger Globe mill produces tissue wadding from purchased kraft pulp,
and the Neenah Paper Mill produces fine business paper from purchased
cotton sulfite pulp and produces rag pulp for its own use. An experimental
mill, which is testing a tissue-forming machine, is located at Badger
Globe. Process water is obtained from a well and from the Fox River. Fox
River water is treated by sedimentation, flocculation, sand filters, and
is chlorinated.
Process wastewaters from all mills are treated in a joint treatment
system located at the Neenah Paper Mill Division.
Wastewater from the mills and waste discharge from the influent sand
fi1ter are pumped through a traveling screen and degritter to a jet
aerated channel with 24-hour retention. Ammonia and phosphoric acid are
added in the channel. From the channel, aerated effluent flows by
gravity to the 105-foot clarifier located concentrically in the center
of the channel. The clarifier effluent is then treated in a 76-foot
po.lishing clarifier prior to discharge to the Fox River.
Preceding page blank
-------
Badger Globe
Experimental
Mill
t
Neenah Paper
Row
Degritrer
Aera tion
Channel
Figure 20, Kimberly-Clark Badger Globe & Heenah Paper Waste
Treatment System
-------
Sludge from both clarifiers is thickened in a dissolved air flotation
unit (DAF)s pumped to centrifuges for dewatering, and then hauled to a
landfill site. Centrate and excess flow from the DAF unit are returned
to the jet-aerated channel. Polymer and alum are available if needed
for coagulation and flocculation in the polishing clarifier, thickener,
and centrifuges.
Bergstrom Paper Company
Neenah, Wisconsin
Bergstrom manufactures various grades of writing papers from reclaimed
fiber and virgin pulp. The recycled material goes through a deinking
process prior to blending with virgin pulp. The combined pulp is refined
prior to sheet formation on one of three Fourdrinier machines.
Wastewaters generated in the deinking operation, paper production and
process water treatment are directed to a 120-foot diameter primary
clarifier,where chemicals are added to aid settling. The primary
effluent is directed to a Zurn-Attisholz (Z-A) two stage biological
treatment system. Waste-activated sludge is sent from the first storage
aeration tank to an air flotation unit. The concentrated waste sludge
is then pumped to the vacuum filter facility for dewatering prior to
being hauled to the company landfill site. The air flotation effluent
is returned to the first-stage aeration tank, and nutrients for the Z-A
system are added to this stream. The Z-A system effluent is discharged
through a parshall flume with a totalizer to Little Lake Butte des
Morts. A refrigerated, flow proportional, automatic sampler is used by
the mill to collect effluent samples.
-55-
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Primary Ciarifier
Bar
Screei
Paper Mill Wastes
Deinking Wastes
tUmei
X v EH
2=^W* FIH^y -*.-<-
w ^T^
*
Landfm.^ 1 pj|ter pren
Or
Filtrate
Acid, yX^ ^"V
Polymer /\ /\
i / N^X \
V/iV
xxj^-ixr
Y"
1 j >
1 Flotation I ^
Thickener I X
.Sludge % ^b __ _ \
Settling Aeration J Settling Aeration |
Tank 2 Tank 2 A* Tank 1 Tank 1 ^
Final Effluent >, . x
To Little Lake Butte des Morts
1 J
-< - ^
1 , .!; ,._ />
s
s
,-v Combined
i) Raw Effluent
^) Primary Eff luc
[|) Final Effluent
Figure 21, Bergstrom Paper Mill Waste Treatment System
-------
For this study the mill's raw effluent, primary effluent, and final
effluent were sampled as indicated on Figure 21.
Kimberly-Clark Corporation
Lakeview Mill
Neenah, Wisconsin
Kimberly-Clark Corporation (Lakeview Mill) manufactures sanitary
tissue products from a furnish of 2/3 purchased virgin pulp and about
1/3 high-grade secondary fiber. Hydrapulpers are used to supply.furnish
to the five paper machines. Disk and drum savealls as well as OSM.
« '' ' \,
screens are used to reclaim fiber from white water.prior to discharge to
the waste treatment system. Process water is obtained from Little Lake
Butte des Morts and from wells located on company property. Process water is
clarified and chlorinated prior to use in the mill.
Process wastewaters are directed to a 125-foot clarifier. Additional
inputs to the clarifier include sludges from the intake water treatment
plant, raw water screen rejects, and centrate from the sludge presses
and centrifuges. De-watered sludge is then hauled to a landfill site.
A portion of the clarified effluent is returned to the mill for reuse
and excess waste is discharged to Little Lake Butte des Morts.
Raw and final effluent samples were collected.
George A. Whiting Paper Company
Menasha, Wisconsin
The George Whiting Company manufactures approximately 20 tons per day of
fine specialty paper from purchased kraft pulp on one paper machine.
Process water is obtained from the City of Menasha.
-57-
-------
Saveall overflows, boiler blowdown, and floor drainage are collected
and pumped to a primary clarifier. The primary clarifier effluent is
discharged to the Menasha Channel of the Fox River. Sludge from the
clarifier is drawn off to a holding tank followed by polymer addition
and dewatering on a centrifuge. Solids are hauled to a landfill site
and centrate is returned to the clarifer.
Samples were obtained from the raw and final wastewater streams.
Wisconsin Tissue Mill
Menasha, Wisconsin
Wisconsin Tissue Mill produces napkins, placemats, table covers, and tray
covers from purchased virgin pulp and reclaimed fiber. The recycled
stock is deinked, before it is blended with virgin pulp and is refined
prior to formation of a sheet on one of two Fourdrinier machines.
Wastewater generated during deinking, pulp preparation,, and paper production
is directed through a mechanically cleaned bar screen and grit chamber
before entering the 70-foot primary clarifier. Polymers and bentonite
are added to the wastewater prior to discharge to the primary clarifier
for coagulation. Primary clarifier effluent is pumped to a Zurn-Attosholz
(Z-A) two-stage activated sludge secondary treatment system after addition
of phosphoric acid. The secondary treatment effluent is directed to a
52-foot storage reservoir from which a portion of the final effluent is
reused by the mill and excess flow is discharged to the Fox River.
-58-
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Solids removed by the primary and secondary treatment systems are directed
to a 52-foot gravity thickener where chlorine is added to retard decomposition
and prevent odor problems. The thickened sludge is dewatered, after
polymer addition, on two centrifuges. The dewatered sludge is hauled to
a sanitary landfill. Centrate and thickener overflow are returned to
the influent wet well.
For this study samples were collected of the raw, primary, and final
effluents as indicated on Figure 22.
Riverside Paper ' ....-
Appleton, Wisconsin
Riverside Paper manufactures book, bond, and construction paper from
deinked and purchased virgin pulp. Approximately 75 percent of the
paper is made from secondary fibers, a major portion of which come from
papers having wax coatings. The wax is removed in a trichlorethylene
solvent extraction process prior to the normal deinking operation. Spent
solvent is directed to a still and condenser to remove wax and polyethylene.
The secondary fiber is then screened, thickened, and bleached prior to
use in the mill. Process water is obtained from the Fox River and is
treated with alum and chlorine. Water treatment plant sludge is discharged
to the Appleton municipal sanitary sewer.
The two paper machines in the mill are equipped with savealls to recycle
fiber back into the process. Clear water from the savealls is discharged
to the Fox River. Wastewater from the deinking process and other sources
is discharged to the municipal sanitary sewer.
-59-
-------
{Deinking)
Paper Mill
I
OS
o
Wet Well
Combined Raw
Effluent
Primary Effluent
Final Effluent
Figure 22. Wisconsin Tissue Mill Waste Treatment System
-------
For this study a sample was collected from the discharge to the Fox
River.
Consolidated Papers, Incorporated
Appleton, Wisconsin
Consolidated Papers, .Incorporated at Appleton produces an annual average
of 189 tons a day of bleached sulfite pulp from purchased wood chips.
Chlorine is the principal bleaching agent. Calcium bisulfite cooking
acid is produced on site. The pulp is produced in nine digesters with
the cooking acid. This process is followed by screening, fractioning,
washing, bleaching, and further washing prior to sheet formation on a
vacuum cylinder machine. Lap [wet sheet) pulp is the final product from
the mill. Spent sulfite liquor is evaporated and processed into "spray "
dried products at a plant adjacent to the mill.
Process water is obtained from the Fox River and is treated in an accelerator
with additions of alum, chlorine, and polymers. The main mill sewer
carries wastes from floor drains, accelerator sludge, evaporator plant
condensate, bleach plant washwater, and other mill wastewaters and discharges
to the Fox River. There was no external waste treatment during the
investigation.
Samples were collected from the intake water and from the process waste
final effluent.
Midtec Paper Corporation
Kimberly, Wisconsin
Midtec Paper Corporation manufactures groundwood pulp and coated fine
paper from groundwood and purchased bleached kraft pulp. Five Fourdrinier
-61-
-------
paper machines and an off-machine coater are used for paper production.
The majority of process water is obtained from the Fox River and treated
either in a sedimentation basin plus sand filters or in an accelerator.
Incoming water is chlorinated and process water is occasionally chlorinated
for slime control. At the time of the survey,the company operated a
primary wastewater treatment system consisting of primary clarification,
sludge thickening, sludge centrifuging,and land disposal. Mill effluent
was pumped to a grit chamber where grit, screenings, and trash were
dewatered and conveyed to a container for disposal as solid waste. From
the grit chamber waste flowed to two 135-foot primary clarifiers.
Clarified effluent was discharged to the Fox River and sludge was pumped
to a 65-foot sludge thickener. Sludge from the thickener flowed to two
centrifuges,where it was dewatered and hauled to a landfill site.
Centrate was returned to the grit chamber.
The system was upgraded in December, 1977 by the addition of a jet
aeration system ahead of the clarifier for biological oxidation. A
third centrifuge has also been added to increase dewatering capacity.
Samples were collected from the raw mill effluent and final effluent
discharged to the Fox River. Sample locations are indicated on Figure
23.
NCR Appleton Papers
Combi ned Locks, Wisconsin
Appleton Papers manufactures NCR and telephone directory paper from
blends of purchased and chemi-mechanical manufactured pulp, and secondary
fibers. A portion of the pulp is bleached with hydrogen peroxide prior
-62-
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Primary Clarifier 1
a\
to
Raw Wastes
Coarse Screen
Grit Chamber
Centrate
Outfall To River
Raw Wastes
Final Effluent
Sludge Hauled To Landfill
Figure 23. Midtec Paper Corp. Waste Treatment System
-------
to use on one of the paper machines. Spent liquor from the chemi-
mechanical pulping process is discharged to an incineration system
(copeland process) that consists of liquor and concentrated liquor
holding tanks, evaporator, fluidized bed reactor, and scrubber. Process
wastewaters are collected and passed through a rough screening facility
prior to being pumped, along with effluent from the copeland facility,
to two 80-foot diameter primary clarifiers operating in parallel.
Solids are dewatered on two vacuum filters, after which they are hauled
to the company landfill site. Filtrate is returned to the clarifier.
Effluent from the twin clarifiers is pumped to an oxygen reactor system
(Unox) for final treatment. High purity oxygen flows into the three-
stage aeration tank along with primary treatment effluent. The tank is
covered to retain gaseous oxygen and maintain positive pressure to
ensure forward flow to the tank and avoid back-mixing from stage to
stage. Nutrients are fed-to the influent, in the form of ammonia and
phosphoric acid.
From the reactor, flow is to the clarifier, from which sludge flows to a
vacuum filter for dewatering and clarified effluent is discharged to
the Fox River. Effluent from the vacuum filter is returned to the Unox
reactor influent.
Samples were collected from the raw effluent, primary effluent, and final
effluent to the Fox River. Sampling points are illustrated on Figure
24.
GPO B»l-*«»-«
-64-
-------
Wet Well
o\
Mill Effluent
Liquor
(?) Combined Raw Waste
(D Primary Effluent
(3) Final Effluent
Unox System
To River
Pellets Hauled
For Recycling
^
Sludjfe
H'
Landfills
Figure 2*J. NCR, Appleton Paper Division Waste Treatment System
-------
Thilmany
Kaukauna. Wisconsin
The Thllmany Pulp and Paper Company produces about 431 tons a day of
.unbleached
-------
Paper Mill Effluent
ON
1
Pulp Mill Effluent
Primary Ctarifier
Aerated Lagoon
Lagoon
To River
fj) Raw Paper Mill Effluent
m Final Combined Effluent
Figure 25. TMlmany Pulp & Paper Waste Treatment System
(before May i6, 1977)
-------
took place prior to final discharge. The automatic sampler was not
refrigerated or flow proportional.
Samples of raw paper mill waste and final effluent were collected from
this system as shown on Figure 25.
The present treatment system is shown on Figure 26. Expansion of the
effluent treatment facility consisted of a nutrient feed system, UNOX
oxygen dissolution system complete with oxygen generator, liquid oxygen
storage, and secondary clarification. Proportional refrigerated samplers
are located to collect samples of the main mill sewer, pulp mill effluent,
combined effluents with nutrients before the UNOX system, and the final
clarifier effluent line.
During normal operation, paper mill waste flows by gravity through a bar
screen and Is then pumped to a primary clarifier for removal of suspended
solids. Solids are dewatered by a pressure filter and are disposed of at a
landfill. Clarified effluent flows by gravity to the UNOX reactor after
being combined with aerated lagoon effluent and nutrients.
Pulp mill waste, after ammonia and phosphoric acid nutrients are added,
flows through a -bar rack and is raised to the aerated lagoon. Up to
nine floating aerators, located in the approximate 10-day detention
lagoon aid removal of biodegradable materials. Pumps raise the aerated
lagoon effluents for transfer to the UNOX reactor after being combined
with the primary clarifier effluent and nutrients.
The combined primary clarifier and aerated lagoon effluents, together
with sufficient recycled biological solids to maintain a mixed liquor
suspended solids (MLSS) concentration of about 4,800 mg/U are introduced
-68-
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Primary Clarrfier
ON
VO
Effluent
Pulp Mill
Effluent
_i _ _JS- ^^92
Aerated Lagoon
0 Raw Paper Mill Effluent
(|) Pulp Mill After Aerated Lagoon
(3) Final Effluent
Unox Oxygen
Reactor Basin
To River
Landfill
Figure 26, Thilmany Pulp & Paper Waste Treatment System
(after May l6, 1977)
-------
into the first stage of the UNOX reactor. Sufficient oxygen C90 percent
purity) to satisfy the BOD is also introduced into the first stage. The
oxygen is supplied by a 14-ton 2-day oxygen generating system. Surface
aerators assure mass transfer of oxygen and adequate mixing in the first
and subsequent stages. The liquid and active solids remain in the UNOX
reactor for about 45 minutes and then flow to the secondary clarifiers.
A flow distributor ahead of the secondary clarifier divides the UNOX
reactor effluent flow equally between the two secondary clarifiers. The
biological solids present in the influent stream settle to the bottom of
the clarifiers. Sufficient biological solids are recycled to the UNOX
reactor to assure proper MLSS concentrations, with the excess being
combined with the primary solids in the sludge tanks. These solids are
dewatered and hauled to a landfill. The secondary clarifier-treated
effluent flows to the second lagoon (about 1.5 days retention time)
"prior to discharge to"the Fox River.
Samples from the new system were collected from the mill raw, aerated
lagoon, and final effluents. Sampling locations are shown on Figure 26.
Nicolet Paper Company
De Pere,Wisconsin
The Nicolet Paper Company manufactures glassine and grease-proof specialty
paper from purchased kraft and sulfite pulp. After repulping and
refining., the sheet is formed on one of four Fourdrinier paper machines.
All paper machines are equipped with flotation savealls. Process water
is obtained from the Fox River.
-70-
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Settling Lagoon
H
I
Boiler Slowdown \
Water and Wastes '
^
^
"^lillt
\
S
To River
Paper Mill Effluent,
I Raw Effluent
\ Final Effluent
Cenlrate
To Landfill
Figure 27. Nicolet Paper Co. Waste Treatment System
-------
Process wastewaters from the papermaking operation and all of the
sludge generated in the water treatment plant are directed to the waste
treatment plant through a 14-inch force main. Each of the three lift
stations in the mill is equipped with an emergency overflow to the Fox
River. During sample collections no discharges occurred from these
overflows, but they are used occasionally.
The waste treatment plant consists of two 56-foot diameter clarifiers
and sludge dewatering centrifuges. Flow through the clarifiers is
measured by means of a magnetic flow meter and is recorded on an integrator
totalizer. A refrigerated automatic sampler collects samples of clarifier
effluent proportional to flow. Clarified effluent is discharged to the
Fox River.
Sludge from the two clarifiers is dewatered to approximately 15 percent
solids in one of two centrifuges. The cake is disposed of by a private
contractor, and centrate is returned to the clarifier.
Boiler blowdown and some cooling water are discharged to a settling
lagoon adjacent to the treatment plant.
Samples were collected of the raw effluent from the mill, and final
effluent from the treatment system as indicated on Figure 27.
Fort Howard Paper Company
Green Bay, Wisconsin
Fort Howard Paper Company manufactures various tissue products from
reclaimed secondary fiber and purchased virgin pulp. The reclaimed
fiber is washed, bleached, combined with virgin pulp, and refined prior
-72-
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to sheet formation on one of the company's nine paper machines. Process
water is obtained from the Fox River and is clarified and chlorinated
prior to use.
