INDUSTRIAL POLLUTION OF THE
LOWER MISSISSIPPI RIVER
IN LOUISIANA
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Region VI Dallas, Texas
SURVEILLANCE AND ANALYSIS DIVISION
April 1972
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INDUSTRIAL POLLUTION
OF THE
LOWER..MISSISSIPPI RIVER IN LOUISIANA
ABSTRACT
Waste waters from 60 industries discharging to the
Mississippi River from the Baton Rouge area to its
mouth have been analyzed and found to contain organic
chemicals and toxic metals in high concentrations.
Municipal wa-tfer supplies were found to contain
organic compounds in trace amounts which are believed
to be the cause of the off-flavors in these supplies,
and which may present a potential threat to the
health and wellbeing of the consumers. Fish exposed
to the river water developed objectionable tastes
within seventy-two hours. Violations of taste and
odor criteria in the river and in fish flesh were
identified.
United States
Environmental Protection Agency
Region VI
Dallas, Texas
Surveillance & Analysis Division
April 1972
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FOREWORD
In 1967, at the time this study was requested by
the State of Louisiana, concern had developed over the
quality of the Mississippi River water as a drinking
water supply. Complaints of off-flavors - variously
described as "oily" or "chemical" - in the drinking water
of New Orleans and nearby communities were occurring with
increasing frequency- Fishermen were finding that fish
caught in the reach of the river below Baton Rouge were
no longer saleable because of these same bad tastes.
The deterioration of the water quality in the river
closely paralleled the explosive development of a petro-
chemical industrial complex which began in the middle
1950's and which by the end of the 1960's had resulted
in the location of over 60 major industries from Baton Rouge
to the mouth of the river. Most of the industries discharged
their partially treated or untreated wastes to the river.
As this investigation progressed from 1969 through 1971,
results of the findings were made available to industry.
This factor, coupled with a complete review of all industrial
waste permits by the State of Louisiana and the initiation
of the Refuse Act Permit Program jointly by the Environmental
Protection Agency and the Corps of Engineers, resulted in
the beginning of an active program by industry to reduce
the waste discharges to the River. Some of the immediate
improvements are reflected in the data in this report. Fur-
ther substantial improvements in the quality of the waste
discharges are expected within the next two to three years
as the ongoing waste abatement programs are developed and
completed.
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CONTENTS Page
FOREWORD i
LIST 'OF TABLES v
LIST OF FIGURES vii
INTRODUCTION 1
Authority 2
Scope 2
Objectives 2
Acknowledgements 3
SUMMARY OF FINDINGS 4
CONCLUSIONS 7
RECOMMENDATIONS 8
I. DESCRIPTION OF STUDY AREA AND PERTINENT PROBLEMS 11
II. EVALUATION OF THE POLLUTION POTENTIAL OF
INDUSTRIAL WASTE DISCHARGES 14
Determination of Water & Waste
Characteristics 14
Toxic Substances 16
Heavy Metals, Cyanides & Phenol 16
Lead 17
__.__Ť__________ ___ __ _ _ _ _ ^ j
. *") A
. Łt_^
Cadmium 24
Chromium 26
Arsenic 27
Mercury 29
Cyanides 31
Phenols 32
Total Solids 32
Trace Heavy Metals in Phosphate
Rock Waste 38
Organic Chemicals 39
Taste and Odor 48
Tainting of Fish Flesh 52
Toxicity of Selected Organic Chemicals 64
III. WATER QUALITY STANDARDS VIOLATIONS 86
IV. INDUSTRIAL WASTE TREATMENT 88
REFERENCES 101
11
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CONTENTS (Continued Page
APPENDIX 109
LIST OF FIGURES 11°
LIST OF TABLES HI
EXHIBIT A - Letter to Commissioner James M.
Quigley, Commissioner, Federal
Water Pollution Control Adminis-
tration, U. S. Department of the
Interior from Leslie L. Glasgow,
Chairman, Louisiana Stream
Control Commission 112
EXHIBIT B - Location Map 114
EXHIBIT C - Plant Locations (Schematic) 115
EXHIBIT D - Analytical Techniques 116
1. Raw and Finished Water 116
Mega Sampling 116
Carbon Drying 116
Mega Extraction 116
Fractionation and Identification
of Organics in Carbon-Chloroform
Extract 117
2. Industrial Wastes 117
Sampling Procedures 117
Organic Analysis 117
Other Parameters 120
Methodology Used in Organic
Identifications 120
EXHIBIT E - Threshold Odor 122
Scope and Application 122
Summary of Method 122
Sample Handling and Preservation 122
Interferences 123
Apparatus 123
Reagents 124
Precedure 126
Calculations 129
Precision and Accuracy 131
References 131
111
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CONTENTS (Continued) Page
EXHIBIT F - Analytical Results 132
Detection Limits 137
EXHIBIT G - Industrial Waste Threshold Odor
Numbers and Odor Contributions 139
IV
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LIST OF TABLES Page
1. Raw and finished water mega samples collected 15
2. Industries having heavy metals discharges five
pounds per day or greater 18
3. Industries discharging phenolics in quantities
of ten pounds per day or more 33
4. Industries with high solids loads, total solids
50,000 pounds per day or more, volatile solid
25,000 pounds per day or more 35
5. Organic compounds in the finished water at the
Public Health Service Hospital at Carville, La.,
and identified in wastes of specified industries 49
6. List of all organic compounds found in the U. S.
Public Health Service Hospital finished water 41
7. Organic compounds found in the Carrollton Water
Plant (New Orleans) finished water and identified
in wastes of specified industries 42
8. List of all organic compounds found in the
Carrollton Water Plant (New Orleans)
finished water 43
9. Organic compounds in the raw water at the
Jefferson Parish #2 Water Plant and identified
in wastes of specified industries 44
10. List of all organic compounds found in the
Jefferson Parish #2 Water Plant - raw water 45
11. Industries with high organic waste loads,
Chemical oxygen demand 40,000 pounds per day
or more, Total organic carbon 20,000 pounds
per day or more 46
12. Raw river water, 1969 threshold odors 49
v
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LIST OF TABLES (Continued) Page
13. Station Locations, Lower Mississippi River
fish tainting study, October-November 1971 58
14. Station data, Lower Mississippi River fish
tainting study 59
15. Flavor (fish) and threshold odor (water)
data, Lower Mississippi River fish tainting
study " ~"~~ ol
16. Organic chemicals isolated from raw &
finished waters and industrial wastes 70
17. Mammalian chronic toxicity of organic
pollutants found in finished water from
Carrollton and U. S. Public Health
Service Hospital 75
18. Acute toxicity of organic pollutants 78
19. Carcinogenicity in mammals of organic
pollutants in water supplies 82
20. Proposed or existing industrial waste
treatment 89
VI
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LIST OF FIGURES Page
I Fish Flavor Scores 62
II River Water Threshold Odor Scores 63
vii
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INTRODUCTION
In the spring of 1964, a conference on pollution
of interstate waterways of the Lower Mississippi River
and its tributaries was called by the Secretary of Health,
Education, and Welfare. The Secretary, "...having reason
to believe that pollution of the Mississippi River was
responsible for recent (1963-64) fish kills and was endan-
gering the health and welfare of persons in States other
than those in which the discharges originate" caused a
conference to be convened on May 5 in the Federal Office
Building, New Orleans, Louisiana. The conferees, repre-
senting the states of Louisiana, Mississippi, Arkansas,
Tennessee, and the Federal Government met for two days to
review evidence related to the alleged pollution. The
conference adjourned after adopting a set of conclusions
and recommendations which have been reported elsewhere (65).