The wastewater treatment system is composed of a primary clarifier for
paper mill wastes, settling and aeration lagoons, and secondary
clarifier for deinking wastes. Deinking wastes are directed to one or
two of the five settling lagoons for solids separation. The remaining
lagoons are at some stage of dewatering. The lagoons are operated on a
rotation basis,and a lagoon completes its cycle in 4 to 6 weeks.
.Settling lagoon effluent then flows into three mechanically aerated
basins. Nutrient addition to the mixed liquor is accomplished by
adding ammonia to the aeration basin influent and phosphoric acid to the
return activated sludge. Effluent from the aeration...basins flows to the
180-foot deinking final clarifier. Final clarifier effluent is then
combined with effluent from the 180-foot mill clarifier and discharged
to the Fox River.
Sludge from the mill and deinking clarifiers is pumped to conditioning
tanks,where lime and calcium hypochlorite are introduced. The combined
sludges are then directed to the settling lagoons and are ultimately
removed to a landfill site.
Samples were collected only from Fort Howard's final effluent.
The treatment system and sampling location are indicated on Figure 28.
-73-
-------
Paper IVIiU Effluent
l£L,-i!an
^
tion j
H < I
Stabiliz
>
f ' If
t
4-
160'
X
510'
4-
Settling LagoonsJ
Two In Use At One Time
Other Three Allowed To
Sludge Removal To Landfjlt
^ J * J
4-
For
~
Waste Sludge
138'
X
438'
"n r*i
Aeration Lagoons
L^
.
Recycle Sludge V"~
Nutrients
0 Final Effluent
Figure 28. Fort Howard Paper Go. Waste Treatment System
-------
American Can Company
Green Bay, Wisconsin
American Can manufactures tissue products from calcium-base sulphite
pulp and purchased pulp. Cooking acid is produced on site and is supplied
to four digesters, along with chips and steam. Following digestion the
pulp is bleached and refined prior to sheet formation on one of six
paper machines. Process water is obtained from the Fox River and is
clarified and chlorinated prior to use.
Excess paper machine Whitewater, water treatment sludges, and boiler
house wastewaters are directed to one of three lagoons. One lagoon is "
always in use while the others are being dewatered for solids removal ,to
a landfill site. Effluent from the lagoons is discharged to the Fox
River.
Other wastesconsisting of spent sulphite liquor, solids rejects, and
bleach liquor making, spray drying, and digester area lossesare directed
to the Green Bay Metropolitan Sewerage District.
Samples were collected of the raw effluent discharged to the lagoons and
the final effluent from the lagoons, which is discharged to the Fox River.
Proctor & Gamble Paper Products
Green Bay, Wisconsin '
Proctor & Gamble Paper Products manufactures various tissue products
from ammonia-base sulphite pulp and purchased pulp. Pulp and paper
production averages about 1,000 tons a day. Cooking acid is produced on
-75-
-------
site and Is supplied to the dtgesters, along with chips and steam. Follow-
ing digestion the pulp is cleaned, bleached, and refined prior to sheet
formation. Process water is obtained from the Fox River and is clarified
and chlorinated prior to use.
Sludge from the process water clarifier is thickened in an air floatation
unit, mixed with particulate scrubber solids, and centrifuged prior to
disposal by a private contractor. Excess Whitewater and final effluent
are discharged to the Fox River. Other wastewater, consisting of Whitewater
and losses from the pulp mill and paper machines, is directed to the Green
Bay Metropolitan Sewerage District.
Samples were collected from the final effluent discharged to the Green Bay
sewage district and from the process water intake.
Green Bay Packaging
Green , Jay, _.
Green Bay Packaging produces about 300 tons a day of corrugating medium
from neutral sulfite semichemical pulp-, and repulped waste corrugated
boxes and clippings. Process water is obtained from Green Bay and the
Fox River.
The mill operates with an essentially closed Whitewater system. Excess
water is removed from the system by a reverse osmosis (RO) plant.
Wastes from the Whitewater system are fed to the RO unit and are separated
into uncontaminated water Cperroeate) and a concentrate of Whitewater
solubles, which is returned to the countercurrent washing system in the
pulp mill. Feed to the RO plant contains 4 to 6 percent dissolved solids
-76-
-------
consisting of wood extractives and sodium lignosulfonates. After passage
through the RO unit, a portion of the concentrate is returned to the pulp
mill and the remainder is recycled for combining with fresh feed. Permeate
is discharged to the Fox River. Figure 29 is a schematic of the treatment
system including the sample location.
-77-
-------
CO
Feed
Mill Sewers
Reverse Osmosis
\/
Permeate
/
Concentrate To
Pulp Mill
->
Mill Effluent
To River
k 1) Final Effluent
Figure 29. Green Bay Packaging Waste Treatment System
. 4
k 4
-------
SEWAGE TREATMENT PLANTS
Neenah-Menasha Sewerage Commission
Menasha, Wisconsin
The Neenah-Menasha Sewerage Commission operates an activated sludge
type sewage treatment plant serving a population of about 39,000 people.
The plant consists of three 75-foot primary clarifiers, two aeration
channels, and two 120-foot secondary clarifiers. Raw wastewater enters
the system through a barscreen and wet well and then flows to the primary
clarifiers, which receive a portion of the activated sludge from the
final clarifiers. Primary clarifier effluent flows to the duel "aeration
channelss which also receive activated sludge. Aeration channel effluent
flows to the two final clarifiers. Effluent from the final clarifiers
is then chlorinated before discharge to the lower end of the North
Menasha channel at the head of Little Lake Butte des Morts.
Excess activated sludge and primary clarifier sludge is pumped to a
holding tank, flotations and vacuum filter system. Filtrate is returned
to the raw influent and filter cake is incinerated. Figure 30 is a
diagram of the treatment facility and sampling locations.
Town of Menasha Sanitary District (East)
Menasha, Wisconsin
The Town of Menasha, East Side Sewage Treatment Plant utilizes dual
activated sludge contact stabilization tanks for secondary treatment.
The plant serves a population of about 6,500 and consists of a comminutor,
contact aeration, settling basins reaeration, and aerobic digestion in
twin units followed by chlorination. Sludge is hauled to a landfill or
-79-
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Raw By-Pass
do
O
Primary By-Pass
Aeration
Ae ration
I
^
Activated . Sludge
}
I Wet Well
I £,
Sludge
Flotation Holding Tank
Figttre 30. Heenah-Menasha Sewage Treatment System
-------
farm fields in the area. Effluent is discharged to Little Lake Butte
des Morts.
Town of Menasha, Sanitary District No. 4 (West)
Neenah. Wisconsin
The existing sewage treatment plant utilizes contact stabilization
for secondary treatment. The plant consists of a comminutor, lift
station, contact aeration, settling basin, reaeration, aerobic digestion,,
and chlorination. The plant discharges to Little Lake Butte des Morts.,,
and a compliance monitoring survey conducted in May, 1977 indicates the
plant operates efficiently under normal flow. The plant had a high
chlorine residual when surveyed.
Butte des Morts Utility District
Appleton. Wisconsin
The Butte des Morts Utility District Sewage Treatment Plant consists of
a bamnnutor, contact stabilization activated sludge unit, and clarifier.
Effluent from the clarifier is chlorinated prior to discharge to Mud
Creek a short distance from its junction with the Fox River. Liquid
alum is added near the clarifier inlet for phosphorus removal. Digester
sludge flows to a lagoon and is hauled from there to a landfill or to
agricultural fields in the area. Major industries discharging to the
plant include Rich Products (bakery grease) and Fox Operations (painting
waste). Final effluent samples were collected.
-81-
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Appleton Sewage Treatment Plant
Appleton, Wisconsin
The City of Appleton operates an activated sludge-type sewage treatment
plant that was placed in operation in 1964. During this survey the
plant was in process of expansion. The facility serves a population of
about 58,000, and the following significant industries discharge to the
facility: Fox River Paper Company, Riverside Paper Company, NCR Appleton
Papers, Appleton Mills, Stokely Van Camp, Consolidated Badger Co-op, and
Foremost Food.
The treatment plant consists of the following: solids grinding and
degritting, four primary clarifiers, four aeration basins with installed
piping for various operational modes, two final clarifiers, and chlorine
contact tank for effluent disinfection prior to discharge to the Fox
River, About 400 Ibs a day of chlorine is used for disinfection of final
effluent and about 300 Ibs a day is used on outfall 002, which discharges'
primary effluent. Solids collected from the primary and final clarifiers
are anaerobically digested prior to dewatering by vacuum filtration.
Dewatered solids are hauled to a landfill site.
Phosphorus removal is achieved by precipitation, using ferric chloride
added as a conditioner in the sludge dewatering process. Additional
amounts of ferric chloride are added at the plant intake and aeration
basin effluent. In addition, polymer is added to the raw sewage to aid
in primary clarifier settling. Figure 31 is a diagram of the facility
and sampling locations.
-82-
-------
I
Co
U)
Primary Clari
Primary
Aeration
Raw
Grit Chamber
Return Sludge
Sludge
Digestion
Tanks
Vlandfill
Secondary
Clarifier
Chlorination
Final
-0 - ^
To
Figure 31. Appleton Sewage Treatment Plant
-------
Kimberly Sewage Treatment Plant
Ktmberly, Wisconsin
The Kimberly Sewage Treatment Plant ceased operation when connection
with the Heart of the Valley Sewage Treatment Plant was completed. The
Kimberly STP was in operation at the time of this study and consisted o1
preaeration and grit removal, primary clarifier, two aeration basins,
two final clarifiers, and chlorination prior to discharge directly to
the Fox River. Phosphorus removal was accomplished by addition of
liquid alum to the primary clarifier effluent. The plant served a
population of about 6,500. One final effluent sample was taken.
Little Chute Sewage Treatment Plant
Village of Little Chute, Wisconsin
The sewage treatment plant consisted of the following units: comminutor,
two mechanical sewage lifts, preaeration basin with mechanical aeration
and grit removal, two circular activated sludge systems operated in
Parshall tank configuration with the contact, reaeration and digestion
zones outside, and the clarifier inside. Aerobically digested sludge
was pumped to a holding tank prior to disposal. Disinfection occurred in
the final clarifier effluent. Liquid alum was added to the clarifier
influent for phosphorus removal.
Supernatant from the sludge holding tank was drawn off and rerouted
through the plant. When clear supernatant could no longer be drawn, the
liquid sludge was hauled by tank truck to a farm field near Little
Chute.
This facility is scheduled for dismantling after connection to the Heart
of the Valley Sewage Teatment Plant. One final effluent sample was
taken.
-84-
-------
Heart of the Valley Metro Sewerage District (HVMSD)
(Kaukauna, and Combined Locks)
Kaukauna, Wisconsin _____
The HVMSD (Kaukauna) Sewage Treatment Plant serves the City of Kaukauna,
Kimberly, Little Chute,and the Village of Combined Locksa total domestic
population of about 21,000 and several minor industrial contributors.
Only the City of Kaukauna and Village of Combined Locks were serviced by
this facility during the investigation.
At the time of the survey the treatment plant consisted of a bar screen,
barminutor, two primary clarifiers, three aeration tanks, two~'final
clarifiers, chlorine contact tank, sludge degritter, gravity sludge
thickener, two anaerobic sludge digesters, and two sludge lagoons;*- "'
About 40 pounds of chlorine were utilized daily for the disinfection of
the plant effluent. The chlorine feed rate was manually regulated, based
on residual chlorine readings.
The two sludge digesters were operated in series. The digested sludge
from the secondary digester was normally hauled by truck to agricultural
land for ultimate disposal. The two lagoons were utilized when the
liquid sludge could not be hauled.
The final discharge point is located underwater in the Fox River. A
total plant bypass is located ahead of the plant and discharges through
a separate outfall. This bypass is only utilized in the event of a
power outage. Raw and final effluent samples were taken.
-85-
-------
Wrightstown Sewage Treatment Plant
Greenleaf, Wisconsin
The Wrightstown Sanitary District operates an extended aeration sewage
treatment facility followed by a polishing pond. Raw sewage flows
directly to the aeration basin and from there to the clarifier. Effluent
from the clarifier is chlorinated prior to entering a polishing/detention
pond. Activated sludge is returned to the aeration basin, and waste
sludge from the aeration basin and clarifier is pumped to a sludge
holding tank when necessary. Supernatant from the sludge holding tank
is returned to the system and waste sludge is hauled away.
Effluent from the detention pond flows to a ditch that leads to the
East River,which flows several miles before entering the Fox River.
This plant would be expected to have only minimal impact on the Lower
Fox River or Green Bay. One final effluent sample was taken.
DePere Sewage Treatment Plant
DePere.,, Wisconsin ._
The DePere Sewage Treatment Plant serves a population of about 30,000
people. Significant industrial dischargers i'nclude Morning Glory Dairy
and Armour & Company.located in the town of Ashwaubenon, and U.S. Paper
Mills of DePere.
Wastewater treatment consists of degritting and primary clarification
followed by conventional activated sludge and final clarification.
Clarified effluent is chlorinated prior to discharge to the Fox River.
Waste-activated sludge,along with primary sludge, is thickened prior to
being further treated in anaerobic digesters. Return activated sludge
-86-
-------
Sludge
Co
-a
L
Wet Well
Grit Chamber
Figure 32. DePere Sewage Treatment System
-------
1s preaerated. Alum 1s added to the aeration tank effluent for phosphorus
removal. A private contractor hauls the digested sludge to a lagoon
south of DePere. Figure 32 is a diagram of the plant and sampling
locations.
Green Bay Metropolitan Sewerage District (GBMSD)
Sreen Bay, Wisconsin
Joint treatment of the wastewaters from American Can Company and Proctor
& Gamble Paper Products is provided through a tripartite agreement
between the GBMSD, the City of Green Bay, and the two industries. Other
significant dischargers include the following: Reimer Meat Products; Ultra
Plating; Gardner Denver; Chicago & Northwestern Transportation Company;
Packerland Packing Company; Green Bay Soap Company; L.D. Schreiber Cheese
Company, Incorporated; Green Bay Food Company; Green Bay Canning Company;
The Larsen Company; Pauly Cheese Company; Fairmont Foods Company; Food
Machine Corporation; Green Bay Drop Forge; Sure Way Supermarkets No.'s 5
& 6; Gold Bond Ice Cream; Diana Manufacturing Company; Fort Howard Steel
& Wire Company; Model-Royal Cleaners & Launders; F. Hurl but Company;
Mrs. Karl's Bakery; and Lov-It Creamery, Incorporated.
Wastewater treatment consists of screening and degritting raw metro wastes,
followed by primary clarification. Clarified metro wastes are then combined
with the paper mill wastes and discharged to aeration tanks for treatment in
the contact-stabilization mode of the activated sludge process. Wastewater
then flows to final clarifiers and a chlorine contact tank prior to being
discharged to the Fox River/Green Bay.
-88-
-------
Phosphorous removal is accomplished by the addition of alum to primary
clarifier influents.
Solids handling facilities consist of gravity thickeners, dissolved air
flotation thickeners, sludge holding tanks, heat treatment (Zimpro wet
air oxidation) units, decant tanks, equalization tanks, grease concentrators,
vacuum filters, and multiple hearth incinerators. Effluent from these
units is returned to the raw sewage wet well, and effluent from the air
flotation units is returned to the primary clarifier effluent along with
return activated sludge.
Sludge produced in the treatment process is incinerated and the ash is
hauled to a landfill site. Figure 33 is a schematic of the treatment
facility and indicates sampling locations.
-89-
-------
I
?
Figure 33. Green Bay Metropolitan Sewerage District
R iver
-------
Table 2. Average Flow, BOD and Suspended Solids Discharged to the Fox River.
Discharger Discharge Period
Kimberly-Clark
Corp. Badger
Globe & Neenah
Bergstrom Paper Co.
Kimberly-Clark,
Lake View
George Whiting
Wisconsin Tissue
Riverside Paper
Consolidated
Appleton
Midtec Paper
NCR Appleton Papers
Thilmany
Nicolet Paper Co.
Fort Howard Paper.