Of principal interest here is Recommendation No. 3 which
says, "A technical committee composed of the conferees or
their designees be established to direct and advise in the
identification and abatement of all sources of pollution
affecting the main stream of the Lower Mississippi. The
Department of Health, Education, and Welfare will partici-
pate and aid in the investigation project."
On March 23, 1967, Dr. Leslie L. Glasgow, Chairman of
the Louisiana Stream Control Commission, wrote to Mr. James
M. Quigley, Commissioner, Federal Water Pollution Control
Administration, U. S. Department of the Interior, requesting
technical assistance (see Appendix, Exhibit A). In response
to this request, and in compliance with Recommendation No.
3 of the 1964 Enforcement Conference, a project plan was
prepared, approved and field work started in early 1969.
This report presents the results of this study and is con-
sidered to respond both to Recommendation No. 3 of the 1964
Conference insofar as it pertains to Louisiana and to Dr.
Glasgow's request of 1967.
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AUTHORITY
The study reported herein is authorized by the Federal
Water Pollution Control Act, as amended, Section 5 (b) and
Section 10 (d).
SCOPE
The study area comprises the main stem of the Lower
Mississippi River from St. Francisville, Louisiana, near
the Mississippi-Louisiana state line, downstream to Venice,
Louisiana (see Appendix, Exhibit B). The period covered
extends from January 1969 through June 1971.
OBJECTIVES
The general objective of the study is to determine
water quality degradation in the Lower Mississippi River
Basin through the identification of hazardous industrial
wastewaters which endanger human health and the health of
the aquatic biota and cause off-flavors in food fish and
drinking water supplies.
Specific objectives are to:
1. Evaluate the pollution potential of industrial
discharges from St. Francisville, Louisiana, to
Venice, Louisiana.
2. Identify drinking and stream water quality
standards violations.
3. Support - by providing technical data - state
action, and subsequent federal action, if
necessary, to stop violations of standards
and abate pollution.
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ACKNOWLEDGEMENTS
Special appreciation is expressed to Dr. A. A. Rosen
and his staff at the Federal Water Quality Laboratory in
Cincinnati for consultation, guidance, staff training,
and the loan of equipment. The cooperation and assistance
of the Executive Secretary of the Louisiana Stream Control
Commission and his staff contributed greatly to the success
of this study. Assistance was also provided by The Dow
Chemical Company, Midland, Michigan, in the analysis of
special samples and by the managers and environmental
engineers of the industries discharging to the Lower Missis-
sippi River. Consultation, advice, and analytical support
were provided by personnel of the Robert S. Kerr Water
Research Center, Ada, Oklahoma, the Analytical Quality
Control Laboratory, the Robert A. Taft Engineering Center,
and National Field Investigation Center, all in Cincinnati,
Ohio, and the Southeast Water Laboratory in Athens, Georgia,
and the Bureau of Sport Fisheries and Wildlife, Denver,
Colorado. To all of these and to all others who participated
in this study we extend our sincere thanks.
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SUMMARY OF FINDINGS
1. Liquid wastes from sixty major industries discharge
to the Lower Mississippi River in Louisiana in a two
hundred and fifty-eight mile stretch between St. Francis-
ville and Venice.
2. The Mississippi River in this reach serves as the
source of raw water for forty water utilities that provide
water for approximately 1.5 million people.
3. Cyanides, phenols, arsenic, lead, cadmium, copper,
chromium, mercury and zinc were present in samples of
industrial wastes.
4. Forty-two industrial plants each contributed over five
pounds per day of at least one heavy metal each to the river.
5. Twenty-two plants each discharged wastes containing five
or more pounds per day of lead each to the river.
6. Twenty-nine plants each discharged wastes containing
five or more pounds of chromium per day.
7. Twenty-nine -plants each discharged wastes containing
five or more pounds of zinc per day to the river.
8. Eight plants each discharged wastes containing five or
more pounds per day of cadmium to the river.
9. Five plants each discharged wastes containing five or
more pounds per day of arsenic to the river.
10. Five plants discharged wastes containing measurable
amounts of cyanide to the river.
11. Seventeen plants each discharged wastes containing ten
or more pounds per day of phenolics to the river.
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12. Forty-six organic chemicals in trace amounts were
present in the raw or treated water supplies from three
water plants - the U. S. Public Health Service Hospital
at Carville, the Carrollton plant of the City of New
Orleans and the Jefferson Parish #2 Water Plant at
Marrero. Thirteen of these were present in wastes from
seven industrial plants.
13. An additional forty-four organic chemicals were pre-
sent in the wastes from ten industrial plants. These
chemicals were not found in the finished water of the
three municipal water plants.
14. Fifteen plants each discharged wastes with 40,000
pounds or more per day of chemical oxygen demand and
ten discharged 20,000 pounds per day or more of total
organic carbon.
15. Thirty-two plants each discharged 50,000 pounds per
day or more of total solids and twenty-six discharged
25,000 pounds or more of volatile solids.
16. The average threshold odor in the raw water at six
water treatment plants increased from 7.3 at river mile
260 to 12.0 at river mile 99.
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17. The characterization of the river water odor varies
from "earthy" or "musty" upstream to "chemical" or "petro-
chemical" downstream.
18. All of the sixty industrial plant discharges were
found to have discernible odors. Each was capable of
causing detectable odors in flows ranging from 758 billion
gallons per day to 50 thousand gallons per day. The
average flow of the Mississippi River at New Orleans is
considered to be 500,000 cubic feet per second or 323
billion gallons per day.
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19. Threshold odor numbers at the intake of downstream
water utilities indicate that odor; contributions from
stream industries are still present when the waters are
taken in for treatment to become potable water.
20. A survey of fishermen and wholesale fish dealers
revealed that fish caught in the reach of the river
below Baton Rouge were not saleable because off-flavors
in the fish made them unacceptable to the public.
21. Experimental fish placed downriver from major indus-
trial complexes developed pronounced off-flavor after 72
hours of exposure to the river water.
22. Six organic chemicals found in trace quantities in the
finished water supplies at either the U.S. Public Health
Service Hospital at Carville or the New Orleans Carrollton
Plant, or both, have been shown by others to induce histo-
pathological changes in animals in chronic toxicity studies.
23. Three of the organic compounds found in trace quanti-
ties in the finished water supplies of the U.S. Public
Health Service Hospital at Carville and the Carrollton
plant at New Orleans have been shown by others to be car-
cinogenic.
24. Many of the industries investigated in this study have
initiated waste abatement programs as required by the State
of Louisiana and/or by the Refuse Act Permit Program of the
Corps of Engineers and the Environmental Protection Agency-
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CONCLUSIONS
1. This report fulfills the request for technical
assistance from the Louisiana Stream Control Commission
dated March 23, 1967 and Recommendation No. 3 of the
1962 Lower Mississippi Enforcement Conference.
2. Industrial waste discharges are contributing signif-
icant quantities of hazardous and/or undesirable pollutants
to the Mississippi River in Louisiana.
3. The industrial waste discharges are the principal cause
of the persistent "oily-petrochemical" odor in the public
water supplies downstream from Baton Rouge.
4. The industrial waste discharges are the principal cause
of the tainted flesh of fish caught in the Mississippi River
downriver from Baton Rouge.
5. The trace organics in the Mississippi River drinking
water supplies are a potential threat to the health of the
1.5 million people who consume this water, particularly
the elderly, those that are ill and children.
6. The water quality standards of the State of Louisiana
and the Federal Government relating to taste and odor pro-
ducing substances are being violated by industrial waste
discharges to the Lower Mississippi River in Louisiana.
7. Past industrial waste abatement practices of
Mississippi River industries were not adequate to control
the discharges of heavy metals or organics.
8. Ongoing industrial waste abatement programs should
remove and/or reduce many of the hazardous discharges to
the river.
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RECOMMENDATIONS
Based on the findings and conclusions contained in
this Report, and in order to protect and enhance the
suitability of the Lower Mississippi River as a source
of raw water supply, it is recommended that:
1. The State of Louisiana in cooperation with the
Environmental Protection Agency review the proposed waste
abatement programs of all industries identified in this
Report as having excessive discharges of odorous compo-
nents, organics and heavy metals to insure that each waste
abatement program will adequately reduce the discharge of
these components to an acceptable level.
2. The Environmental Protection Agency, through
appropriate Federal permit programs review all industrial
permit applications to insure that all existing and planned
waste treatment facilities are designed for maximum reduc-
tion of halogenated compounds, complex organics and heavy
metals. The effluent concentrations and consequent loadings
of heavy metals, complex organics and halogenated compounds
should be consistent with information contained in Water
Quality Criteria Data Book, Volumes 1 and 3 and other appro-
priate toxicological summaries and subsequent rules and
regulations that from time to time may be promulgated.
3. The State of Louisiana take action to insure that
all future industrial expansion is accompanied by best
available waste treatment practices.
4. Municipal water treatment plants install treatment
facilities designed to (a) obtain optimum removal of organic
contaminants and heavy metals, and to (b) provide increased
protection of the water supplies from accidental spills of
chemicals and oil upstream from the municipality's raw
water supply intake structure.
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5. Municipalities using the Mississippi River as
a source of drinking water expand their finished water
monitoring programs to include organic and heavy metals
analyses on a weekly basis.
6. The United States Public Health Service consider
modifying the water treatment plant at their Carville,
Louisiana hospital to include the addition of facilities
designed to remove organic contaminants.
7. Appropriate medical agencies or foundations under-
take epidemiological investigations to determine the chronic
effects on humans of low level intakes of combinations of
organic contaminants such as those found in the Mississippi
River water supplies as described in this report.
8. The State of Louisiana take appropriate action to
insure that:
a. The State Board of Health has adequate legal
authority to cause (1) immediate cessation or im-
poundment of discharges which contain noxious,
poisonous, or otherwise objectionable substances
into any source of water supply, (2) immediate
revocation of any permit for a discharge containing
objectionable substances where such substances
adversely affect in any manner the public water
supply, or are noxious, poisonous or carcinogenic,
or otherwise threaten the public health and welfare
or enjoyment of the public water supply; and
b. State and local prosecutors have adequate legal
authority, acting on requests from any agency, de-
partment or commission of the State to secure such
relief as may be necessary to abate the presence
of objectionable substances present in a public
water supply before or after treatment for potable
water.
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9. An investigation be undertaken of the Mississippi
River estuary to determine the extent of heavy metal, com-
plex organic, halogenated compound and other pollution
upon shrimp, fish, shellfish and other biota in the food
chain.
10. A continuing assessment be made of the water quality
of the Lower Mississippi River to determine the effectiveness
of abatement practice schedules.
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CHAPTER I
DESCRIPTION OF STUDY AREA AND PERTINENT PROBLEMS
The Mississippi River rises in Minnesota and flows
southward 2,350 miles to the Gulf of Mexico, draining
over 40 percent of the United States and part of Canada.
The Lower Mississippi River Basin begins at the mouth
of the Ohio River (Cairo, Illinois) and encompasses parts
of the states of Missouri, Kentucky, Arkansas, Tennessee,
Mississippi, and Louisiana. The alluvial valley of the
Lower Mississippi River is a broad, gently sloping low-
land which begins below Cape Girardeau, Missouri, and
extends to the Gulf of Mexico. This lowland extends more
than 600 miles, varies in width from 30 to 125 miles and
is bordered by abrupt escarpments. Tributary flows join
the main river at various locations. The lowland extends
up these tributaries many miles beyond the broad flat
basins in the vicinity of the junctions.
The flow of the Mississippi River in the lower basin
is large, ranging from a record high at Vicksburg,
Mississippi, of 2,280,000 cubic feet per second (cfs) on
May 4, 1927, to a low of 100,000 cfs on October 17, 1939.
However, both extremes preceded control structures and
probably never again will be approached.
Flows in the lower Mississippi River are affected by
diversions into the Atchafalaya River through the Old
River diversion channel near Coochie, Louisiana (approx-
imately R.M. 315). The U. S. Geological Survey reports
that "the average flow of the Mississippi River below the
diversion channel is probably meaningless." A more real-
istic appraisal of flow conditions to be expected can be
made using data from the Vicksburg gaging station. Contin-
uous record has been collected at this site since 1931.
The average flow of the river during that period was 551,100
cfs. Annual averages varied from a high of 843,900 cfs for
the 1950 water year to a low of 272,000 cfs for the 1931
water year ( 69) .
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The main stem of the lower Mississippi River is
leveed to near its mouth. Outside the levees the area
comprises woodlands and large farms. The more important
tributaries to the Mississippi River in the Lower Missis-
sippi River Basin are the St. Francis, White, and Arkansas
flowing from the west and the Hatchie, Wolf, Yazoo, and
Big Black Rivers draining from the east. All of these
discharge into the Mississippi above the Louisiana-
Mississippi state line and their points of confluence are
above the study area covered in this report.
The Atchafalaya River is the major distributary of
the Mississippi River. Water diverted from the Mississippi
River joins the Red River to form the Atchafalaya River.
In addition to the Atchafalaya distributary, water from
the Mississippi River is pumped over the levee at Donald-
sonville, (R.M. 175) into Bayou Lafourche to provide raw
water for four water plants located on this bayou. The
Mississippi and Atchafalaya Rivers discharging into the
Gulf, form an extensive and exceedingly valuable estuary
which is the nursery ground for a large part of the Gulf
of Mexico's commercial and sports marine fisheries. The
Mississippi River, its tributaries and its distributary
are valuable sources of fresh water commercial and game
fish. As will be discussed later, fish caught in the main
stem of the Mississippi River are no longer saleable be-
cause of tainted flesh.