Company
American Can Company
Proctor & Gamble
Green Bay Packaging
Neenah-Menasha STP
Town of Menasha,
East
Town of Menasha,
West
Butte des Morts
Utility District
Appleton STP
Kimberly STP
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
1977
11/76-09/77
10/76-09/77
10/76-09/77
02/77-09/77
10/76-09/77
10/76-09/77
Flow
MGD
3.96
3.723
0.903
0.273
1.711
0.734
1.181
7.358
4.497
22.8
2.435
18.21
3.65
5.031
0.96
8.77
0.56
0.55
0.74
10.17
0.43
BOD Suspended Solids
mg/L Ibs/day mg/L Ibs/day
7.7
191.5
50
88
11.9
84
1520
98
79
32.5
19.1
i
29.3
18
41
45
12.85
23.78
12.84
49.1
67.27
24.16
255
8528
1090
201
170
450
14973
7278
4131
6192
646
4450
1016
1925
607
940
111
59
303
5706
87
13.6
304.4
13
58
16.5
138
88
135
57
.48.5
20
33.4
Not
76.4
8
26.02
17.92
12.06
94.4
88.25
30.16
450
13556
317
143
235
480
867
10082
2970
9219
675
5080
Available
3565
102
1903
84
55
583
7485
108
-91-
-------
Table 2. Continued
Little Chute STP 10/76-09/77 0.57 33.89 161 15.84 * 75
Heart of the Valley 02/77-09/77 1.9 9.75 154 12.55 199
Wrightstown STP 11/76-09/77 0.113 83.6 79 61.0 57
DePere STP 10/76-09/77 2.05 71.3 1219 38.5 658
Green Bay Metro
Sewerage District 01/77-09/77 10.28 18.23 1563 26.7 2289
-92-
-------
VI. RESULTS AND DISCUSSION «
PULP/PAPER MILL AND SEWAGE TREATMENT PLANT EFFLUENTS
The results of GC/EC analyses and suspended solids measurements of
wastewaters are presented in Table 3. The sampling location within the
various facilities is indicated on the treatment system figures described
previously in the wastewater treatment facility section. The detection
limit for PCBs and pentachloroanisole was 0.2 ug,/L and 0.1 ug/L, respectively.
The.detection limit for the chloro-phenols and chloro-guaiacols depends
o,n GH column conditions and whether and acid fraction was methylated
before injection. When thfe project began, adequate hood space to safely'
methylate this fraction was not available. Until'that time, the' acid"
fraction was directly injected onto the SP-1000 acid-treated column in
the GC/EC, resulting in less sensitivity (ca_. limit of 10 ug/L for PCP).
Another problem with the analysis of chloro-phenols and chloro-guaiacols
concerned their degradation in solution in bright light. Their degradation
was minimized by methylation.
Polychlorinated biphenyls were Detected in the discharge of 12 of the 26
facilities sampled. Arochlor 1242 was the predominant mixture detected.
However, other mixtures (Arochlor 1248 and 1254) were occasionally
detected,as noted in Table 3. Concentrations of PCBs ranged from the
limit of detectability (0.2 ug/L) to 8,200 ug/L in one sample from the
grit chamber wet well of Wisconsin Tissue Mill. The data in Table 3
indicate significant PCB concentrations are associated with mills using
recycled fiber in their process. The data also indicates that PCBs are
associated with suspended solids and efficient solids removal also
-93-
-------
Table 3. Pulp and Paper Mill, and SewageTreatment Plant Effluents -Quantified Results
Chloro-organics (ug/L)
Pulp and Paper Mills
1. Kimberly Clark - Badger
Globe, Joint Treatment
2. Bergstrom Paper Company
__o
_£.
4. Kimberly Clark Lake View
5. George Whiting Paper Co.
Date
11/30/76
2/28/77
2/28/77
2/28/77
7/19/77
11/30/76
1/26/77
1/26/77
2/28/77
2/28/77
3/02/77
3/02/77
3/02/77
7/18/77
7/19/77
8/09/77
11/30/76
2/28/77
3/24/77
3/24/77
7/19/77
11/30/76
7/19/77
7/19/77
Samp! e
Source
Final
Raw
Primary
Final
Final
Final
Raw
Final
Raw
Final
Raw
Primary
Final
Raw
Final
Final
Final
Final
Raw
Final
Final
Final
Raw
Final
Sampl e
Type
grab
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
6 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
grab
4 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
24 hr. comp.
4 hr. comp.
grab
24 hr. comp.
Suspended
Solids
(mg/l)
144
40
26
5
-
-
-
2840
540
-
-
-
2580
195
148
-
40
660
13
18
-
48
46
Pentachloro- Pentachloro-
phenol anisole Others**
PCB* (PCP) (PCA) by GC
<0.2 <1 0.07
<0.2 <10 <0.05
<0.2 <10 0 .12 4CP 2.2
0.3 - 0.14
<0.2 <0.1 0.05
9.5 10 4CG 14, 3CG 12,
x DHA 3200
79 - x
69 <1 0 x
80 1 - 4CG 6
29 x
56 < 1
<10 < 5 <0.1 3CG 10.5.
25 <1 0 x
16
0.2 <10 <0.1
0.15 - <0.1
19.0 <10
1.2 <20 <0.1
<0.3 <0.1 <0.1 3CP< 0.1
<0.2 <0.1
<0.2 <1.0 0.04
<0.2 0.35 <0.1
-------
Table 3. Continued
Chloro-organics (ug/L)
Pulp and Paper Mills Date
6. Wisconsin Tissue Mill 11/30/76
2/28/77
2/28/77
2/28/77
7/18/77
7/19/77
10. Riverside Paper Company 12/02/76
12/02/76
11. Consolidated Papers, 12/02/76
Appleton 12/02/76
7/21/77
8/10/77
13. Midtec Paper 12/02/76
3/02/77
3/02/77
7/20/77
7/21/77
16. Appleton Papers 12/02/76
3/03/77
3/03/77
3/03/77
7/21/77
7/21^77
17. Thilmany Pulp and Paper 12/03/76
3/03/77
3/03/77
Sample
Source
Final
Raw
Primary
Final
Wet Well
Final
Final
Final
Raw
Final
Final
Final
Final
Raw
Final
Raw
Final
Final
Raw
Primary
Final
Raw
Final
, Final
Raw
Final
Sample
Type
grab
24 hr.
24 hr.
24 hr.
grab
24 hr.
Split
Split
grab
grab
24 hr.
grab
24 hr.
24 hr.
24 hr.
24 hr.
24 hr.
24 hr.
24 hr.
24 hr.
24 hr.
grab
grab
5 hr.
grab
2 hr.
comp.
comp.
comp.
comp.
Grab
Grab
comp.
comp.
ccmp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
Suspended Pentachloro- Pentachloro-
Solids phenol anisole Others**
(rag/L) PCB* (PCP) (PCA) by GC
2020
72
10
21880
5
_
-
_
-
79
37
_
860
38
750
23
_
1550
62
35
936
98
_
580
68
.3 <10
25
2.2 <10
1.4 <10
8200
< .2 < 1
<0.1 <10
<0.1 <10
<0.2
7(1254) x
<0.2
_
<0.1 <10
<0.2 OJ
< 0.2 40
<0.2 -20
<0.3 <1
<0.2 <10
<0.2
<0.2 <20
<0.2
<0.2
-------
Table 3. Continued
Chloro-organlcs (ug/L)
Pulp and Paper Mills Date
21.
23.
_D
24.
25.
26.
7/21/77
7/21/77
7/21/77
Nicolet Paper Company 12/05/76
3/04/77
3/04/77
3/08/77
3/08/77
7/24/77
Fort Howard Paper Company 12/06/76
3/05/77
4/15/77
4/15/77
7/25/77
8/09/77
American Can Co., Green 12/07/76
Bay 1/26/77
1/26/77
3/06/77
3/06/77
7/26/77
Proctor and Gamble Paper 12/07/76
Products 3/06/77
3/06/77
7/26/77
Green Bay Packaging 12/07/76
7/26/77
Sample
Source
Raw
Lagoon
Final
Final
Raw
Final
Raw
Final
Final
Final
Final
Final
Final
Final
Final
Final
Raw
Final
Raw
Final
Final
Final
Intake
Final
Final
Eff.
to River
Eff.
Sample
Type
24
24
24
24
hr.
hr.
hr.
hr.
comp.
comp.
comp.
comp.
grab
24
24
24
24
hr.
hr.
hr.
hr.
comp.
comp.
comp.
comp.
Suspended Pentachloro- Pentachloro-
Solids phenol am* sole Others**
(mg/L) PCB* (PCP) (PCA) by GC
216
168
76
_
108
10
196
13
21
grab
24
24
24
24
24
24
24
24
24
24
24
24
HoO 24
24
24
24
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
hr.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
grab
67
50
76
50
102
_
516
17
388
17
58
_
4
116
72
44
< 0.
-
< 0.
< 0.
< 0.
< 0.
.2 (1242
< 0.
< 0.
3.
1.
2.
12
7.
5.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
0.
1 8
33
1 18
2 <10
3 <10
2 <10
+ 54)<10
2 <10
2 < 5
7 <10
2 <10 .
0 <10
<10
7 12
4 x
2 <10
2 <10
2 <10
2 <10
2 <10
2 <1 .0
2 <10
2 <1 .0
2 <10
3 <1 .0
2 <10
37 <0.3
< 0
0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< 0
< o
0
0
< 0
< 0
< 0
< 0
< 0
0
.1 3CP 9.0
-
.13
.1
.1
.1
.1
.1
.1
.1
.1
.1
.1
.1
-
.1
.1
.1
.1
.1
.2
.1
.5
.1
.1 3CP< 0,5
.1
.01 4CP< 0.2, 3C
to River
-------
,ie 3. Continued
Chloro-organics (ug/L)
Sewage Treatment Plants Date
3. Neenah - Menasha STP 11/30/76
11/30/76
2/28/77
2/28/77
3/08/77
Sample
Source
Raw
Final
Raw
Final
Raw
Sample
Type
Suspended
Solids
(mg/L)
grab
24
24
24
24
hr.
hr.
hr.
hr.
comp.
comp.
comp.
comp.
176
12
324
<
<
Pentachloro-
phenol
PCB* (PCP)
6.
0.
0.
0.
1.
6
1
2
2
0
(1248 +
3/08/77
3/08/77
7/19/77
7. Town of Menasha East 12/01/76
8. Town of Menasha West 12/01/76
9. Butte des Morts Utility 12/02/76
District 12/02/76
12. Appleton STP 12/02/76
12/02/76
3/02/77
3/02/77
3/02/77
7/21/77
7/21/77
14. Kimberly STP 12/02/77
15. Little Chute STP 12/02/76
18. Heart of the Valley STP 12/03/76
3/03/77
3/03/77
j> 7/21/77
Primary
Final
Final
Final
Final
Final
Final
Raw
Final
Raw
Primary
Final
Raw
Final
Final
Final
Final
Raw
Final
Final
24
24
24
24
24
24
hr.
hr.
hr.
hr.
hr.
hr.
grab
comp.
comp.
comp.
comp.
comp.
comp.
80
9
18
-
-
<
<
<
<
0.
0.
0.
0.
0.
<0.
-
<
grab
24
24
24
24
24
24
24
hr.
hr.
hr.
hr.
hr.
hr.
hr.
comp.
comp.
comp.
comp.
comp.
comp.
comp.
-
448
136
40
340
78
<
<
0.
23
0.
1.
0.
0.
1.
0.
<0.
grab
grab
24
24
hr.
hr.
comp .
comp.
grab
86
46
6
<
0.
<0.
<
0.
<0.
<0.
37
2
2
1
1
2
2
2
4
4
6
3
2.
2
2
2
2
2
2
_
2.3
1
_
54)
_
2.3
<0.2
<10
<10
< 0.1
<10
^
<2.0
<20
<10
<10
9
<10
<0.1
<5.0
<10
<1.0
<10
0.25
Pentachloro-
anisole Others**
(PCA) by GC
o!
0.
0.
0.
0.
0.
0.
< 0.
-------
0
-------
removes RGBs from the final effluent. Other studies have also linked
PCBs with particulates in water and wastewater (69, 83). Wisconsin
Tissue Mill operates an efficient waste treatment system as indicated by
analyses of its wastewater samples. Samples collected on February 28,
1977 show both suspended solids (2020 mg/L) and PCBs (25 ug/L) were high
in the raw wastewater. However, the primary clarifier and final effluent
samples show a dramatic decrease. In the final effluent, the PCS concentration
was reduced from 25 to 1.4 ug/L while suspended solids were reduced from
2020 to 10 mg/L. Similar relationships are shown by the sample analyses
from Kimberly-Clark Lake View and the Neenah-Menasha and Appleton
Sewage Treatment Plants. Samples collected on November 30, 1976 from
the Meenah-Menasha STP were not analyzed for suspended solids, but PCBs
were reduced from 6.6 ug/L in raw to OJ ug/L in final effluent. Samples
collected from the same facility on March 8, 1977 show a reduction in
suspended solids from 324 to 80-mg/L and a corresponding reduction in
PCBs from 1.0 to .37 ug/L. The Appleton STP samples show PCB raw to
final effluent reductions from 23 to < 0.2, 1.4 to .6, and 1.3 to <0.2 ug/L
with corresponding suspended solids reductions.
Similar reductions for other chloro-organic compounds may also occur
and. include the following compounds identified by GC analysis:
tetrachlorophenol, trichlorophenol, tetrachloroguaiacol, trichloroguaiacol
and dehydroabietic acid. This relationship needs further study.
Most of the PCBs entering a sewage treatment plant becomes dissolved in
or absorbed on the suspended particulate matter and are removed with the
sludge during the primary and secondary stages of treatment (99, 69,
65). The same relationship has been considered valid for PCBs in wastewater
-99-
-------
from paper mills using recycled paper fibers as a raw material (88).
Recent work on effluents from pulping and bleaching mills indicates
effective removal of many organic toxicants by most of the waste treatment
systems under investigation (59). However, very little removal of fatty
acids, resin acids, or bleach toxicants occurred during primary clarification,
which suggests that these compounds were not associated with the suspended
solids removed.
Table 4 presents data on wastewater effluents extracted from Table 3.
The data are presented to show relationships among suspended solids, PCB
concentration, and stage of waste treatment at selected paper mills and
sewage treatment plants.
Table 4, Relationship between PCB concentration and suspended solids in
paper mills and sewage treatment plants.
Mill
Bergstrom Paper Co.
Kimberly-Cl ark-
La keview
Wisconsin Tissue
Mill
Neenah Menasha STP
Appleton STP
Date
2/28/77
2/28/77
3/24/77
3/24/77
2/28/77
2/28/77
2/28/77
3/08/77
3/08/77
3/08/77
3/02/77
3/02/77
Sampl e
Source
Raw
Final
Raw
Final
Raw
Primary
Final
Raw
Primary
Final
Raw
Primary
Suspended
Solids
(mg/L)
2840
540
660
13
2020,
72
10
324,
80
9
448
136
PCB
(mg/L)
79
68
19
1.2
25
2.2
1.4
1.0
0.37
<0.2
1.4
0.4
-100-
-------
Table 4. Continued
Mill Date
3/02/77
7/21/77
7/21/77
DePere STP 3/04/78
3/04/78
Sample
Source
Final
Raw
Final
Raw
Final
Suspended
Solids
(mg/L)
40
340
78
260
35
PCB
(mg/L)
0.6
1.3
0.2
0.5
0.6
In general, there is a decrease in PCB concentration with advanced
treatment and suspended solids removal. It should be noted that-Bergstrom.
Paper Company has nearly the same waste treatment .system as Wisconsin
Tissue Mill. However, Bergstrom's treatment system does not appear to
be efficient in removing solids or PCBs. This may be a function of
loading or waste character* Further investigation of this situation is
necessary.
Some laboratory measurements were made on final effluents to demonstrate
that additional solids removal could reduce PCB levels beyond what is
currently being achieved.
Table 5 presents the results of a test to measure the effect of filtration
of Fort Howard^ final effluent PCB concentration. By passing the waste
water through a Reeve Angel (Grade 202) filter, 54 percent of the PCBs were
removed. This reduction may be partly due to absorption to the filter
as well as to removing particles that have PCBs associated with them.
-101-
-------
Table 5. Effect of Filtration on PCB Concentration in Final Effluent
from Fort Howard Paper Company.*
Test
PCB Concentration (ug/L)
Unfiltered
Fi1tered
7.7
4.2
Reduction = 46%
* Filtration through a Reeve Angel Grade 202 filter.
Table 6 shows results of measurements on the effect of centrifuging
selected final effluents. Centrifugation was effective in removing 46 percent
of the PCB content in final effluent from Fort Howard Paper Company and
the Bergstrom Paper Company. The same treatment was able to remove 29 percent
of the trichloroguaiacol present in the final effluent of the Consolidated
Paper Company,even though the solids were already low.
Table 6. Effect of Centrifugation on Selected Chloro-organics in Final
Effluents.
Mill
Suspended Solids
Before Centrifugation
(mg/L)
Concentration (ug/L) %
Before After Removal
Fort Howard
Paper Company
Bergstrom Paper
102
148
PCB
5.4
16.0
2.9
8.7
46
46
Company
Consolidated Paper
Company
37
Trichloroguaiacol
43 35
29
-102-
-------
The data suggest that additional waste treatment could be effective in
<&.<
removing PCBs and perhaps other chloro-organics from waste waters.
The significant concentrations of pentachlorophenol found in some of the
Thilmany Pulp and Paper Company wastewaters were traced to the use of
"Nalco 201." Nalco 201 contains 16 percent pentachlorophenate and 8
percent trichlorophenate. This product was being used in an alum truck
to control slimes. It was also found that "Halco 76-31," which contains
chlorophenate, was being used as a slimicide in recycled trim (broke)
paper. The mill has indicated these compounds are no longer used.
Other compounds detected and quantified by GC/EC in Table 3 were usually
accomplished only after their identification by GC/MS and when standards
were available. A complete tabulation of compounds identified, and
unidentified compounds characterized, by GC/MS, is presented in the
Appendices.