The general area of interest in this study is the
stretch of the Mississippi River main stem from the
Louisiana-Mississippi state line, River Mile (R.M.) 305,
to the Head of Passes at River Mile 0. The Head of Passes
is the point at which the Mississippi divides into three
channels and the delta begins. The initial area studied
covered that portion of the river from St. Francisville,
Louisiana, (R.M. 260) to New Orleans, Louisiana, (R.M. 105),
It was later extended to Venice, Louisiana, (R.M. 2) to
include industries located below New Orleans. Sixty indus-
trial plants are located on, or adjacent to, the banks of
the Mississippi River and discharge into it in this two
hundred and fifty-eight mile water way. Among these are
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the largest petroleum refinery in the United States,
several smaller refineries and numerous and diverse
petrochemical and chemical manufacturers. Most of these
industries utilize the Mississippi River water as a
process or cooling water source, or both, and all of them
discharge their partially treated or, in some cases,
untreated wastes under a State permit system to the
river. All industries have submitted implementation
plans to the State to treat their wastes. The State is
requiring the equivalent of secondary treatment by
December 31, 1972. Decreases and/or elimination of some
of the problems described in this report can be expected
after this date. Heavy metals such as mercury, arsenic,
lead, zinc, copper, chromium, cadmium, and zinc have been
found in waste discharges in addition to phenols, cyanides,
and a wide array of organic compounds. These wastes are
believed to be the major cause of offensive tastes and
odors in the drinking water of the approximately 40
communities providing water to about 1.5 million people.
In addition, there is reason to believe that tastes are
being imparted to fish in this stretch of the river to
such an extent that wholesale and retail fish dealers will
not handle fish caught in these waters because of repeated
complaints by customers of "off" flavors often described
as "oily" or "chemical."
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CHAPTER II
EVALUATION OF THE POLLUTION POTENTIAL
OF INDUSTRIAL WASTE DISCHARGES
Wastes that are discharged to the Mississippi River
from sixty industrial plants between St. Francisville,
Louisiana (R.M. 260), and Venice, Louisiana (R.M. 2) have
been collected and analyzed. These analyses have disclosed
that these discharges contain excessive quantities of heavy
metals and organics. Since the Mississippi River serves as
the drinking water supply for over 1.5 million people below
Baton Rouge, the addition of these manmade materials - many
of them toxic and odorous - is undesirable.
DETERMINATION OF WATER AND
WASTE CHARACTERISTICS
A two-part investigation was undertaken in the deter-
mination of characteristics of water and wastes. The first
part was designed to remove and concentrate the trace
organics from the raw and treated river water. In order to
obtain sufficiently large samples of the organics to allow
identification, a largescale, activated carbon filter -
called a Mega Sampler - was used (see Appendix, Exhibit D -
Analytical Techniques for description of the mega sampling).
Eleven mega samples were collected during the course of the
investigation (see Table 1). The' chloroform extract of the
mega samples provided the raw material for the identification
of most of the higher boiling organics; the saturated carbon
was also used in one precedure for direct elution of the
lower-boiling organics.
The second phase of the study involved the sampling
and analyses of the industrial waste discharges to the
Mississippi River. Twenty gallon composite samples of the
waste outfalls were collected. One portion of the composite
was extracted with solvents for trace organic analysis, and
portions of the balance were analyzed for up to twenty-seven
physical and chemical parameters. (Analytical Techniques
are described in Appendix, Exhibit D.) A list of all
companies sampled, locations, sampling dates, and analytical
results will be found in Exhibit F of the Appendix.
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TABLE I
RAW AND FINISHED WATER MEGA SAMPLES COLLECTED
Date
Apr 1969
Jan 1970
Sept 1969
Sept 1969
Jan 1970
Mar 1969
Mar 1969
May 1969
Jun 1969
Aug-Sept 1969
Aug-Sept 1969
Water Sample
Supply Size
System (1000 qal)
Crown
Crown
USPHS
USPHS
Zellerbach
Zellerbach
Hospital
Hospital
Carrollton
Jeff.
Jeff.
Jeff.
Jeff.
Jeff.
Jeff.
Parish #2
Parish #2
Parish #2
Parish #2
Parish #2
Parish #2
181
121
96
228
300
87
106
100
99
108
177
Average
River Flow
(1000 cfs) Type
670
570
205
205
580
690
470
720
360
260
260
Raw
Raw
Raw
Finished
Finished
Raw
Raw
Raw
Raw
Raw
Finished
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TOXIC SUBSTANCES
Everything in our environment is composed of chemical
substances, and most of these pose minimal danger to man
or the environment. However, some pose a serious danger,
particularly those involved in redistribution and chemical
alteration resulting from man's activities when he engages
in economic exploitation and disposal.
Selected metals, their compounds, and certain synthe-
tic organic chemicals are perhaps the best examples of toxic
substances which can adversely affect man and his environ-
ment.
This investigation did not include analyses of toxic
heavy metals in the finished municipal water supplies.
However, because these metals all have soluble forms, and
many are known to enter the food chain, e.g. mercury, a
delineation of the major discharges of these substances is
considered a critical part of this study.
HEAVY METALS, CYANIDES AND PHENOL
Metals are recovered from ore deposits either directly
or as byproducts in the course of refining other metals.
Metallic salts formed during these recovery and refining
processes can escape as waste products into surface and
ground water.
After substances enter the environment, they may be
diluted or concentrated by physical forces, and they may
undergo chemical changes, including conbination with other
chemicals that affect their toxicity. The substances may
be picked up by living organisms which may further change
and either store or eliminate them.
The results of the interaction between living organisms
and chemical substances are often unpredictable, but such
interaction may produce materials that are more dangerous
than the initial pollutants. One example is the conversion
of inorganic mercury into methyl mercury.
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Synergism is another complicating interaction. Two
or more compounds acting together may have an effect on
organisms greater than the sum of their separate effects.
For example, the toxic effects of mercuric salts are
accentuated by the presence of trace amounts of copper (62).
Cadmium acts as a synergist with zinc and cyanide in the
aquatic environment to increase toxicity (53, 54, 55).
The presence of heavy metals in industrial waste de-
picted in Table 2 shows that the frequency of occurrence
in quantities of five pounds or more per day in the forty-
two waste samples listed was greatest for chromium and
zinc at 29, next for lead at 22, and for other metals less
frequently- Toxicity, or properties otherwise hazardous
to humans or aquatic biota, vary widely and are discussed
in brief detail below.
Lead gives greatest cause for concern of the three
metals found most often because of the relatively large
quantities discharged and the fact that, as reported in
the Public Health Service Drinking Water Standards, 1962,
(63) "when taken into the body, it can be seriously inju-
rious to health, even lethal, if taken in by either brief
or prolonged exposure. Prolonged exposure to relatively
small quantities may result in serious illness or death."
(63) The Public Health Service Drinking Water Standards
place the following limits on lead as they relate to human
health.