More than 100 compounds identified by GC/MS are listed in Table 7. Appendix
A also lists the compounds, along with their source, location, and extract
of the sample(s) containing them. The data in Appendix A show how each
mass spectrum was identified, along with pertinent literature references.
The compounds are listed as they were detected, except for those identified
as methylated derivatives. Other compounds, which were characterized but
remain unidentifed, are listed in Appendix B.
To assess the significance of the compounds detected in this study,
certain categories were assigned. Twenty compounds in Table 7 appear in
the EPA consent decree (CD) Priority Pollutant List (20). These include
some nonchlorinated compounds that are not detected efficiently by
-103-
-------
Table 7 , Chlorinated and Nonchlorinated Organic Compounds Identified in Samples from the
Lower Fox River Watershed.
*Acenapthene
Acetone, Tetrachloro-
Acetovam'llone
Aniline, Trichloro-
Anisole, Pentachloro-
*Anthracene (or Phenanthrene)
Bezene, Dichloro-di ethyl -
Benzoate, Dimethyl -
Benzoate, Methyl-methoxy-
Benzoic acid
Benzoic acid, Isopropyl-
Benzophenanthrene, Methyl-
or (Benzanthracene, Methyl-}
Benzophenone
Benzothiazole
Benzothiazole, Hydroxy-
Benzothiazole, Methyl-thio-
Benzyl alcohol
Biphenyl
Biphenyl, Methyl-
Bisphenol A
Bisphenol A, Chloro-
Bisphenol A, Dichloro- (2 isomers)
Bisphenol A, Tetrachloro-
Bisphenol A, Trichloro-
Borneol, Iso-
Caffeine
Camphor, Oxo-
Carbazole
*Chlordane
*Chrysene
*DDD
*DDE
*DDT
Dodecane
FATTY ACIDS
Heptadecanoic Acid
Laurie Acid
Myristic Acid
Oleic Acid
Palmitic Acid
Stearic Acid
FATTY ACIDS. METHYL ESTERS
Methyl palmitat^
Methyl stearate
*Fluoranthene
Guaiaol
Guaiacol, Dichoro-(3 isomers)
Suaiacol, Tetrachloro-
Guaiacol, Trichloro- (3 isomers)
Heptadecane
*Hexachlorocyclohexane (Lindane)
*Hexach1orocyclopentadiene
Hexadecane
Indole, Chloro-p- Menth-4-ene-3-one
Naphthalene, Isopropyl-
Naphthalene, Methyl-
Nonadecane
Octadecane
Pentadecane
Phenanthrene, Methyl-
*Phenanthrene, Methyl-
*Phenol
Phenol, p-Tertiary Amyl-
*Phenol, Chloro-
Phenol, p-(cC -chloroethyl)-
Phenol, Decyl-
*Phenol, Dichloro- (2 isomers)
Phenol, Ethyl-
Phenol, Nonyl- (3 isomers)
*Phenol, Pentachloro-
Phenol, Tetrachloro-
(2,3,4,6 or 2,3,5,5)
Phenol, Trichloro-
* (2,4,6)
(2,4,5 or 2,3,4)
Phenol, Trichloro-dimethoxy-
Phenol, Undecyl-
Phenyl, Decane
Phenyl Dodecane
Phenyl Undecane
Phosphate, Tributyl-
PHTHALATES
*Dibutyl Phthalate
*Diethyl Phthalate
*Dioctyl Phthalate
*Polychlorinated Biphenyls (PCBs)
Propan-2-one, l-(4-hydroxy-3-methoxy
phenyl) or guaiacyl acetone
*Pyrene
RESIN ACIDS
6,8,11,13 Abietatetraen-18-oic AciJ
Dehydroabietic Acid
Oxo-dehydroabietic Acid
Pimaric Acid
Sandaracopimarie Acid
RESIN ACIDS, METHYL ESTERS
Methyl Dehydroabietate
RESIN ACIDS. CHLORINATED
Chlorodehydroabietic Acid (2 isomers)
Dichlorodehydroabietic Acid
RESIN ACID METHYL ESTERS, CHLORINATED
Methyl Chlorodehydroabietate
Methyl DiChlorodehydroabietate
Salicylic Acid
Syringaldehyde
Syringaldehyde, Chloro-
Tetradecane
Toluene, Dichloro-
Vanillin
Vanillic Acid
Veratrole, Dichloro-
Veratrole, Trichloro-
Xylene, Dichloro-
Xylene, Trichloro-
*Compounds found on EPA Consent Decree Priority Pollutant List (20).
-104-
-------
GC/EC. Other compounds observed in pulp and paper mill wastes match
those found to be toxic to fish by other investigators, including Fox et
aji_. (21), Leach and Thakore (22-28), Lockhart and Leach (29), McKague
et_al_. (30), Rogers and Keith (31), and Walden (32). Compounds prefixed
with P/T (toxics from paper mill wastes) in Appendix A include chloro-
guaiacols, resin acids, chloro-resin acids, and oleic acid. Many other
compounds previously reported in paper mill wastes were also found in
this study and are designated by the prefix P. These include acetovanillone,
fatty acids, guaiacol, guaiacyl acetone, methyl thiobenzothiazole,
syrin-galdehyde, vanillin, and vanillic acid. Of the remaining compounds
in Appendix A, six are polycytlic aromatic "hydrocarbons (PAHs). Two . ,,
compounds commonly used in industry, i.e. no-nyl phenol (present in
surfactants) and benzotniazole (an antioxidant), appear in Appendix A,
Alkanes, such as hexadecane, have been used in kerosene-based defoamers
(Webb et al_. (33)). Bisphenol A< could have been used as a fungicide
(39). :
Some compounds found in final effluents were quantitated by GC/FID
(flame ionization detector) and/or GC/MS. Various effluents and extraction
efficiencies were experienced; therefore only concentration ranges (in
ug/L) are given here: benzothiazole (10-30), hydroxybenzothiazole (10-
30), methyl thiobenzothiazole (10-40), trichloroguaiacols (10-60),
tetrachlorophenol (2-20), pentachlorophenol (5-40), dehydroabietic acid
(100-8500), and PAHs (0.5-10). The concentrations of these generally
corroborate earlier investigations by Rogers (90), Rogers and Keith (31)
Keith (45), Brownlee and Strachan (34),and others noted in Appendix A.
-105-
-------
Although a few samples contained ehloro-guaiacols, many contained various
isomers of the mono to penta chloro-phenols as well as PCBs. The source
of chloro-phenols in mill wastewaters has not yet been determined.
Chloro-phenols could have been used by paper mills for slime control.
Since chloro-guiacols were not found in some mill wastewaters, this may
indicate that these mills do not bleach their pulp or that they purchase
pulp and/or de-ink recycled paper. Bergstrom Paper Company, Mill 2,
which acquires its pulp equally through purchase and de-inking, is one
major exception. Its wastewater contained not only chloro-guaiacols and
chloro-phenols but also relatively large amounts of resin acids, especially
dehydroabietic acid (up to3.2mg/L). This resin acid appears to be the
most stable of the resin acids,as shown by Brownlee and Strachan (34)
and Fox et_ al_. (35). The toxicity of resin acids to fish has been
known since 1936. The lethal threshold concentration of dehydroabietic
acid for young sockeye salmon was found to be 2 mg/L by Rogers (90).
Leach and Thakore (28) reported a 96 hr. LC 50 of 0.75 mg/L for dehydroabietic
acid using coho salmon. The resin acids and fatty acids from this mill
could have come from the use of rosin or tall oil (89). Our observations
of chloro-phenols corroborate work by Lindstrom et_ aj_. (36). However,
we did not detect any chloro-catechols. Whenever chloro-vertrole derivatives
were detected in methylated acidic fractions, chloro-guaiacols had been
detected in these acidic fractions before methylation.
Given the sampling locations, it is very difficult to determine which
chloro-organic compound found in a particular mill was added during
production, formed in the mill, or formed during wastewater treatment.
It is possible, but yet unproven, that chloro-guaiacols, chloro-resin
acids, chlorosyringaldehyde, chloro-toluenes, chloro-xylenes, chloroindole,
-106-
-------
some chloro-phenols and, tentatively, some chloro-bisphenol A's were
formed at some point in the mill by reaction with chlorine. It is !
possible that some of the unidentified compounds listed in Appendix B
could have been chlorinated in the paper-making process.
SURFACE WATER AND SESTON
Surface Water
Fox River surface water samples were collected at the 25 stations shown
on Figure 34. Sampling was concentrated near Green Bay, Appleton, and
Neenah-Menasha because of the presence of most paper mills and sewage
treatment plants in these areas. The results of chloro-organic analyses
are presented in Table 8 in downstream order.
The low concentrations found in surface water were expected because of
the low solubility of chlorobiphenyls in water. Some values for PCB
solubility are shown in Table 9. Although there is some disagreement
regarding the solubility of PCBs in water, it is generally agreed the
solubilities are low and tend to decrease with increasing chlorine
content. If PCB concentrations greater than the theoretical solubility
in water were found, it would most likely be due to PCBs associated with
suspended solids.
*
It is difficult to draw any conclusions from the data in Table 8 since
most samples did not have chloro-organic concentrations above the analytical
detection level. However, some general comments can be made to explain
the concentrations found:
-107-
-------
12
U
13
Lake
Wirmebago
Figure 3k. River-water Sampling Locations
-108-
-------
Table 8. Concentration of Chloro-organics (ug/L) Found in Unfiltered
Fox River Water in Downstream Order.
Sample Number
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
Date
2/27/77
7 719/77
11/30/76
2/27/77
2/27/77
11/30/76
2/27/77
7/20/77
3/02/77
2/02/76
3/02/77
3/03/77
12/03/76
7/23/77
3/03/77
7/25/77
3/04/77
12/06/76
7/25/77
3/04/77
3/05/77
3/05/77
3/05/77
3/05/77
12/08/76
PCB
<0.1
-------
Table 9. Solubility of Chlorobiphenyls in Water*
Compound
4,4'-
Trichlorobiphenyls
2,4,4'-
2',3,4-
2,2',5-
Solubility (ppm)
(Wollnofer et (Haque and Schmedding,
aK, 1973) 1975)
Monochl orobi phenyl s
2-
3-
4-
Di chlorobiphenyls
2,4-
2,4'-
2,4'-
5.9
3.5
1.19
1.40
1.50
1.88 0.673 + 0.004
0.08
0.085
0.078
0.248 + 0.004
Tetrachlorobi phenyls
22' 55'-
2;2''»3^r-
2,2',3,5'-
2,2'S4J41-
2,3',4,4'-
2,3',4',5-
Pentachlorobi phenyls
2,2',3,4,5'-
2,2',4,5,5'-
Hexachlorobiphenyl
2,2'S4S4',5,5'
0.046
0.034
0.170
0.068
0.058
0.041
0.175
0.022
0.031
0.0088
0.0265 + 0.008
0.000953 + 0.00001
Octachlorobiphenyl
2,2',3,3'94,4',5f5l- 0.0070
Decachlorobiphenyl 0.015
* Adapted from Kornreich, M. et. al., 1976 (92)
-no-
-------
(1) The Fox River is not saturated with PCBs unless only the very
highly chlorinated isomers are present. The presence of only highly
chlorinated PCBs is unlikely because most commercial mixtures contain a
variety of isomers,from monochloro to at least heptachlorobiphenyl.
The PCB mixture most frequently identified was Aroclor 1242, having been
found in approximately 90 percent of the samples. Aroclor 1242 is composed
mainly of tetrachlorobiphenyl and lesser chlorinated isomers (92). Aroclor
1248 and 1245 were only found occasionally.
(2) Although all surface water concentrations were low,it.should be
noted that the highest concentrations were found in areas affected by dis-
chargers using recycled paper fibers and other sources discharging PCBs.
Thus it appears that higher water concentrations of PCBs are localized and
are related to nearby point sources. This finding was expected from
information provided by a previous report (88).
Seston
For the purposes of this investigation,seston is defined as the whole
heterogenous mixture of living and nonliving substances captured by
filtering water through a #20 (80 urn) mesh net. PCB residues have been
found in plankton sieved through a 106 urn net (91). It was recognized
that temporal and spatial variations in plankton species composition
and particle size affect net-capturing efficiency. Many species of
plankton, especially diatoms, can pass through an 80 urn net. However,
most chloro-organic compounds are believed to be associated with effluent
suspended solids and may not be available to living seston in high
concentrations. Because the samples represented a fraction of the
river's particulate load, unfiltered water samples were collected at
four locations for comparison.
-Ill-
-------
The results of chloro-organic measurements on seston samples collected
in downstream order are presented in Table 10. Sample site locations are
designated on Figure 35. The PCB concentrations are for the volume of
water filtered and are thus directly comparable with river water concentrations
The lower detectable levels of PCBs in the seston samples are due to the
large volume of water filtered (190-3800 liters). The samples were not
analyzed on a dry weight basis because of the possibility of compound
loss during the drying process.
Immediately apparent from Table lOare the low concentrations of PCBs
associated with seston in the bulk water. The significance of these
levels compared to river water is addressed later in this section. Also
apparent is that, as the river water travels downstream, the PCB concentration
in seston increases. The increase is steady, from values below detection
limits in the Neenah Channel (0.002 ug/L) to 0.029 ug/L at the river
mouth. This suggests seston is accumulating PCB throughout the length
of the river. The data also suggest PCBs in seston are related to
suspended solids discharged in effluents, since effluents are the major
chloro-organic source. Thus, effluent suspended solids are likely to
make up a significant portion of the river suspended solids. A previous
study of seston in the Fox River (11) indicated waste paper fibers
discharged to the river tended to settle out a short distance below
outfalls. High PCB concentrations in sediments support the theory that
PCBs and other chloro-organies are carried to the river bottom with
particulate matter. This is one reason why river seston does not contain
high PCB concentrations.
CPO 82164»9
-112-
-------
Table 10. Chloro-organic Concentrations (ug/L) Associated with Fox River Seston.
Sample #
1*
2
3
4
5
6
7
8
9*
10*
11*
12
13
14
15
16
Water Volume
Date Filtered (liters) PCB Pentachloroanisole
7/19/77
7/19/77
7/19/77
11/23/76
7/20/77
7/21/77
7/22/77
7/22/77
7/23/77
7/25/77
7/25/77
7/26/77
7/26/77
7/26/77
11/23/76
7/26/77
190
380
190
3800
190
190
190
190
190
190
190
190
190
190
1900
190
0.002
0.006
0.003
0.13
0.015
0.006
0.024
Lost
0.025
0.020
0.030
0.013
0.024
0.018
0.020
0.029
x = 0.016
0.05
0.02
0.045
0.05
0.1
0.05
Seston and Surface Water Relationship
On four occasions, unfiltered riverwater was sampled at the same time
and location as seston. Thus the PCBs associated with a size fraction
of seston in the water column was investigated. The results of these
measurements are shown in Table 11.
The data indicates that about 11 percent of the PCB concentration was asso-
ciated with the seston. Although only three locations were described, it
appears this ratio was relatively consistent. Since the amount of PCB
in unfiltered water was always much-greater than the amount associated
with seston, some observations can be made:
-113-
-------
Omit 1.5 Miles
TV
/ Wrightstown
Z*Z=p Hwy. 96
Kaukauna
Uttle\Lake Butte des Morts
Menasha
(2)
Pigtare 35. Seston Sampling Locations
-------
(1) The PCBs in the water column must be either dissolved or
attached to particulates smaller than 80 urn. The PCBs1 hydrophobia
nature should cause them to cluster together or around organic impurities
such as oi1-1 ike droplets. Thus they would have been sampled as dissolved
material. Further study will be required to determine if PCBs are
associated with particules less than 80 urn.
(2) Once PCBs enter the river system, they can either settle out
or float to the water surface. The accumulation of PCBs in sediment is
evidenced by the high concentrations found there. However, similar to
hydrophobic/lipophilic chlorinated hydrocarbon pesticides, PCBs and
their commercial mixtures can be enriched on the surface of water in the
lipid phases of a surface organic microlayer (93).
Table 11. PCB Concentration in River Water and Seston
Sample
Riverwater
2
14
16
19
Number
Seston
1
9
10
11
PCB
Riverwater
0.05
0.24
0.14
0.30
ug/L
Seston
0.002
0.025
0.020
0.030
% PCB Associated
with Seston
N.A.
10
14
10
X = 11
This exposes them to both vaporization into the atmosphere and destructive
ultraviolet radiation from the sun. The absence of PCBs from most water
samples is probably due to a combination of these effects.
-115-
-------
When suspended solids from an effluent containing PCBs are dense enough
to settle out of the water column, they will become part of the bottom
sediment. However, a. fraction of the PCB-contaminated discharge will
remain suspended and become part of the river's seston load. Thus, as
water travels down the Lower Fox River, the concentration of PCB-contaminated
seston becomes greater with an increase in the number of discharge
points it passes.
SEDIMENT
Sediment samples for PCB analysis were collected at the 34 stations
indicated on Figure 36, and results of the analysis are found in Table
12. Station 1 was established in the Menasha Channel above any known
point sources and the PCB concentration was less than 0.05 mg/kg. Nine
of the remaining 33 samples were found to contain less than 1 mg/kg, and
24 samples contained PCB concentrations ranging from 1.2 to 61.0 mg/kg
on a dry weight basis.