"Limits and Ranges of Lead Affecting Health
Physiologically safe in water:
Lifetime - 0.05 mg/1
Short period, a-few weeks- 2-4 mg/1
Harmful range in water:
Borderline - 2-4 mg/1 for 3 months
Toxic - 8-10 mg/1, several weeks
Lethal _ unknown, but probably more
than 15 mg/1, several weeks"
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TABLE 2
INDUSTRIES HAVING HEAVY METALS DISCHARGES
FIVE POUNDS PER DAY OR GREATER1
Company
Plant or Division
Allied Chemical Corp.
Ind. Chem. Div.
Spec. Chem. Div.
Plastics Div.
Geismar Complex
American Cyanamid Co.
BASF Wyandotte Corp.
Location
Baton Rouge
Baton Rouge
Scot landvi lie
Geismar
Avondale
Geismar
Date
Sampled
As
4-14-70
7-25-70 15
*12-2/3-70
*7-19-71
6-22-70
4-28-70
6-29-70 20
2-2-70
*7-26-71
4-7-70
*2-10/ll-71
Pb
570
56
78
7
7
5
20
172
Heavy Metals2
Cd Cu Cr
20 20 200
7
42
20 10 75
17
68
69
52
- #/Day
Hg Zn
232
13
16
59
6
Borden, Inc.
Borden Chem. Div.
Geismar
*6-28-71
28
15
The Celotex Corp.
C. F. Industries
Marrero
Donaldsonvilie
*9-21-70
11-16-70
*8-2-71
43
10
28
44
8
Chevron Chemical Co.
Oronite Add. Div.
Belle Chasse
*l-25-71
*8-10-7l
8
22
-------
TABLE 2 (Continued)
Company
Plant or Division
Ciba-Geigy Chemical Corp.
Copolymer Rubber & Chem.
Corp.
Cos-Mar Plant, Borg Warner
Corp., Marbon Div.
Crown Zellerbach Corp.
The Dow Chemical Co.
E. I. DuPont de Nemours
& Co., Inc.
Enjay Chemical Co.
Ethyl Corp.
Freeport Mineral Co.
Freeport Chem. Co. Div.
Location
St. Gabriel
Baton Rouge
Carville
St. Francisville
Plaquemine
LaPlace
Baton Rouge
Baton Rouge
Uncle Sam
Date
Sampled
8-25-70
1-14-70
5-3-71
7-6-70
*5-19-71
11-2-70
*6-21/22-71
3-2-70
*5-4-71
6-14-71
6-9-71
1-14-70
7-25-70
4-27/28-71
6-24-71
*10-5-70
*ll-3-70
As_ Pb
56
36
48
7
5
3700
529
301
250
Heavy Metals2
Cd Cu Cr
6
38 26
6 16
8
9
6 34
10 82
47 13
8
36 12
36
38 ** 188
- #/Day
Hg_ Zr\
14
46
22
20
630
216
-------
TABLE 2 (Continued)
Company
Plant or Division
Ge o r g,i a Pa c i f i G Co rp.
Cirossett Div.
Gulf Oil Co., U.S.
Gulf Oil Chemical Co.
Hercules, Inc.
Allemania Plant
Hooker Chemical Co.
Humble Oil & Ref. Co.
Kaiser Alum. & Chem. Corp.
Chemicals Div.
Metals Div.
Location
Port Hudson
Venice
Welcome
Plaquemine
Hahnville
Baton Rouge
Baton Rouge
Chalmette
Gramercy
Gramercy
Date
Sampled
As
5-4-70
*6-15-71
8-31-70
*ll-23-70
2-24-70
*5-25/26-71
*6-7-71.
*6-7/8-71
*6-8-71
7-21-70
8-30/31-71
8-31/9-1-71
*11-30-70
3-31-70
7-21-70 31
9-28/29-71
9-29/30-71
9-7/8-71
9-8/9-71
Pb
140
485
889
218
400
354
352
40
500
90
61
323
148
Heavy Metals2
Cd Cu Cr
15 15
120
42
74
8 55
7 35
7 1 67
52 145
396 36
14
5
55 139
32 112
- #/Day
Hg Zn.
105
65
74
72
140
1080
1317
61
405
187
919
423
-------
TABLE 2 (Continued)
Company
Plant or Division
Monochem, Inc.
Monsanto Co.
Murphy Oil Corp.
Rollins Purle, Inc.
Rubicon Chemicals, Inc.
Schuylkill Metals Corp.
Shell Chemical Co.
Stauffer Chemical Co.
Ind. Chem. Div.
Location
Geismar
Luling
Meraux
Baton Rouge
Geismar
Baton Rouge
Geismar
Norco
Baton Rouge
St. Gabriel
Date
Sampled
As
*6-22/23-71
2-9-70
1-18-71
M-12-71
1-21-70
5-11-70
7-13-70
2-16-70
6-1-70
*2-8-71
Heavy Metals2 - #/Day
Pb Cd Cu Cr Hg Zn
23
104 52 10
5 15
7
7
5 12
25 91
36 7
27 20
9
Tenneco Oil Co.
Triad Chemicals
Chalmette
Donaldsonville
Baton Rouge
1-11-71
9-8-70
*8-3-71
48
11 11
27
25
19
Union Tank Car Co.
The five pounds per day has been selected arbitrarily for screening purposes and does not
imply that lesser quantities of heavy metals are acceptable.
2See Appendix, Exhibit F for additional data.
*Net loads (see explanation page 132)
**Interfering substances made determination invalid and/or questionable.
-------
According to Boyland (8) in another study by him and
co-workers, it was shown that lead salts induce cancer of
the kidney in rats but do not appear to do so in men. On
the other hand, Boyland (8) described studies by Dingwell
and Lane which associated heavy exposure to lead with in-
creased incidence of cerebrovascular catastrophies.
As stated above, lead was the third most prevalent
metal in waste discharges containing five pounds or more
per day. The Ethyl Corporation, manufacturers of tetra-
ethyl lead, discharged the greatest amount, 3700 pounds
in one day, on July 25, 1970. Since that time and in
part as a result of this investigation, the company has
undertaken an extensive program to reduce the lead in
their wastes. The most recent sample, June 24, 1971,
shows a considerable decrease to 301 pounds per day. A
desirable goal is to reduce the lead in their effluent to
concentrations not exceeding that found in Mississippi
River water (mean of 0.05 ppm).
The Hooker Chemical Corporation at Hahnville shows
relatively high lead in its discharge. Three samples
collected in less than a month had concentrations repre-
senting the following loads.
Cone. Lead
Date Sampled mg/1 Flow MGD Lbs/Day
May 26, 1971 (Comp.) 2.8 20.74 485
June 8, 1971 (Comp.) 1.2 22.18 218
June 7, 1971 (Grab) 4.8 22.18 890
The problem of high lead was discussed with the plant
management when it was learned that a lead recycling
facility which had been installed was a failure. A lead
precipitation pond had been used successfully for several
months but had recently been giving trouble. In order to
eliminate the lead problem permanently, the company has
begun a program of replacing all the lead seals on the
caustic-chlorine cells with a new type of equipment that
22
-------
will eliminate the lead completely. The first third of
the cells are scheduled to be changed by September, 1971,
the next third by the middle of 1972 and the last third
by the end of 1972.
The Allied Chemical Corporation, Industrial Chemicals
Division, (North Works), when informed that their lead
discharges were in excess of 100 pounds per day, traced
the source of the lead to their caustic-chlorine, Hooker
diaphragm cells and initiated measures to impound and
treat these wastes. Since then they have been discharging
less than 80 pounds per day and plan to reduce this further.
The presence of lead in discharges from chlorine-
caustic production units is due to the use of lead as a
conductor in the anodes of diaphragm cells. The lead is
sealed from the anolyte by a mastic. Because of various
operation problems, the mastic cracks and allows the
acidic anolyte to attack the lead. Most of the lead chlo-
ride thus formed leaks from the cells due to their type of
construction. This lead chloride either drips to the
sewers or is washed off the cells during washdown operations,
There are five plants using diaphragm cells along the
Mississippi River and their discharge of lead daily ranges
from 15 - 200 pounds per day- There are two ways to cure
this problem. The present graphite anodes can be replaced
with dimensionally stable anodes (titanium metal) which
require no lead in the anode of the cells. This eliminates
the problem completely- The effluent from these plants can
also be treated with carbonate at a pH of about 9. The
resulting basic lead carbonate is then precipitated and can
either be settled or filtered. This type of treatment
system when properly operated will reduce the lead content
to the 6-10 pound per day range.
Copper is not considered to be a cumulative systemic
poison. It is an essential element in low concentrations
in man's diet with a daily requirement estimated at 2.0 mg
(63). However, even small doses, as low as 0.015 mg, (63)
23
-------
are known to be lethal to algae, snails, mussels, barnacles,
etc. (48) The Public Health Service Drinking Water Standards
(63) for copper state, "Inasmuch as copper does not consti-
tute a health hazard but imparts an undesirable taste to
drinking water, it is reasonable to establish the concen-
tration of 1.0 mg/1 as the recommended limit."
Copper was found in wastes from thirteen industrial
plants in amounts of five pounds or more per day. The
largest load, 396 pounds, occurred in wastes from the Kaiser
Aluminum & Chemical Corporation at Chalmette, Louisiana, on
November 30, 1970.
Zinc has no known physiological effects on man except
in high concentrations. However, zinc is toxic to fish, a
characteristic that is intensified by synergism with copper.
The Drinking Water Standards (63) state that, "Inasmuch as
zinc in water does not cause serious effects on health but
produces undesirable esthetic effects, it is recommended
that concentrations of zinc be kept below 5.0 mg/1."
Zinc was one of the metals most frequently foun<3 in
amounts of five pounds or more per day, in forty-two waste
discharges. The greatest amount, 1,317 pounds, was found
in the waste samples of the Kaiser Aluminum & Chemical
Corporation, Baton Rouge, on August 31-September 1, 1971.
Cadmium is recognized by the Public Health Service "to
be an element of high toxic potential. " (63), McKee and
Wolf state (48), "Consumption of cadmium salts causes cramps,
nausea, vomiting and diarrhea. Oral ingestion has been the
cause of a number of human deaths." The 1962 Drinking Water
Standards include the following, "...because suspicion has
been cast on the presence of minute amounts of cadmium in
the kidney as responsible for adverse renal arterial changes
in man, concentrations of cadmium in excess of 0.01 mg/1 in
drinking water are grounds for rejection of the supply."
Studies by Schroeder (53, 54) linked hypertension to
increased retention of cadmium in the kidneys when he noted
that most human subjects dying from hypertensive complica-
tions showed in their kidneys either increased amounts of
24
-------
cadmium or increased ratios of cadmium to zinc compared to
subjects dying of a variety of other diseases. These
findings in man have been substantiated experimentally in
animals.
In additional studies, laboratory breeding mice exposed
to concentrations of cadmium, lead, or selenium produced
abnormal offspring (55) .
A toxicology investigation of patients suffering from
the "itai-itai" disease revealed the presence of a high con-
tent of cadmium in the bones and internal organs of the
patients, in rice, other plants, and soil in a restricted
district along the Jintsu River in Toyama Prefecture, Japan,
upstream from point of waste discharge from a mine (39).
As a consequence of these findings, Kobayashu (39)
conducted animal studies in which rats were fed cadmium.
He observed that the experimental rats excreted more cal-
cium than that assimilated from their food while the control
group showed the opposite phenomena. This hypercalcium
excretion is one of the characteristics of the itai-itai
disease in humans. From these results, it was concluded
that the itai-itai disease was induced by cadmium in waste
from the mine.
In another Japanese study by Yamagato and Shigematou
(72) it was estimated that man consumes normally 60 micro-
grams of cadmium per day, but in the area of occurrence of
itai-itai disease the consumption was more than 600 micro-
grams per day. The main source of the cadmium was foodstuffs,
of which about half was contributed by rice.
Boyland (8) cited epidemiological evidence from an
article by Kipling and Waterhouse which indicated that
cadmium compounds were a cause of prostatic cancer in man.
However, in a study by Roe and others, as stated by Boyland
(8), cadmium compounds administered to rats were shown to
induce testicular tumours of the interstitial cells.
25
-------
This is an example of a frequently observed phenom-
enon of a carcinogen inducing tumours of different organs
in different species. Cadmium resembles zinc in its
chemistry but biologically it is a zinc antagonist. The
prostate gland has a high content of zinc and it is perhaps
for this reason, as attested by Boyland (8), that the chronic
toxic effect of cadmium is exerted on this organ in man.
Cadmium in quantities of more than five pounds per
day was present in eight waste discharges, the greatest load
of 71 pounds per day occurring in a sample of wastes from
Kaiser Aluminum & Chemical Corp., Baton Rouge, Louisiana,
on August 31, 1971. Kaiser's waste discharge from the
Metals Division at Gramercy had loads of 55 pounds per day
on September 8, 1971 and 32 pounds per day on September 9,
1971. Concentrations corresponding to twenty pounds per
day was present in samples from the discharges of the Allied
Chemical Corporation at the Industrial Chemical Division,
Baton Rouge, Louisiana, on April 14, 1970, and at the
Geismar Complex, Geismar, Louisiana, on June 26, 1970.
Reference to Exhibit F will disclose discharges of lesser
amounts. As with other toxic heavy metals, the goal should
be no cadmium discharged.
Chromium is not known to be either an essential or
beneficial element in the body- Its toxic properties for
man have not been clearly established. When inhaled,
according to the 1962 Drinking Water Standards, chromium
is a known carcinogenic agent for man. It is not known
whether cancer will result from ingestion of chromium in
any of its valence forms. The Public Health Service (63)
concludes "that a concentration of 0.05 mg/1 is sufficiently
low to cause no effect on health."
In investigating pulmonary and gastric forms of chronic
poisoning with chromium compounds, cardiovascular function
was studied in 230 workers of a potassium bichloride indus-
try. Kleiner and coworker (38) concluded that the disorders
revealed in the bioelectric and mechanical activity of the
myocardium could come both from the overcharging of the
right heart in patients with pulmonary pathology and be
also due to the general toxic effect of chrome on the vessels
and the myocardium.