Analysis of sediments from proposed dredging projects during the past
few years suggested that PCB concentrations greater than 1 mg/kg are
associated with localized point sources (12). Guidelines established by
EPA (12) classify sediments containing PCB concentrations of 10 mg/kg or
higher as polluted and unacceptable for open lake disposal. The pollution
classification of sediments with PCB concentrations between 1.0 and 10.0
mg/kg are to be considered on a case-by-case basis. The Wisconsin DNR
considers sediments containing 1 mg/kg or more as a potential hazard and
has tentatively established the following guidelines concerning dredge
spoil disposal:
-116-
-------
DePere
Omit 3 Miles
Omit 1.5 Miles
Wrightstown
Hwy.96
Kaukauna
\Omit 0.7 Miles
Kimberly
College Ave.
Appleton
Hwy. 10
Lake Winnebmgo
Little\.ake Butte des Morts
1
Neenah
Figure 36. Sediment Sampling Locations
-117-
-------
Table 12. PCB Concentrations in Stdiment
Station No. and Location
Collection PCB Other
Late (mg/kg) Compounds*
(dry weight) (ing/kg)
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.
32.
33.
34.
Menasha Channel
Directly below Bergstrom
300 yards below Bergstrom
Little Lake Butte des Morts CNWRR
Bridge
Little Lake Butte des Morts CNWRR
Bridge
Little Lake Butte des Morts Outlet
Appletqn Yacht Club
Above lower Appleton Dam
Below Consolidated
1 Mile below Consolidated
Above Kimberly Dam below Midtec
Above lower Little Chute Dam
Below Thilmany Paper
Above Rapide Croche Dam
Above Little Rapids Dam
Above DePere Dam
Across from Ft. Howard Outfall
Below Ft. Howard, CNWRR bridge
Near Mouth of East River
Above Green Bay STP Near Mouth
Below Green Bay STP Outfall
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
Green Bay
5/23/77
5/23/77
5/23/77
5/23/77
11/24/76
5/23/77
11/24/76
5/23/77
5/23/77
6/22/77
5/23/77
5/23/77
6/04/77
6/04/77
6/04/77
6/22/77
5/23/77
5/23/77
5/24/77
5/24/77
11/24/76
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
5/24/77
<0.05
1.4
61.0
1.3
5.5
21.0
8.2
9.0
1.2
3.6
0.9
5.1
4.8
5.8
5.0
0.18
0.96
18.3
13.0
2.1
38.0
7.5
7.2
4.7
0.12
1.8
0.46
5.6
< 0.05
11.0
2.6
-------
1 mg/kg (dry weight) no restrictions
1-10 mg/kg (dry weight) spoil must be disposed of in a contained area
10 mg/kg (dry weight) use of silt screen required; spoil must be
disposed of in a clay-sealed disposal area
or in a licensed toxic and hazardous waste
disposal area.
Table 13 is a list of areas polluted with PCBs, according to EPA guidelines.
Table 13. Location of Sediment with PCS Concentration Greater than 10 mg/kg.
Station No.
3
6
18
19
21
30
Location
300 yards below Bergstrom
Little Lake Butte des Morts
outlet
CNWRR bridge below Ft. Howard
Near mouth of East River
Below Green Bay STP outfall
Green Bay near Sable Pt.
PCB (mg/kg)
61.0
21.0
18.3
13.0
38.0
11.0
Station 8, above the lower Appleton Dam contained 9 mg/kg. Other
stations located in the prevailing eastward current between the mouth of
the Fox River and Sable Point in Green Bay contained 2.6 to 7.5 mg/kg of
PCBs.
The data indicate the sediments of most of the Lower Fox River and the
east side of Green Bay to Sable Point are polluted with significant
concentrations of PCBs. It should be noted the highest concentrations
-119-
-------
were found in silt deposition areas downstream from PCS containing
discharges. Station 30 in Green Bay was located near a bar extending
from Sable Point, which is probably a silt deposition area.
The sediment samples were collected from the top 6 inches of sediment in
all cases. This roughly indicates the PCBs found were recently deposited
and are probably still accumulating,although the sedimentation rates
were not determined. Studies in the Santa Barbara Basin suggest that a
substantial portion of the chlorinated hydrocarbons entering the sea
from diverse sources is being deposited in the sediments (94). Also}
data gathered from the major drainage basins of the United States indicate
widespread occurrence of PCBs in bottom sediments (95). The data also
reinforce the statement that PCBs are associated with solids and that
efficient suspended solids removal is important in treating wastes for
chloro-organic compounds.
CLAMS
A total of 74 clams (Anodontoides ferussacianus) were placed at 10
locations along the Fox River and in Green Bay to determine the potential
bioaccumulation of PCBs. Three original specimens were analyzed as
control specimens for chloro-organic compounds. All were below the
limit of analytical detectability for the chloro-organics screened
during this project. Fifteen clams were retrieved from 4 locations for
chloro-organic analysis. The remaining clams were lost to either vandalism
or lack of survival. Table 14 presents the data obtained, and Figure 37
illustrates the relationship of PCB uptake to time.
-120-
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Table 14. PCB Analysis of Clams* Placed in the Fox River
1.
2.
3.
4.
5.
6.
a
S 7.
i
Location
Green Bay
0.5 mile above
0.5 mile above
Green Bay
Date Placed
Wrightstown
Wrightstown
Below Depere Dam
0.5 mile above
0.2 mile below
Wrightstown
Appleton STP
5/25/77
5/24/77
5/24/77
5/25/77
5/24/77
5/24/77
5/24/77
Date Recovered
6/3/77
6/3/77
6/3/77 ;
6/22/77
6/22/77
6/22/77
6/22/77
Days in Place
9
10
10
27
28
28
28
Clams Retrieved PCB (ug/kg)
2
2
1
2
2
2
4
260
240
250
740
255
300
600
*Anodontoides ferussacianus
-------
700 «
800.
BOO*
!
400
ee
200-
100.
& BELOW APPLETON
O BELOW WRIGHTSTOWN
m BELOW DEPERE
0 GREEN BAY
10
20
DAYS
30
Figure 37. PCS BioaecumulEtion in Clam Tissue
-------
The original intent of this portion of the study was to take two or
three clams from each site at various time intervals over a 3 month
period for PCB analysis. This procedure should have indicated a rate
and a maximum range of PCB bioaccumulation in the Fox River system. The
loss of most of the clams was disappointing, but the data obtained do
indicate that PCBs bioaccumulate in clams at a rapid rate. The mean
uptake rate for the samples collected below DePere and above Wrightstown
was 10 ug/day for 28 days. The mean uptake rate for the Appleton and
Green Bay samples was 24 ug/day for 28 days. The data on chloro-organics
in sediment (Table 12) indicates the higher PCB uptake in clam locations
also, have higher sediment concentrations. This tends to indicate the
uptake rate of PCBs is related to the concentration of PCBs in the
sediments.
A ntore detailed study would be required to firmly establish a relationship
between uptake rate, maximum bioaccumulation} sediment concentration,and
water concentration. There is no way to determine from this study if
the source of PCBs was from new material or from PCBs already present in
the sediment.
An attempt was made to analyze clam tissue for compounds other than
PCBs; however, the lab methods could not be finalized during the time
period available. Tentative identification of pentachloroanisole (PCA)
was made on two samples from above Wrightstown. The PCA could not be
reliably quantified because the apparent concentration of 0.005 ug/kg
was too low for GC/MS analysis.
-123-
-------
The data obtained on clam tissue indicate that clams are an excellent
indicator organism for chloro-organic compounds, as indicated by other
studies (96, 9). Live clams are rarely found in the Fox River and the
eastern portion of Lower Green Bay. This may be due to bioaccumulation
of toxic substances in conjunction with low dissolved oxygen concentrations.
Dissolved oxygen concentrations are improving due to improved waste
treatment; however, the clam population may not be able to return due to
the polluted nature of the bottom sediments.
FISH
Polychlorinated biphenyls in the environment can cause a variety of
problems.. One of"the most important is their effect on the fishery.
High concentrations of PCBs are toxic to fish, but of greater significance
is chronic exposure resulting from the consumption of contaminated fish
by higher vertebrates including man. The U.S. Food and Drug Administration _
tolerance level for PCBs in the edible portion of fish is 5 ppm, and a
lower level of 2 ppm has been proposed (88). The Canadian Food and Drug
Directorate tolerance level is 2 ppm (88).
Thirty-five fish fillet samples were analyzed and all contained quantifiable
PCB concentrations. The detailed data are found in Table 15. PCB
concentrations found in fish below the DePere Dam ranged from 0.4 mg/kg
in a bowfin to 90 mg/kg in a carp. Sixteen of the 35 samples exceeded
the FDA tolerance of 5 mg/kg. Fish from Little Lake Butte des Morts
contained higher PCB concentrations than fish from DePere. However, the
sizes and fat content of Little Lake Butte des Morts fish were generally
-124-
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Table 15. Lower Fox River Fish Sampling and Analysis Results
Sample Location Date Common Name
Little Lake Butte des Morts April 77
(5)
Below OePere Dam April 77
(5)
(5) ,.
(4)
(5)
N. Pike
N. Pike
Walleye
Walleye
Carp
Carp
Carp
Carp
Carp
Carp
Carp
Carp
Carp
Carp
Carp
N. Pike
N. Pike
N. Pike
Walleye
Walleye
Bowfin
Y. Perch
Y. Perch
Y. Perch
Y. Perch
W. Sucker
W. Sucker
Length
(mm)
688.3
769.6
411.5
424.2
406.4
444.5
406.4
469.9
546.1
584.2
558.2
508.0
533.4
596.9
X=518.6
454.7
530.9
497.8
452.1
330.2
647.7
X=203.7
X=196.9
X=171.5",
X=184.9
429.3
482.6''
% Fat
0.5
0.8
1.5
2.4
1.2
1.7
2.0
2.3
4.6
5.4
5.8
6.1
6.1 .
9.0:
12.5
0.5
0.7
1.0
2.6
4.9
0.4
~\ 1.0
" 2.6
2.8
3.2
0.6
. 0.6
PCB* Other Chi oro-organics
(mg/kg) (mg/kg)
2.4 (1242)
2.3 (1242)
1.8 (1242)
5.2 (1242)
2.7
10.0 (1242)
4.3 (1242)
13.0
16.0
28.0
30.0
18.0
[1242)
1248)
1242)
1242)
PCA < 0.005
PCA 0.020
PCA = 0.060
PCA = 0.036
PCA <0.010
Dieldrin <0.010
20.0 (1242)
39.0 1
50.0 |
[1242)
[1242)
2.5 (124)
3.2 (1248)
3.0
6.8 (1248)
4.5 (1248)
0.5
1.0 (
: 5.3 <
1248)
1248)
Dieldrin< 0.010
6.6 (1248)
5.4 (1248)
1.4
2.5 (1248)
Dieldrin 0.008 ,
-------
Table 15. Continued
Date Common Name
Below DePere J*. Sucker
W. Sucker
W. Sucker
W. Sucker
Carp
Carp
Carp
Carp
Length
(mm)
482.6
381
452.1
431.8
439.4
325.1
259.1
375.9
% Fat
1.0
1.0
1.8
2.3
0.7
1.6
6.9
9.0
PCB* Other Chloro-organics
(mq/kq) (ma/ka)
2.3 (1248)
4.4 (1248)
3.2
4,2
2.5 (1248/1254)
6.6 (1248)
4.4 (1242)
90.0 (1248)
Dieldrin<0.010
Dieldrin 0.012
Dieldrin 0.010
Dieldrin 0.022
Dieldrin<0.010
* Number in parentheses indicates Aroclor mixture most similar to the PCBs in sample.
ro
en
i
-------
greater than DePere fish, which may partially account for their greater
level of PCBs. If fish of the same approximate length and fat content
are compared, little difference is apparent. This study supports the
findings of others that high fat content fish, such as carp, contain
higher concentrations of PCBs (97). PCBs are fat soluble and thus tend
to accumulate in fat tissue. Figure 38 is a regression analysis of the
correlation between fat content and PCB concentrations for all the
various species sampled.
The data indicate Fox River fish accumulate significant quantities of
PCBs, However, the effect of PCBs on organisms in the Fox River ecosystem
cannot be determined from this study.
An attempt was made to identify and quantify compounds other than'PCBs
in fish tissue, but the same analytical problems encountered with clam
tissue were experienced with fish. The presence of PCA in a range of 20
to 60 ug/kg in walleye and northern pike tissue from Little Lake Butte
des Morts was verified. Laboratory studies have shown that PCA is
readily accumulated from water by fish and is retained in fish tissue
for days after contaminated specimens are placed in PCA-free environment
(98). Chemical extraction losses were thought to be significant for PCA
in fish tissue. Therefore, higher concentrations of PCA and the presence
of other organic compounds are probable. The insecticide Dieldrin was
occasionally found in the 0.008-0.022 mg/kg range below the DePere Dam.
Because of the free movement of fish, correlation between tissue concentrations
and location may not be valid. However, the flow of the Fox River is
controlled by a series of dams that restrict fish movement. In addition
-127-
-------
ro
eo
2'0
40
PCB mg/kg
2,78
Y« 2.88
SDX« 11.63
X- 9.20
Coef. of Cor re I. * .88
50
D Carp
V N. Pike
O Sucker
Perch
V WaM«ye
BowfiVi
90
Figure 38. Correlation oJT PCB Concentration to Tat Content in Fish
-------
there are no other significant point sources of chlorinated organics in
the area under investigation. It appears valid to assume most chlorinated
organic compounds found in fish tissue originated from sources discharging
to the Fox River.
The PCB data in Table 15 indicate the commercial mixture most similar to
the PCB found in the fish sample. Aroclor 1242 was predominant in
Little Lake Butte des Morts fish, while Aroclor 1248 was the major
mixture in fish at the sampling s-ite below the OePere Dam. Chrotnatograms
of 1242 and 1248 are very similar in component peaks and are differentiated
by relative peak heights. Thus the presence of 1248 or a more highly
dvlorirvated mixture such as 1254 in the sample could mask the presence
of 1242. The presence of 1248 in the fish at the downstream site (DePere)
may indicate the presence of a source of one of the PCB mixtures with
more chlorine than 1242. .In fact this has been observed in the present
investigation. Table 3 indicates several sources of Arocolor 1248 or
1254 that could introduce these mixtures to the downstream fish. Also,
biological mechanisms may alter the components of 1242,making it appear
as 1248 when chromatographed.
SNOWMELT
Contributions of chlorinated hydrocarbons to surface waters may be
derived from atmospheric deposition. The importance of precipitation
scavenging and aerial deposition as a source of these substances has not
been fully addressed. However, atmospheric transport was an important
route for spreading the organo-chlorine DDT throughout the biosphere(13,14).
Additional recent studies indicate atmospheric inputs as the present
major source of PCBs to Lake Michigan at a rate of 5,000 kilograms per
-129-
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05} perhaps becaus-e URe Hichtgan's drainage basin is small compared
to the surface area of the laRe. However, most river systems display
the reverse relationship. In the Fox-Wolf River system the ratio of
water surface to drainage basin is less than 6 percent. Thus, direct addi-
tions of atmospheric pollutants to .the river are not as great as the amount
potentially delivered by runoff.
Snow was collected to yield a quantitative estimate of chloro-organics
entering the river system by land runoff of melted snovr. This kind of
sample was chosen because: *;
1. Snow forms a ground cover that may collect chloro-organic
deposition. Thus, snow should contain an Integration of all the
impacted chlorinated hydrocarbons during the lifetime of the layer.
2. Snow may contain the precipitation scavenged fraction of chloro-
organics as well as chloro-organics adhering to particulates
originating from local windblown sources.
3., PCBs and similar compounds are relatively insoluble in water
under most natural conditions. Thus, analyses of runoff may not
indicate the most significant fraction of these substances moving
through the environment. Therefore, snow sampling appeared to be
an attractive method for measuring chloro-organics available for
runoff events.
A total of 19 snowmelt collections were made during January and February
of 1977 in the Fox-Mo!f River drainage basin. Locations are shown by
Figures 39 and 40. More intensive sampling was conducted in the City of
-130-
-------
FOX-WOLF RIVER BASIN
Area Enlarged 111
Figure 39
Scale in Miles
Figure 39. Snow Sampling Locations
-131-
-------
U)
r\J
14
16-
15
18
19
Figure Uo. Snow Sampling Locations
-------
&r«en. Bay vicinity because of its industrial nature and varied sources
of chloro-organics. Approximately half the collections were made away
from the urban areas in the basin. The results of PCB measurements are
presented in Table 16. There was no effort to measure other chloro-
organics in snowmelt.
Table 16. Results of PCB analysis on snowmelt samples from the Fox-Wolf
River drainage basin.
Sample Number
1
2
3
4
5
6
7
8 , .
9
10
11
12
13
14
15
16
17
18
19
PCB Microgram/liter
< 0.2 . ./ . -.