26
-------
Chromium was one of the metals most frequently pre-
sent in the forty-two waste discharges with a peak amount
of 200 pounds per day being found in wastes from the
Allied Chemical Corporation, Industrial Chemicals Division
at Baton Rouge, Louisiana, on April 14, 1970. Chromium is
widely used as a corrosion inhibitor in industrial cooling
water systems particularly when such systems are closed.
Since there are other corrosion inhibitors available to
industry and ion-exchange techniques available for removing
and recycling chromium, industry's goal should be essen-
tially zero or no greater than background discharge.
Arsenic has toxic properties that are well known.
There is evidence that it may be carcinogenic and the
intake of as little as 100 mg usually results in severe
poisoning. Even at low level intakes a considerable portion
is retained with a single dose requiring as long as ten days
for complete disappearance. This slow excretion is in part
the basis for its cumulative effects (63). 1962 Drinking
Water Standards of the Public Health Service states,"... the
concentrations in excess of 0.05 mg/1 are grounds for re-
jection of the supply."
Studies have shown that long periods of arsenic and
molybdenum exposure changed the sex ratios of mice and rat
offspring (53).
Four companies other than Kaiser (see following
paragraphs for discussion of the Kaiser problem) were found
to have arsenic in their waste discharges. These were the
Allied Chemical Corporation plant at Geismar with 19.6
pounds per day, the Industrial Chemicals Division of Allied
Chemical Corporation at Baton Rouge with 15.4 pounds per day,
the Schuylkill Metals Corporation at Baton Rouge with 2.6
pounds per day, Union Tank Car Co. at Baton Rouge with 9.3
pounds per day, and the Celotex plant at Marrero. The latter
plant was discharging over 43 pounds per day of arsenic at
the time of sampling, September 21, 1970. They have a per-
mit from the Louisiana Stream Control Commission to dis-
charge 160 pounds per day. The arsenic in the wastes
comes from arsenic trioxide which is used on exterior wood
products to inhibit the growth of fungi and for termite
control. At a meeting of the Louisiana Stream Control
Commission on January 12, 1971, the Celotex Corporation
advised that treatment to eliminate arsenic from the waste
27
-------
discharge was under study. The Commission .approved the
report after stating that the industry will be expected to
eliminate all arsenic after completion of the study and
implementation of its findings.
The Kaiser Aluminum and Chemical Corporation is the
fourth discharger of arsenic. A sample of waste from the
Baton Rouge plant showed in excess of 0.061 pounds per day
on July 21, 1970, and 31 pounds per day from the Gramercy
plant on the same date. Later data, however, showed less
than detectable quantities of arsenic in the Kaiser "red
mud". Arsenic determinations on a high solids material
such as spent bauxite are difficult to perform because of
the interferences from high concentrations of iron, alum-
inum and other metals. In a report prepared by Kaiser on
April 16, 1971, arsenic was reported to range from 6 to
300 pounds per day in the Baton Rouge plant's spent bauxite
discharge and from 4 to 208 pounds per day in the Gramercy
plant's discharge.
The other heavy metals contained in the spent bauxite
include lead, manganese, zinc and traces of mercury.
These are inherent in the raw material, bauxite, from which
alumina is extracted. Since it is virtually impossible to
remove these heavy metals from this waste material before
discharging to the river, the only practical way to prevent
these metals from reaching the river is through total
solids impoundment. Kaiser attempted for many years to
find a practical and ecologically sound method of total
impoundment. Only recently, however, have they successfully
demonstrated a technique for dewatering the "red mud". This
method, still in the developmental stage, should allow
Kaiser to retain on land the "red mud" solids and allow some
recirculation of the spent caustic liquor. A market for
these dried solids which contain high concentrations of iron
hopefully will be developed by Kaiser. At the time of this
writing, Kaiser plans to have the "red mud" out of the river
by July, 1974 at the Gramercy plant and by July, 1975 at the
,Baton .Rouge plant.
The other bauxite consumer located on the Mississippi
River, in addition to the two Kaiser plants discussed
above, is Ormet at Burnside. At the present time Ormet
28
-------
retains and settles all of their muds and recycles the
resulting clear liquor into the plant. Their discharge
does not contain in any measurable amount the metals out-
lined above.
Mercury and mercuric salts are highly toxic to humans,
although mercury was long thought environmentally inert.
When discharged into a river, for example, it was believed
to settle to the bottom and remain there. Then in 1960,
it was reported that 111 persons had died or suffered
serious neurological damage near Minamata, Japan as a re-
sult of eating fish and shellfish which had been contaminated
by mercury discharged into Minamata Bay by a plastic manu-
facturing plant (35). Since then it has been shown that
metallic mercury can be changed by bacteria under anaerobic
conditions into methylmercury, a compound far more toxic
than metallic mercury, and that it can enter the food cycle
through uptake by aquatic plants, algae, lower forms of
animal life and fish (56). Equally significant, studies
have shown that the concentration factor in the fish could
be 3000 or more to one (34). Thus, harmless levels of
mercury in water can be concentrated to hazardous levels in
fish.
Clegg (15) reported that the embryotoxic or teratogenic
effects of alkyl mercurial compounds on laboratory animals
result from direct toxic action of the compound on the fetus
or embryo, and possibly also by damaging the gametes prior
to fertilization.
The finding of mercury in finfish and shellfish in
many parts of the United States in 1970 and the removal of
large quantities of canned and frozen seafood from the mar-
ket because of its high mercury content emphasize the
undesirability of the release of mercury in any form or
quantity to the waters of the Lower Mississippi River Basin
or elsewhere in this nation.
The concern over mercury is well founded. Some organic
mercury compounds are accumulated in humans, concentrate
in the brain, cause tremors and mouth ulcers, and produce
birth defects because of chromosome breakage. (9).
29
-------
At the time of this study there were three plants
along the lower Mississippi River operating mercury cell
chlorine-caustic plants. BASF Wyandotte has committed
to close down the operation of their mercury cells by
December 31, 1973, and Stauffer Chemical will continue
their operation, with the addition of removal systems.
Dow Chemical at Plaquemine shut down permanently and
dismantled the mercury cell caustic-chlorine cells, on
December 23, 1970.
Analysis for mercury in waste discharges from the
Dow Chemical Company of Plaquemine in January 1970 dis-
closed concentrations in the order of 2.4 ppm. This com-
puted to a loss of several thousand pounds per day of
mercury. Realizing that losses of this magnitude of a
costly metal such as mercury could not realistically be
sustained by an industry, it was presumed that the 25
minute composite collected contained a "slug" of mercury.
Subsequent discussion with Dow personnel revealed that
during the sampling period the company was in process of
diverting their caustic-chlorine mercury cell wastes to
provide a mercury treatment facility. Part of this con-
struction involved the dredging of effluent canals
containing high levels of mercury, apparently resulting
in the release of slugs of mercury laden material in their
outfall canal. Samples taken since that time disclosed
only traces of mercury, generally below the minimum detect-
able concentration.