< 0.2
< 0.5
0.15
< 0.1
- < o.i " -. ' ""
< 0.2
< 0.1
< 0.2
< 0,2
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
< 0.2
It is difficult to make conclusions on the significance of. chloro-
organics levels in snowmelt when all analyses except one yielded PCB
concentrations less than the analytical/detection limit. The one reported
PCB concentration was just at the detection limit,and this indicates
other samples may have contaminated PCBs, but at very low concentrations.
-133-
-------
Therefore, it is impossible to compare sample locations, since all results
were essentially the same. But it is useful to compare these data with
the results of similar investigations in the area.
In a separate study conducted during March of 1976, the Wisconsin DNR
collected eight snowmelt samples in the Lower Fox Valley, from Neenah to
Green Bay (16). Collection methods and sample size were similar to
those used in this study. The results indicated levels less than 0.1 ug
PCB/L of snowmelt in all samples except one,which was reported at less
than 0.2 ug/L. The difference between these detection levels is not
significant. Thus, for 2 consecutive years, PCBs were not detected in 2-
2.5 liters of snowmelt from the Lower Fox River Valley. However, in
larger volumes of snow sampled in the Chicago area, PCBs were consistently
detected in four samples(15). In the Chicago investigation, enough snow
was melted to yield 6 - 12.7 liters of water. Concentrations of PCBs
ranged from 0.0601 to 0.3272 ug/L. These concentrations were just at or
below the level of detectability. The ability to report these small
concentrations reflects the extraction of a larger sample size. A
significant finding of the same investigation was that the concentration of
PCBs in precipitation (rainfall) was as high in northern Michigan as it
was in Chicago. These concentrations were found in the range of 0.1 -
0.2 ug/L by extracting 1.3 - 77.5 liters of water.
In another study conducted at Isle Royale National Park in Lake Superior,
concentrations of 0..230 ug PCB/L were found in snow samples(17).
-134-
-------
The following data from a 1975 snowmelt study conducted in Wisconsin
(18) indicated PCBs were present in snow.
Table 17. PCB Levels in Snowmelt Water, 1975(18)*
City PCB (micrograms per liter)
Green Bay 0.01
Grafton (None Detected)
Kewaskum (None Detected)
Racine 0.17
Kenosha 0.22
Madison 0.24
Milwaukee 0.20
*Sampling methods and sample volumes were not reported.
The question of snowmelt samples representing precipitation is
open to discussion. There is no well-defined correlation between levels
of PCBs in snow cover and levels in precipitation. However, the data
will indicate the amount of PCBs available for land runoff during storm
events or melt periods that may eventually be channelled into the area
of investigation.
PCBs are found in similar concentrations at many locations,so it is
likely they are dispersed by atmospheric transport mechanisms. Because
these locations bracket the Fox-Wolf River drainage system, it is reasonable
to suspect PCBs are present in the precipitation and snow covering the
area. Although a great majority of the data from this study did not
indicate the presence, of PCBs, there is reason to suspect the sample
size was not adequate for analyses.
-135-
-------
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213 (1973).
-140-
-------
55. Matsuraoto, G., R. Ishiwata-ri and T. Hanya. Gas Ch-roroatographic-
Mass Spectrometric Identification of Phenols and Aromatic Acids in
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56. McNeil, E. E., R. Otson, W. F. Miles and F. J, Rajabalee. Determination
of Chlorinated Pesticides in Potable Water. J. of Chromatog. 132,
277-286 (1977).
57. Sovocool, G. W., R. G.- Lewis, R. L. Harless, N. K. Wilson and R. D.
Zehr. Analysis of Technical Chlordane by Gas Chromatography/Mass
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58. Kopperman, H. L., D. W. Kuehl, and G. E. Glass. Chlorinated Compounds
Found in Waste-Treatment Effluents and Their Capacity to Bioaccumulate.
In Jolley, R. L. (Ed.), Ref. 76, pp. 327-345 (1976).
59. Easty, D. B., L. G. Borchardt, and B. A. Webers. Removal of Wood-
Derived Toxics from Pulping and Bleaching Wastes. EPA Report No.
600/2-78-031, 89 p. (1978).
60, Hrutfiord, B. F., T. S. Friberg, D. F. Wilson, and J. R. Wilson.
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660/2-75-028 June (1975).
61. Brownlee, B. and W. M. J. Strachan. Distribution of Some Organic"
Compounds in the Receiving Waters of a Kraft Pulp and Paper Mill,
. J. Fish-. Res. Bd. Can. 34, 830-837 (1977).
62. Landner, L., K. Lindstrom, Karlsson, J. Nordin and L. Sorenson.
Bioaccumulation in Fish of Chlorinated Phenols from Kraft Pulp Mill
Bleachery Effluents. Bull, of Environ. Contam. and Toxicology, 18
(6), 663-673 (1977).
63. Thakore, A. N. and A. C. Oehlshlager. Structures of Toxic Constituents
in Kraft Mill Caustic Extraction Effluents from 13r and 1^ Nuclear
Magnetic Resonance. Can. J. Chem. 55, 3298-3303 (T977).
64. Jolley, R. L;, S. Katz, J. E. Mrochek, W. W. Pitt, Jr., and W. T.
Rainey. Analyzing Organics in Dilute Aqueous Solutions. Chemtech
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65. Dube, D. J., G. D. Veith and G. F. Lee. Polychlorinated Biphenyls
in Effluents from Sewage Treatment Plants in Southeastern Wisconsin.
J. Water Poll. Contr. Fed. 46, 966 (1974).
66. Ayer, F. A. (compiler). Proceedings of the 1975 National -Conference-
on Polychlorinated Biphenyls. EPA Report No. 560/6-75-004, 471 p.
(1976).
67. Bergh, A. K. and R. S. Peoples. Distribution of Polychlorinated
Biphenyls in a Municipal Wastewater Treatment Plant and Environs.
The Sci. of the Total Environ. 8, 197-204 (1977).
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68. Veith, G. D. Recent Fluctuations of Chlorobiphenyls (PCBs) in the
Green Bay, Wisconsin Region. Environ. Health Persp. 1, 51-54
(1972).
69. Lawrence, J. and H. M. Tosine. Polychlorinated Biphenyl Concentrations
in Sewage and Sludges of Some Waste Treatment Plants in Southern
Ontario. Bull. Environ. Contam. and Tox. 17 (1), 49-56 (1977).
70. Brown]ee, B.t M. E. Fox, W. M. J. Strachan, and S. R. Joshi.
Distribution of Dehydroabietic Acid in Sediments Adjacent to a
Kraft Pulp and Paper Mill. J. Fish. Res. Bd. Can. 34, 838-843
(1977).
71. VilTeneuve, D. C., A. P. Yagminas, I. A. Marino and G. C. Becking.
Toxicity Studies on Dehydroabietic Acid. Bull, of Environ. Contam.
and Tox. 18 (1). 42-47 (1977).
72. Zinkel, D. F., L. Zank and M. F. Wesolowski. Diterpene Resin Acids
A Compilation of Infrared, Mass, Nuclear Magnetic Resonance,
Ultraviolet Spectra and Gas Chromatographic Retention Data (of the
Methyl Esters). USDA, Forest Products Laboratory, Madison, Wisconsin
174p. (1971).-
73. Carlson, R. M., R. E. Carlson, H. L. Kopperman and R. Caple. Facile
Incorporation of Chlorine into Aromatic Systems During Aqueous
Chlorination Processes. Environ. Sci. and Tech. 9 (7), 674-675
(1975).
74. Carter, M. H. Techniques for Optimizing A Quadruple GC/MS Computer
System. EPA Report No.. 600/4-76-004, 27 p. March (1976).
75. Chang, T. L., T. E. Mead and D. F. Zinkel. Mass Spectra of Diterpene
Resin Acid Methyl Esters. J. Am. Oil Chem. Soc. 48, 455-461 (1971).
76. Jolley, R. L. (Ed.), Proceedings of the 1975 Conference on the
Environmental Impact of Water Chlorination, ORNL CONF 751096, Oak
Ridge, Tennessee, (1976).
77. Keith, L. H. (Ed.). Identification and Analysis of Organic Pollutants
in Water. Ann Arbor Science Publishers, Inc., Ann Arbor, Mich.,
718 p. (1976).
78. Mass Spectrometry Data Centre. Eight Peak Index of Mass Spectra.
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79. Morris, J. C. The Chemistry of Aqueous Chlorine in Relation to
Water Chlorination. In Jolley, R. L. (Ed.), Ref. 76, pp. 27-41
(1975).
80. Trost, B. M. Personal Communications, University of Wisconsin
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81. Zinkel, D. F. and G. C. Engler. Gas-Liquid Chromatography of Resin
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82. Stokstad, M. Wisconsin 1978 Water Quality Inventory Report to
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83. Nadeav, R. J. and R. A. Davis. Polychlorinated Biphenyls in the
Hudson River (Hudson Falls - Fort Edward, New York State). Bull
Env. Contam. and Tox. 16 (4), 436-444 (1976).
84. American Public Health Association. Standard Methods for the
Examination of Water and Wastewater, 14th ed. APHA, New York,
(1975).
85. Hesselberg, R. J. and J. L. Johnson. Column Extraction of Pesticides
from Fish, Fish Food and Mud. Bull. Env. Contam. and Tox. 7, 115-
120 (1972). , , .
86. Thompson, J. F. (Ed.). Analysis of Pesticide Residues in Human and
Environmental Samples. EPA, Res. Triangle Park, N. C. (1974).
87. USEPA. Fed. Reg. Part II, Vol. 38, Nov. 28 (1973).
88. Kleinert, S. J. Sources of Polychlorinated Biphenyls in Wisconsin.
In Proceedings Nat. Conf. on PCBs. Chicago, IL. Nov. 19-21 (1975).
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Rahway, N. J. (1976).
90. Rogers, Ian H. Secondary Treatment of Kraft Mill Effluents; Isolation
and Identification of Fish-Toxic Compounds and Their Sublethal
Effects. Pulp, Paper Mag. of Can. 74r,, 303-308 (1974).
91. Linko, R. R., P. Rantamaki and K. Urpo. PCB Residues in Plankton
and Sediment in the Southwestern Coast of Finland. Bull. Environ
Comtam. and Tox. 12 (6), 733-738 (1974).
92. Kornreich, M. B. Fuller, J. Dorigan, P. Walker and L. Thomas.
Environmental Impact of Polychlorinated Biphenyls. MITRE Tech.
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93. ETzerman, A. W. Surface Microlayer-Microcontaminant Interactions in
Freshwater Lakes. Ph D Thesis, Univ. of Wisconsin-Madison, W.
Chem. Prog. (1976).
94. Horn, W., R. W. Risebrough, A. Soutar and D. R. Young. Deposition
of DDE and Polychlorinated Biphenyls in Dated Sediments of the
Santa Barbara Basin. Science, 184, p 1197-1199, June (1974).
95. Dennis, D. S. Polychlorinated Biphenyls in the Surface Waters and
Bottom Sediments of the Major Drainage Basins of the United States.
Ref. 88, p 183-194.
96. Clegg, D. E. Chlorinated Hydrocarbon Pesticide Residues in Oysters
(Crassostrea commercial is) in Moreton Bay, Queensland, Australia,
1970-1972. Pest. Monit. J. 8(3) p 162-166. Dec. (1974).
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-------
97. Veith, 6. D. Baseline Concentrations of Polychlorinated Biphenyls
and DDT in Lake Michigan Fish, 1971. Pest Monit. J. 9(1), p 21-29,
June, (1975).
98. Lech, J. 0. and M. Melancon. Hazardous Chemicals in Fish. Inst.
for Envir. Studies, Envir. Monit. and Data Aquisition Group.
Univ. of Wisconsin-Madison, Bulletin #69 p 218-238, December (1976).
99. Choi, P. S. K., H. Nack, and J. E. Flinn. Distribution of Polychlorinated
Biphenyls in an Aerated Biological Oxidation Wastewater Treatment
System. Bull Env. Contam. and Tox. 11 (1) p 12-17 (1974).
100. Wisconsin Department of Natural Resources. Discharge Permit Files.
(1976).
101. U. S. Geological Survey. Water Resources Data for Wisconsin, Water
Year 1977. U. S. Department of Interior. (1978).
GPO B21«4ft11
-144-
-------
APPENDIX1A
COMPOUNDS IDENTIFIED BY GAS CHROMA-TOGRAPHY/MASS SPECTROMETRY
Explanation of table symbols
COMPOUND;
CD - if on the Environmental Protection Agency's Consent Decree Priority Pollutant List
P - Denotes having previously been reported in paper mill wastes
P/T - Denotes toxic compounds from paper mill wastes
Listed alphabetically except when grouped under Fatty Acids, Fatty Acid Methyl Esters, Resin Acids,
Resin Acid Methyl Esters, Resin Acids - Chlorinated, and Resin Acid Methyl Esters - Chlorinated
Listed as detected unless otherwise noted
DISCHARGER; See next page for list of industrial/municipal wastewaters, biota, or sediment analyzed by GC/MS
LOCATION; , "
a Denotes raw wastewater :
b Denotes after primary clarifier effluent
c Denotes lagoon effluent
d Denotes final effluent
EXTRACT:
1 pH greater than 11, methylene chloride-hexane; hexane or 94% hexane/6% ethyl ether florisil eluate
2 pH greater than 11, methylene chloride-hexanej 80% hexane/20% ethyl ether florisil eluate
3 pH less than 3, chloroform redissolved in acetone
4 pH less than 3, chloroform redissolved in acetone, methylated with methyl iodide and re-
extracted into hexane
5 pH less than 3, chloroform redissolved in acetone - without any prior basic extraction (1 sample)
IDENTIFICATION;
Lit. No. Denotes literature reference of mass spectrum used to compare with that from sample analysis
8 Pk Index Denotes Eight Peak Index of Mass Spectra, -2nd ed., 1974 8 most abundant ions
from literature compared with that from sample analysis
Standard A denotes commercially available compound!
Standard B denotes compound synthesized in our laboratory
Standard C denotes compound furnished by others previously reporting it
LITERATURE - PREVIOUS CITATION(S) OF COMPOUND;
(Ref. No., page) Number Listed in Bibliography (in cases of extensive citations, only representative
references are given). Almost all compounds detected in this study were cited in reference
50, which is only included in this table whenever no other references are listed for a compound.
-------
SAMPLES ANALYZED BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY
ENVIRONMENTAL MATRIX LOCATION EXTRACT
Industrial/rounicipal Wastewaters
1. Kimberly-Clark, Badger Globe, Neenah Papers b 2 & 4
d 1
d 3
2. Bergstrom Paper Company a 1
a 1
a 1
a 1
a 2
b 2
d 1
d 2
d 3 & 4
3. Neenah-Menasha Sewage Treatment Plant d 4
11. Consolidated Paper Company a 3 £ 4
d 5
12. Appleton Sewage Treatment Plant a 3
d 3
14. Kimberly Sewage Treatment Plant d 1
16. NCR Appleton Papers a 3 S 4
b 2
d 1
d 2
d 3
17. Thilmany Pulp £ Paper Company d 1
d 4
20. Wrightstown Sewage Treatment Plant d 2
24. American Can Company c 2
25. Proctor £ Gamble Company (Charmin) a 1
a 1
a 2
& 3
a 3
Biota.
Carp 1
Carp 1
Carp 2
Sediment 1
A-2
-------
APPENDIX A
.COMPOUNDS IDENTIFIED BY GAS CHROMATOGRAPHY/MASS SPECTRDMETRY
Available mass spectra of these compounds appear in Appendices D & E
COMPOUND
CD Acenapthene
Acetone, Tetrachloro-
P Acetovanillone
Aniline, Trichloro-
Anisole, Pentachloro-
CD Anthracene (or Phenanthrene ?)
Benzene, Dichloro-diethyl-
Benzoate, Dimethyl
Benzoate, Methyl methoxy-
Benzoic acid
Benzoic acid, [methyl ester
derivative]
Benzoic acid, Isopropyl- [methyl
ester derivative]
Benzophenanthrene, Methyl-
tor Benzanthracene, Methyl-?)
Benzophenone
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
2
11
11
16
17
1
2
1
17
1
11
11
16
12
16
16
11
1
25
b
a
d
a
d
b
b
b
d
b
carp
d
d
a
a
a
a
a
b
a
2
5
5
3
3
2
2
2
1
2
1
5
5
4
3-
3
4
4
2
2
Lit. 47, p. 79
8 Pk Index
Standard A
Standard A
Standard A
Standard A
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk Index
Lit. 47, p. 81
8 Pk Index
(41^,692),
(42,251),
(44,650) ,
(46,246)
(47A65)
(43,333),
(41^,692) ,
NONE
NONE
(50,11)
(51,525),
(52_,124)
NONE
(4JU691) ,
(48,583)
(33,62)
(43^,363)
(45,28)
(48,582-3)
(49,443)
(?)
(?)
(48,593)
, (53_,392)
(?)
(42,443)
-------
COMPOUND
Benzothiazole
(10-30 ug/L in final effluents)
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
Benzothiazole, Hydroxy-
(10-30 ug/L in final effluents)
Benzothiazole, Hydroxy- [methyl
ether derivative]
Benzothiazole, Methyl Thio-
(10-40 ug/L in final effluents)
Benzyl alcohol
Biphenyl
Biphervyl, Methyl-
Bisphenol A [dimethyl ether derivative}
(4,4' Isopropylidene diphenol)
Bisphenol A, Chloro- [dimethyl ether
derivative] (MW 290)
Bisphenol A, Dichloro- [dimethyl
ether derivative] (MW 324) (2 iso-
mers
1
1
2
2
12
16
16
16.
17
25
1
16
17
2
1
1
2
16
16
16
16
17
16
2
2
ive}
2
r
2
b
d
a
d
d
b
a
d
d
a
d
a
d
d
b
a
d
a
b
d
d
d
a
a
a
d
d
4 Standard A (53,389), (33,64)
3
2
3 & 4
3
2
3
2
3
3
3 Standard A NONB(?)
3
3
4
4 Standard A (54,211), (45,28)
3 (53,392)
4 ;
4 ;
2
1
2
3 & 4
3 8 Pk Index (49,440), (51,525),
(45_r74)
1 8 Pk Index (41,692)
1 8 Pk Index (41,692)
4 , Standard A (55,695)
4 Interpret. NONE(?)
Interpret.
Chem. Abs. 82:155630x
-------
I
en
COMPOUND
DISCHARGER LOCATION EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
p
CD
CD
CD
CD
CD
P
P
P
P
Bisphenol A, Tetrachloro- [dimethyl
ether derivative] (MW 392)
Bisphenol A, Trichloro- [dimethyl
ether derivative] (MW 358)
Borneol, Iso-
Caffeine
Camphor , Oxo-
Carbazole
Chlordane (isomer ?)
Chrysene
ODD
DDE
DDT
Dodecane
FATTY ACIDS
Heptadecanoic Acid [methyl ester
derivative}
Laurie Aeid
Myristic Acid
2
2
11
12
11
1
2
1
25
2
12
12
d.
d
d '
a
d
b
a
carp
b
2 carp
2 carp
carp
a
d
.a
a
4
4
5
3
5
2
1
2
2
1
1
1
1
4
3
3 ,
Interpret .
Interpret .
8 Pk Index
Standard A
8 Pk Index
8 Pk Index
Standard A
Standard A
Standard A
Standard A
Standard A
8 Pk Index
Standard A
8 Pk Index
V
g Pk Index
Chem. Abs. 82:155630
NONE(?)
(50,13)
(52,122), (51,526)
NONE(?)
(33,65)
(56,280), (57 )
(43,356), (58,333)
(49,443), (4^,692)
(56,280)
(58,333), (43,357)
<56,280)
(58,333)
(53,389), (33_,70)
(43,357)
(33,75), <44,651),
(45_,28) (5£,524)
(32^,21), (51,524)
(33,77), (44), (31^,2
P/T Oleic Acid [methyl ester derivative]
P Palmitic Acid
Palmitic Acid [methyl ester
derivative]
12
8 Pk Index
3 / 8 Pk Index
Standard A
(51^,524), (45_,27)
<33_,79) (5£) (4£)
(5d,524) (60_,37) (28_)
(33_,79)
(31,21) (61)
-------
3*
I
COMPOUND
P Stearic Acid
Stearic Acid [methyl ester
derivative]
FATTY ACID METHYL ESTERS;
P Palmitate, Methyl-
P Stearate, Methyl-
CD Fluoranthene
P Guaiacol
P/T Guaiacol, Dichloro- (2 isomers)
(2 isomers)
Guaiacol, Dichloro- [methyl ether
derivative] (3 isomers)
P/T Guaiacol, Tetrachloro-
(10-50 «g/L In final effluents)
Guaiacol, Tetrachloro- [methyl ether
derivative]
P/T Guaiacol, Trichloro- (1 isomer)
(10-60 ug/L in (2 isomers)
final effluents) (3 isomers)
Guaiacol, Trichloro- [methyl ether
derivative] (1 isomer)
(2 isomers)
Heptadecane
CD Hexachlorocyclohexane (lindane)
CD Hexachlorocyclopentadiene
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. Mo.,page)
12
24
2
12
11
17
11
11
11
2
11
2
11
2
11
11
2
11
16
14
2
c
a
a
d
d
d
a
d
d
d
a
d
a
d
d
a
2 carp
d
3
4
2
2
2
3
2
5
3
5
3
4
3
5
4
4
3
3
5
4
4
1
1
1
1
8 Pk Index
Standard A
Standard A
Standard A
Standard A
Standard A
Standard C
Standard C
Standard C
Standard C
Standard C
8 Pk Index
Standard A
Standard A
{61) (44) (51,524) (60,
(3.1,21)
(50,26)
(50,33)
37!
(49_,443) (4JU692) (33_,71)
(44,650)
(60_,28) (45_,27) (33^,72)
(61) (36_,19) (46,246)
(59) (62) (23-26) (28)
(46,246)
(59) (44,650) (62) (23-26)
(36,19) (63)
(28) (31) (46_,246)
(49^,445) (36_,19) (31)
(56_,280)
(57,736)
-------
COMPOUND
Hexadecane
Indole, Chloro- (isomer ?)
p-Menth-4ene-3-one
Naphthalene, Isopropyl-
Naphthalene, Methyl-
Nonadecane,
Octadecane
P Pentadecane
Phenanthrene, Methyl-
CD Phenol
DISCHARGER LOCATION
EXTRACT
IDENTIFICATION
LITERATURE
(Ref. No.,page)
Phenol, p-Tertiary Amyl-
CD Phenol, Chloro- [methyl ether
derivative]
Phenol, p- (oc-chloroethyl) -
Phenol, Decyl-
CD Phenol, Dichloro- (1 isomer)
(15-40 ug/L in i- isomers)
final effluents) (2 isomers)
Phenol, Dichloro- [methyl ether
derivative]
16
2
20
11
25
2
2
16
2
16
2
2
16
1
2
2
17
12
12
16
1
16
2
16
1
17
2
11
16
2
11
d
d
d
d
a
b
a
d
d
d
a
d
d
b
a
d
d
a
d
a
d
b
d
d
d
d
d
d
a
d .'
a
1
3
2
5
1
2
1
1
3
1
1
3
1
2
2
3
3
3
3
3
3
2
4
3
3
3
3
5
3
4
4
8 Pk Index
Standard A
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk index
.8 Pk Index
8 Pk Index
Standard A
8 Pk Index
8 Pk Index
8 Pk Index
8 Pk Index
Standard A
Standard A
(49,445) (33,73)
Chem. Abs. 83:131403v
NONE(?)
(33,75)
(49,440) (43,358) (33,76)
(53,392)
(33,78)
(49,445) (33,79)
(43,359) (33,80-1)
(49,443) (41, 692) (33,76)
(64,315) (45,27)
Q3_,81) (44,650)
NONE(?)
(52,140)
NONE(?)
(54,211)
(36,19) C
-------
COMPOUND
P Phenol, Ethyl- {isomer?)
Phenol, Nonyl-
(or Butylated Hydroxytoluene)
(3 isomers)
(3 isomers)
Phenol, Nonyl- [methyl ether
derivative] (3 isomers)
CD Phenol, Pentachloro-
Phenol, Pentaehloro- [methyl ether
derivative]
Phenol, Tetrachloro-2,3,4,6 or
2,3,5,6 isomer
Phenol, Tetrachloro- [methyl ether
derivative]
(2-20 ug/L in final effluents)
Phenol, Trichloro- (isomer ?)
(5-100 ug/L in final effluents)
Phenol, Trichloro- [methyl ether
derivative] (1 isomer)
(2 isomers)
Phenol, 2,4,5 or 2,3,4 Trichloro-
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
11
16
2
16
1
17
2
2
11
12
2
17
?
17
3
11
11
11
2
17
1
3
12
11
11
3
17
12
d
a
d
b
d
d
d
d
d
a
d
d
d
d
d
d
a
a
d
d
b
d
d
a
a
d
d
a
5 8 Pk Index (33,71)
3
2 8 Pk Index (33,78-9)
2
3
3
3
4
5 Standard A (51/525)
3
3 (58_,333) (5_5,697)
3
4 Standard A
4
4
5 Standard A (33_'83) (42_,251) (58,333)
3
4 Standard A
4
4
4
4
3 (SJL'333) (j5.3.'389) (42,251
3
4
4
3 Standard A
3
-------
I
vo
COMPOUND
Phenol, 2,4,5 or 2,3,4 Trichloro
[methyl ether derivative]
CD Phenol, 2,4,6 Trichloro
Phenol, 2,4,6 Trichloro- [methyl
ether derivative]
Phenol, Trichloro-dimethoxy-
Phenol, Trichloro-dimethoxy- [methyl
ether derivative]
Phenol, Undecyl-
Phenyl Decane
DISCHARGER LOCATION EXTRACT IDEMYIPICATIOW
17
16
11
2
2
16
d
a
d
d
d
a
4
3
5
3
4
4
Standard A
Standard A
Standard A
Phenyl dodecane
Phenyl Undecane
Phosphate, Tributyl-
1
17
2
2
2
2
12
2
2
2
2
12
2
2
2
12
12
2
d
d
d
a
a
a
carp
a
a
a
a
d
carp
a
. a
a
d
carp.
a
d
d
3
3
3
1
1
1
1
3
1
1
1
3
1
3
1
i
3
I
3=
3
3 & 4
Interpretation
Interpretation
8 Pk Index
8 Pk Index
8 Pk Index
8 Pfe Index
8 Pk Index
LITERA9RJRE
(Ref. Ho.f
(62)(36,19) (46,246) (53,392)
NONE(?)
NONE(?)
NONE(?)
NONE(?)
NONE(?)
NQNE(?)
(49_,445) (53_,387) (43^,363),
-------
COMPOUND
CD Phthalate, Dibutyl-
CD Phthalate, Diethyl-
CD Phthalate, Dioctyl- (isomer ?)
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
CD
Polychlorinated Biphenyls
(2-7 chlorine isomers)
CD
P/T
P/T
Propan-2-one, 1-(4~hydroxy-3-methoxy
phenyl) (or guaiacyl acetone)
Pyrene
RESIN ACIDS
6,8,11,13 Abietatetraen-18-oic Acid,
[methyl ester derivative] (MW 312)
Dehydroabietic Acid, (MW 300)
(100-8500 u.g/L in final effluents)
Dehydroabietic Acid [methyl ester
derivative] (MW 314)
1
12
25
25
24
2
2
16
12
12
25
2
2
2
2
2
y
11
i
b
a
a
a
t carp
c
a
a
d
a
a
a
a
d
! a
a
2 carp
sediment
carp
b
a
b
2 , Lit. 47, p. 88
3
1 Lit. 47, p. 88
2
1 Standard A
2
2
3 & 4 «
2
3
3 & 4 .
3
1 Standard A
1
1
1
1
1
2
2
3 8 Pk Index
2 Standard A
(4£,445) (5.1,525) (_56_,28
(51,525)
(5a,525) (48,583)
(6.1,833) (56,283)
(65) ; (66J ;
(67) (68) (49_,441) (69)
(5_0_,30)
(49,443) (41,692)
2
11
11
2
17
16
11
d
d
d
a
d
d
a
a
3
5
3
4
4
4
4
Lit. 72 & (45_,
151) "
Standard C
(33_,62) (44_,650) (45_,29)
(70) , (61) (44) (21.) (29_,4)
(5£) (60_,37) (45_,29)
(^3_,66-7) (23-28)
(30) (31,21) (71)
Standard C
-------
COMPOUND
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
P/T
P/T
P/T
P/T
P/T
P/T
P/T
P
P
8,15 Isopimardien-18-oic Acid,
[methyl ester derivative] (MM 316)
Oxo-dehydroabietic Acid, [methyl ester
derivative] (MW 328)
Pimaric Acid (MW=302)
Pimaric Acid, [methyl ester derivative]
(MW 316)
Sandaracopimaric Acid, [methyl ester
derivative] (MW 316)
RESIN ACID, METHYL ESTERS:
Methyl dehydroabietate
RESIN ACIDS, CHLORINATED:
Chlorodehydroabietic Acid, [methyl
ester derivative] (MW 348)
(2 isomers)
Dichlorodehydroabietic Acid, [methyl
ester derivative] (MW 382)
RESIN ACID METHYL ESTERS, CHLORINATED:
Chlorodehydroabietate, Methyl
Dichlorodehydroabietate, Methyl
Salicylic Acid, [methyl ester
derivative]
Syringaldehyde
2
2
2
2
2
24
11
2
2
24
24
16
11
16
25
d
d
d
d
d
c
d
d
d
c
c
a
d
a
a
4
4
3
4
4
2
5
4
4
; 2; '.
2
4 -
5
3 & 4
3
Lit. 72^
Lit. 61, 835
(29,
(61)
3)
(24_,35 + 59)
(45,29) (27) (28)
(30)
(59) (60,37)
Lit. 72 &
(45., 49)
Lit. 72 &
(45,50)
Standard C
Standard C
Standard C
Standard C
Standard C
8 Pk Index
Standard A
(61)
(28.)
(27.,
(59)
(59_)
(5^,
(33_,
(60,37) (45,
(29_,4) (30)
130)
(29i,21)
(29_,4)
29) (27)
(23-26) (28) (63)
(23-26) (28)
NONE(?)
NONE(?)
526)
83) (45,28)
(63.)
-------
I
rv>
COMPOUND
I
Syringaldehyde, Chloro-
Tetradecane
Toluene, Dichloro-
Toluene, Trichloro-
Vanillin
DISCHARGER LOCATION
EXTRACT IDENTIFICATION
LITERATURE
(Ref. No.,page)
Vanillic Acid, [methyl ester
derivative]
Veratrole, Dichloro- (isomer ?)
or (Dimethoxybenzene, Dichloro-)
Veratrole, Trichloro- (isomer ?)
Xylene, Dichloro-
Xylene, Trichloro- or
(trichloroethyl benzene ?)
25
16
2
2
2
2
11
17
16
11
25
17
1
2
2
2
2
2
2
2
a
a
d
a
a
d
d
d
a
a
a
d
b
d
d
d
a
b
d
a
3
1
1
1
1
3
5
3
3
3
3
4
2
2
2
I
I
2
1
1
Standard B
8 Pk Index
Standard A
Standard A
Standard A
8 Pk Index
Lit. 61, p. 835
Standard C
Standard A
8 Pk Index
NONE?
(33_,84) (43_, 359)
(42,251)
NONE?
(44,650) (45,28) (46,246)
(3_3_,85)
(45_,28) (55_,697) (46_,246)
(47,102) (50,491)
(42^251) (50,491)
NONE(?)
(50_,36)
-------
APPENDIX B *
UNIDENTIFIED COMPOUNDS CHARACTERIZED BY GAS eHRQMATOGRAPBY/MASS SPECTROMETRY
Available mass spectra of these compounds appear in Appendix F
LITERATURE
COMPOUND DISCHARGER LOCATION EXTRACT (Ref. No.,page)
Unidentified Resin Acid, [methyl ester
derivative] (MW 316) 2 d 4
Unidentified Resin Acid, [methyl ester
derivative] (MW 318) 2 d 4
Unidentified Resin Acid, [methyl ester
derivative] (MW 328) (2 isomers) 2 d 4
Unidentified Chloro Resin Acid, [methyl ester
derivative] (MW 362)- 1 d 4
Either C^H 0 or C^H compound with an 2 ". a 1 (45,27)
apparent molecular weight of 196, 2 isomers 2 d 1 (40,204)
2 a 1
2 a ,: 1
16 d 1
2 carp 1
25 a 1
carp , 2
1 b . 2
2 b 2
2 a 2
2 d -.-' 2
2 d '"' 3
1 d 3
12 a , -. 3
12 d '; : 3
Monochloro compound with an apparent molecular 2 = a 1
weight of 230 probably ,2 d I 1
above chlorinated (several isomers) 2 a ; ;' 1
2 a ' 1
2 a 1 .
2 carp 1
2 b 2
-------
LITERATURE
COMPOUND DISCHARGER LOCATION EXTRACT (Ref. No.,page)
Dichloro compound with an apparent molecular 2 d 1
weight of 264 probably unknown MW 196 2 a 1
compound chlorinated (several isomers) 2 a 1
2 a 1
2 a 1
carp 1
Trichloro compound with an apparent molecular 2 d 1
weight of 298 probably unknown MW 196 2 a 1
compound chlorinated (several isomers) 2 a 1
2 a 1
2 a 1
Nonhalogenated, with an apparent molecular 2 a 1
weight of 238 2 b 2
2 d 3
carp 2
Monochloro compound with an apparent molecular
I weight of 272 probably unknown MW 238 2 a 1
chlorinated
Dichloro compound with an apparent molecular 2 a 1
weight of 306 2 a 1
Nonhalogenated compound with an apparent 2 a 2 (22)
molecular weight of 272 diterpene related 17 d 1
earp 1
Nonhalogenated compounds with an apparent 2 carp 1 (27-28)
molecular weight of 286 apparently diterpene carp 2
alcohols (up to 7 isomers) 2 a 2 (30)
2 d 2
2 d 3
12 d 3
Monochloro compound with an apparent molecular
weight of 320 2 d 2
Monochloro compound with 339-41 ion cluster 24 c 2
Monochloro compound with 168-70 ion cluster 25 a 1
Monochloro compound with 230-2 ion cluster 25 a 3
-------
LITERATURE
COMPOUND DISCHARGER LOCATION EXTRACT (Ref. No.,page)
Cl IU-LJI u:-j-r ' ' " " 7 ~"' "±' ^ " '- - ' ' .,.......-
3
g Monochloro compound with 244-6 ion cluster 25 a 3
* Dichloro compound with 193-7 ion cluster 25 a 3
" Dichloro compound with 202-6 ion cluster 2 d 3
LO
-------
APPENDIX C
RELATIVE RETENTION TIME INDEX OF
COMPOUNDS/DERIVATIVES IN ACID EXTRACTS
Though similar in polarity to the common higher-loaded Carbowax 20M
column packings, the low-loaded, thermally treated, and deactivated
Ultra-Bond 20M column packing has not been extensively used in
environmental analysis. The reports of Aue (37) and Karasek and
Hill (38) provide the basis for the recent commercialization of this
column packing. Because of our unfarailiarity with the elution
characteristics of this packing, Appendix C provides a tabulated
retention time index relative to aldrin for eluting times of compounds
or derivatives extracted from the acidic fraction. This column packing
resolved pentachloroanisole from tetrachloroveratrole, which was not
possible with 3% OV-17, 6% SP-2401/4% SE-30, or 3% S.P-2100 column packings,
C-l
-------
APPENDIX C
.- Relative Retention Time Index of Compounds/Derivatives in Acid Extracts
GLC Column: 3 a x 2mm i.d. Ultra-Bond 20M 100/120 mesh, temperature programmed
110-250°C at 4°/min, helium flow ca. 15-20 mL/min
Relative retention time index ==
retention time of compound
retention time of aldrin
Retention time of aldrin ca. 14 minutes
Congound/Derivative_
Chloroanisole-(isomer?)
Methyl benzoate
Tetrachloroacetone
Methyl salicylate
Trichloroanisole-(2,4,6)
Guaiacol
Benzyl alcohol
Dichloroanisole-(isomer?)
Benzothiasole
Phenol
Dimethylbenzoate
Tetrachloroanisole-(isomer?)
Dichlorophenol-(isomer?)
Methyl methoxybenzoate
Dichlorophenol-(isomer?)
Ethyl phenol
Nonyl anisole-(isomer?)
Nonyl anisole-(isomer?)
Trichlorophenol-(2,4,6)
Pentachloroanisole
Tetrachloroveratrole
Methyl thiobenzothiazole
Trichloroveratrole-(isomer?)
Benzoic acid
Trichloro-trimethoxybenzene
RRT Index
MW
Significant ions
nj' Ion(s) searched by LMRGC
0.12
0.13
0.15 .,
0.20
0.21
0.22
0.23
0.26
0.27
0.31
0.38
0.42
0.42
0.44
0.51
0.53
0.55
0.57
0.66
0.68
0.73
0.74
0.76
0.78
0.79
142
136
194
152
210
124
108
176
135
94
150
244
162
166
162
124
234
234
196
278
274
181
240
122
270
«w
142
136
83
92
195, 197
109
79
133, 135
135
taBW
94
119, 91,
244, 246
162
135
162, 164
107
149
121
97, 99,,
278, 280
259, 261
148
225, 227
105
270
, 85
, 120
, 210
, 124
, 108
, 161
, 108
117,
., 248
., 164
, 166
, 63,
, 122
, 121
, 163
196,
, 282
, 263
, 181
mUWMNlM
, 240
, 122
, 272
, 212,
, 81
, 168,
150
, 201,
98
198
, 284
, 274,
., 108
, 242
, 77
, 274
167, 169
176, 178
203, 205
276, 278
C-2
-------
-2-
Dichloroguaiacol-(isomer?) 0.87
Methoxybenzothiazole 0.89
Trichlorophenol-(2,4,5 or
2,3,4)
Vanillin
Dichloroguaiacol-(isomer?)
Methyl palmitate
ALDRIN (External Standard)
Acetovanillone
Tetrachlorophenol-(2,3,4,6
/ or 2,3,5,6)
Trichloroguaiacol-(isomer?)
Methyl heptadecanoate
Laurie Acid
Methyl oleate
Trichloroguaiacol-(isomer?)
Methyl stearate
Trichloroguaiacol-(4,5,6)
8,15 Isopimardiene-18-oate
Syringaldehyde
Myristic acid
Methyl pimarate
Methyl sandaracopimarate
Tetrachloroguai aco1
Bisphenol A-dimethyl ether
derivative
Pentachlorophenol
Unidentified Resin Acid
Methyl Ester (RAME) 1.53
Chlorosyringaldehyde 1.54
Caffeine 1.60
Unidentified RAME 1.64
Methyl dehydroabietate 1.65
Palmitic acid 1.68
6,8,11,13 Abietatetraen-
18-oat$ 1.71
Hydroxy-benzothiazole 1.72
206 ' 192, 194
165 136, 165
0.90
0.93
0.97
0.98
1.00
1.03
1.06
1.08
1.13
1.16
1.27
1.27
1.30
1.34
1.36
1.38
1.40
1.41
1.44
1.45-
1.48
1.48
196
152
192
270
362
166
230
226
284
200
296
226
298
- '226
316
182
228
316
316
260
256
264
97, 99, 196., 198
151, 152
177, 179, 149, 151, 192, 194
74_, 87. ... 270
66_, 261, 263, 265
151, 166
230, 232, 234, 236 -
226, 228, 230
74, 87, ... 284
73, 60, ... 200
55,, 74_, 83, ... 296
211, 213, 226., 228
74_, §7, ... 298
226, 228', 230
91, 105, 241, 316
182, 181, 65, 93, 96, 111
73, 60, 129, ... 228
121, 180, 241, 301, 316
121, 301, 316
- -2-60~,< 262, 264
241, 256
264, 266, 268, 270, 165, 167
316 91, 105, 119, ... 241, 257,
301,,316
216 ' 216, 215, 218, 127, 130
194 109, 194
328 253, 313, 328
314 239, 299, 314
256 73, 129, ... 256
312 237, 195, 197, 312
151 151, 96, 123
C-3
-------
Unidentified RAMS
1.76
32S
253, 313, 328
Dichloro-Bisphenol A-dimethyl
ether derivative (?)
Dehydroabietic acid
Chloro-bisphenol A-dimethyl
ether derivative (?)
Chloro-RAME
Chloro-methyl dehydroabietate
isomer A
Stearic acid
Chloro-methyl dehydroabietate
isomer B
Tetrachloro-Bisphenol A-
dimethyl ether deriv. (?) 2.04
Dioctyl phthalate
Trichloro-Bisphenol A-dimethyl
ether derivative (?)
Dichloro-Bisphenol A-dimethyl
ether derivative (?)
Dichloro-methyl dehydro-
abietate
Methyl oxo-dehydroabietate
Chlorinated compounds
Phthalates
Methyl esters of fatty acids
Resin acids (screened for)
Methyl esters of resin acids (RAME)
1.78
1.80
1.81
1.86
1.91
1.93
1.96
2.04
2.06
2.07
2.10
2.13
2.18
324
300
290
362
348
284
348
392
390
358
324
382
328
309, 311, 313, 324, 326
239, 285, 300
275, 277, 290, 292
287, 289, 347, 349, 362, 364
273, 275, 333, 335, 348, 350
55, 73, 129, ... 284
273, 295, 333, 335, 348, 350
377, 379, 381, 383, 392, 394,
396
149, 167
343, 345, 347, 358, 360, 362
309, 311, 313, 324, 326
307, 309, 311, 382, 384
253, 269, 296, 313, 328
35-36
149
74+87
300-302
121, 239, 241, 253, 312, 314,
316, 318 + 328
(?) - Tentative Identification
C-4
-------
APPENDIX D ... , '
MASS SPECTRA OF SAMPLES COMPARED WITH STANDARDS
Appendix D includes many of the mass spectral comparisons of sample spectra
with standard spectra. In the comparison of mass spectra of pentachloroanisole
(page D-3) in Mill 1 with that of a standard, it should be noted that
its presence in the sample was quantitated by GC/EC at 80 ng/L (0.08 ug/L).
The amount injected into the GC/MS for the mass spectrum of this sample was
ca. 8 ng.
D-l
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
Q
or
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PERCENTAGE OF TOTAL
PERCENTAGE OF TOTAL
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF TOTAL
cn
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
1
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PERCENTAGE OF BASE PEAK
A , i , i 1 J u i a
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6T-Q
PERCENTAGE OF BASE PEAK
PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
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-------
o
to
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CO
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PERCENTAGE OF BASE PEAK
PERCENTAGE OF BASE PEAK
CO
Q
err
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PERCENTAGE OF TOTAL
PERCENTAGE OF TOTAL
-------
V
10
LOO STANDARD TETRACHLORO VERATROLE
0,
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in
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF BASE PEAK
M
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PERCENTAGE OF BASE PEAK
PERCENTAGE OF BASE PEAK
Q CO
a a
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-------
APPENDIX E
MASS SPECTRA OF COMPOUNDS IDENTIFIED BY LITERATURE COMPARISONS
Appendix E includes some comparisons between sample spectra and those
from the literature. Also included is a comparison spectra of chlorosyringaldehyde
present in a sample with spectra of a reaction product synthesized in
our laboratory. Chlorosyringaldehyde has not been previously reported
in'the environment. It was found in an acidic fraction of'a. sample from ...' '
Mill 25, location A (influent to wastewater treatment),together with
syringaldehyde, a common degradation product of hardwood lignin (Sarkanen,
(39). To confirm the mass spectrum of chlorosyringaldehyde (E-17), the
chlorination of syringaldehyde was attempted in our laboratory. A
commercial standard of syringaldehyde was added to a solution of 5.25%
sodium hypochlorite (commercial bleach) in aqueous acetic acid. The
reaction proceeded overnight, after which time the reaction product was
extracted with dichloromethane, evapo-concentrated to dryness redissolved
in acetone, and then injected into the GC/MS. A total ion chromatogram
indicated both unreacted syringaldehyde and newly formed chlorosyringaldehyde.
Not only did the retention times of these compounds match those present
in the sample, but the mass spectra also were closely matched. The
apparent isotopic molecular ions of chlorosyringaldehyde (page E-17) at
rn/z 216 and 218 are consistent for a compound with one chlorine atom.
The two ions as well as the fragment ions m/z 215, 201, 173, 145, 130,
127 and others have been shifted 34 mass units higher, which is consistent
with the addition of a chlorine atom at one of the two remaining reactive
sites on the ring. A very small"of dichlorosyringaldehyde was also
detected in the reaction product, but was not found in the sample.
E-l
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100 MILL NO. 2 LOCATION d
w
d.
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PQ
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$2;
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100
150
200
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280 3
[iiniin
DO
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srsri
Tentative Identification METHYL 6,8,11,13-ABIETATETRAEN-18-OATE
Keith, L.H. (Ed»). Analysis of Organic Compounds in Two Kraft Mill Wastewaters,
EPA Report No. 660/4-75-005, 99 p. June (1975).
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PERCENTAGE OF TOTAL
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100
MILL NO. 16 LOCATION a
-
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Tentative Identification BENZYL ALCOHOL
Based on Tabular Data From:
Mass Spectrometry Data Centre.
Eight Peak Index of Mass Spectra. 2nd ed. Vol. 3, Page 2105.
Mass Spectroraetry Data Centre, Aldermaston, U.K. (1974).
FRAGMENT IONS 79 108 107 77 51 91 78 50
PERCENT OF BASE PEAK 100 87 69 55 22 19 11 10
-------
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PERCENTAGE OF BASE PEAK
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PERCENTAGE OF TOTAL
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to
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J
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CH
^iiil|lmililiprii\nl^»U>|li\UitHn»it'
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150
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3
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Tentative Identification CAFFEINE
Based on Tabular Data From:
Mass Spectrometry Data Centre,
Eight Peak Index of Mass Spectra.- 2nd ed. Vol. 1, Page 86*8.
Mass Spectrometry Data Centre, Aldermaston, U.K. (1974).
FRAGMENT IONS 194 109 55 67 82 15 18 42
PERCENT OF BASE PEAK 100 , 59 37 23 18 . 15 11 11
-------
W
GO
100 MILL NO. 1 LOCATION b
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cu
CO
O
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100
150
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M/Z
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Tentative Identification CARBAZOLE
Based on Tabular Data From:
Mass Spectrometry Data Centre.
Eight Peak Index of Mass Spectra. 2nd ed. Vol. 3, Page 2^57.
Mass Spectrometry Data Centre, Aldermaston, U.K. (1971).
FRAGMENT IONS 167 166 139 168
PERCENT OF BASE PEAK 100 26 17 16
11
83.5 70.5 63
954
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G S CSI
W fu,
:Ǥ
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H,
CD
3
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(D
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H-
est Products Laboratory, Madison, WI 17H p. (1971).
Resonance, Ultraviolet Spectra and Gas Chromatographic Retention Data (of the Methyl Esters).
.F. , L. Zank and M.F. Wesolowski. Diterpene Resin Acids A Compilation of Infrared, Mass, Nuclear
m/e
Identification 8,15-ISOPIMARADIEN-18-OATE
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w
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150 200 , 250 280 30C
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Tentative Identification 8,(14),15-ISOPIMARADIEN-l8-OATE
Keith, L.H. (Ed.). Analysis of Organic Compounds in Two Kraft Mill Wastewaters,
EPA Report No. 660/1-75-005, 99 p.-June (1975).
-------
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PERCENTAGE OF BASE PEAK
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Tentative Identification U-HETHYL PHENANTHRENE
Based on Tabular Data From:
Mass Spectrometry Data Centre.
Eight Peak Index of Mass Spectra. 2nd ed. Vol. 2, Page 864.
Mass Spectrometry Data Centre, Aldermaston, U.K. (197H).
FRAGMENT IONS 192 191 189 165
PERCENT OF BASE PEAK 100 66 31 15
163
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APPENDIX F
MASS SPECTRA OF COMPOUNDS NOT IDENTIFIED
Appendix F contains mass spectra of several unidentified compounds.
Included are two similar non-chlorinated compounds with an apparent
molecular weight of 196 (page F-4 and F-5). These two apparent isomers
were often present when other chloro-organic compounds having one to
three chlorines with apparent molecular weights of 230 (pages F-6, 7, 8,
and 9), 254 (pages F-10, 11, and 12) and 298 (pages F-13 and 14) were
found. Mass spectra reported by Fetizon et al. (40) suggest the non-
chlorinated compounds might be diphenylacetaldehyde, trans-stilbene
oxide, or a related compound. Additional mass spectra included in this
appendix show apparent compounds with molecular weights of 290 (page F-
15), 324 (page F-16), 358 (page F-18) and 392 (page F-19). These might
be chloro-'bisphenol A dimethyl ethers which eluted in a methylated
acidic fraction of Mill 2 (page F-3). Compared with the spectra in
Appendix D (page D-10) for bisphenol A dimethyl ether, the spectra of
the chlorinated compounds have base peaks and apparent molecular ions
shifted 34 mass units higher for each additional chlorine.
The mass spectrum in this appendix (page F-20), which has the isotopic
clusters for three chlorine atoms with apparent isotopic molecular ions
at m/z 270, 272 and 274,might represent trichloro-trimethoxy benzene.
Before methylation, the spectrum for this compound was not detected. '
Instead, a later-eluting compound with apparent isotopic molecular ions
m/z 256, 258 and 260 was detected, suggesting trichloro-dimethoxy phenol
which is a more polar compound. By comparing the mass spectrum in this
appendix (page F-20) with that of 3, 4, 5 trichloroveratrole in Appendix
D (page D-25), the same initial losses of M-15, M-43 and M-58 are apparent.
F-l
-------
Additionally., this compound eluted just after tri chl oroveratrol e in the
same methylated acidic fraction of Mill 2 (page F-3).
Also included in this appendix are two isomers of an apparent resin
acid methyl ester (page F-21 and 22) and a possibly related chlorinated
compound (page F-23). The mass spectra of these two apparent isomers
are virtually identical, having an apparent molecular ion of m/z 328
and losses of M-15 and M-75. These two compounds are also very similar to
methyl-oxo-dehydroabietate listed in Appendix E (page E-10), except
the fragment ions m/z 259 and 296 are missing from them. Ion m/z 259
is consistent for the loss of the carbomethoxy group (COOCH^'}. Ion
m/z 296 appears to indicate a loss of 17 (OH') from m/z 313 which is the
(M-CHg") fragment. Since the two compounds eluted much earlier than
methyl-oxo-dehydroabietate but soon after methyl dehydroabietate, we
hypothesize they might represent ethyl dehydroabietate, which would also
have a molecular weight of 328. This hypothesis remains unproven at
the present time.
F-2
-------
COMPOUNDS
TOTAL ION CHROMATOGRAM : METHYLATED ACID EXTRACT OF A PAPER MILL EFFLUENT
Column Conditions: Ultra-Bond 20M, 3m x 2mm,
temperature programmed 110-250°C @ 4°C/min. (or 35 minutes
30
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