Mercury discharge from these plants occurs by routine
losses from the cells, by carry over from the caustic
system, and by air losses in the hydrogen system which
falls to the ground and is either washed down to the effluent
or carried into the effluent by rain. Normal removal systems
consist of pH control, addition of sulfide for precipitation,
settling, filtration, and activated carbon treatment of the
effluent. With this type of treatment the mercury content
of the effluent is reduced to less than 0.5 pounds of
mercury per day. An examination of Exhibit F in the Appendix
will show that mercury discharges of 0.5 pounds or more have
been found in waste discharges from eleven plants.
30
-------
Cyanides are toxic to man when ingested. The 1962
Public Health Service Drinking Water Standards (63), re-
commends that concentrations of cyanide in water be kept
below 0.01 mg CN/1. The Public Health Service adds,
"For the protection of the health of human populations,
concentrations above 0.02 mg CN/1 constitutes grounds for
rejection of the supply."
McKee and Wolf (48) state that "...when toxicities
are expressed in terms of the cyanide ion it must be real-
ized that most of the cyanide in water is in the form of
HCN. It is apparent that HCN rather than the cyanide ion
is the major toxic principle. It must be recognized that
toxicities may vary markedly with pH and a given concen-
tration that is innocuous at pH 8 may become detrimental
if the pH is lowered to 6 or less. On the other hand,
Southgate reported that within the range of 6.0 to 8.5,
pH had no effect on the toxicity of cyanides. In natural
streams, cyanides deteriorate or are decomposed by bacterial
action, so that excessive concentrations may be expected to
diminish with time."
It appears that the toxic properties of this class of
compounds may, under favorable conditions of pH and time,
be expected to disappear. However, in view of the uncer-
tainties of having a favorable pH and enough time for de-
composition to be completed, it is the goal of the Environ-
mental Protection Agency that no cyanides be discharged
into the waters of the Lower Mississippi River or elsewhere
in this nation.
Five industrial plants (see Appendix, Exhibit F) were
found to have detectable quantities of cyanide in their
wastes. These were Rubicon Chemicals, Ind. in Geismar which
was discharging approximately 2.0 pounds per day; Monsanto
Company, near Luling, Louisiana, discharging 30 pounds per
day; American Cyanamid Company at Avondale, Louisiana, dis-
charging 150 pounds per day on Feb. 2, 1970, but having
reduced this to 1.44 pounds per day on June 26, 1971; Enjay
Chemical Company at Baton Rouge discharging 4.4 pounds per
day; and Allied Chemical Corp., Specialty Chemicals Division
at Baton Rouge discharging 2.9 pounds per day.
31
-------
Phenols, while toxic in concentrated solutions, are
more objectionable for their taste and odor .causing pro-
perties. The 1962 Public Health Service Drinking Water
Standards limit the concentration of phenols to 0.001 mg/1
because of tastes resulting from chlorination of water with
higher concentrations.
Table 3 lists 17 plants discharging 10 pounds or more
of phenols to the river each day. Since phenolic compounds
are particularly objectionable in potable water supplies
because of their taste and odor causing properties, no
phenol should be discharged to the waters of the Lower
Mississippi River.
Total Solids are being discharged by 32 industrial
plants in quantities of 50,000 pounds per day or more and
25,000 pounds or more per day volatile solids are being
discharged from 26 plants as indicated in Table 4. Within
this range total solids loads discharged range from a
maximum of 11.5 million pounds per day from the Dow Chemical
Company plant to 52 thousand pounds per day by the Copolymer
Rubber and Chemical Corporation at Baton Rouge. Kaiser
Aluminum and Chemical Company at Baton Rouge discharged the
highest volatile solids load - 1.5 million pounds per day.
These industries are considered to be discharging excessive
quantities of solids. All have been requested by the State
to provide secondary treatment or its equivalent by Decem-
ber 31, 1972.
32
-------
TABLE 3
INDUSTRIES DISCHARGING PHENOLICS IN QUANTITIES
OF TEN POUNDS PER DAY OR MORE
Company
Chevron Chemical Co.
u>
Copolymer Rubber & Chem. Corp.
Crown Zellerbach Corp.
The Dow Chemical Co.
Enjay Chemical Co.
Freeport Minerals Co.
Georgia Pacific Corp.
Hercules, Inc.
Humble Oil & Refining Co.
Division
Oronite Additives
Freeport Chem. Co.
Crossett Div.
Allemania Plant
Location
Belle Chasse
Baton Rouge
St. Francisville
Plaquemine
Baton Rouge
Uncle Sam
Port Hudson
Plaquemine
Baton Rouge
Date
Sampled
*l-25-71
*3-l, 2-71
*3-18-71
*8-10-71
1-14-70
5-3-71
11-2-70
1-20-70
1-15-70
*4-6-71
6-9-71
11-3-70
5-4-70
11-23-70
1-15-70
*6-8-71
Phenolics1
#/Dav
2970
97
125
288
108
35
260
34
266
168
491
55
156
16
1530
322
-------
TABLE 3 (Continued)
Company
Kaiser Aluminum & Chem. Corp.
Monsanto Co.
Rubicon Chemicals, Inc.
Stauffer Chemical Co.
Union Carbide Corp.
UniRoyal, Inc.
Division
Metals Div.
Location
Baton Rouge
Cha lunette
Gramercy
Luling
Geismar
Date I
Sampled
1-19-70
8-30/31-71
8-31,9-1-71
*11-30-70
9-7,8-71
9-8,9-71
5-26-70
1-21-70
4-14-71
'henolics1
#/Day
106
181
244
81
93
81
94
220
134
St. Gabriel
Hahnville
Baker
*2-8-71
1-22-70
7-6-71
28
74
185
The method of analysis for phenol measures not phenol alone but a whole series of organic
compounds that are called "phenolics."
* Net loads (see explanation page332) .
-------
TABLE 4
Company
Allied Chem. Corp.
INDUSTRIES WITH HIGH SOLIDS LOADS^
TOTAL SOLIDS 50,000 POUNDS PER DAY OR MORE
VOLATILE SOLIDS 25,000 POUNDS PER DAY OR MORE
Division
Ind. Chem, Div.
Specialty Chem.
Geismar Complex
U)
Ul
American Cyanamid Co.
BASF Wyandotte Corp.
The Celotex Corp.
Copolymer Rub. & Chem. Corp.
Crown Zellerfoach Corp.
The Dow Chemical Co.
E. I. duPont de Nemours & Co. Inc.
Enjay Chemical Co. Chemical Plant
Location
Baton Rouge
Baton Rouge
Geismar
Avondale
Geismar
Marrero
Baton Rouge
St. Francisville
Plaquemine
LaPlace
Baton Rouge
Date
S_ampled
*7-19-71 6,
6-22-70
6-29-70
2-2-70
4-7-70
9-21-70
5-3-71
1-14-70
11-2-70
1-20-70 11,
*6-21/22-71 6,
3-2-70
1-15-70
*4-6-71
5-9-71
Total
Solids2
#/_d*
307,
322,
405,
111,
270,
52,
280,
620,
500,
280,
98,
3 94 ,
199,
170,
Y_
100
000
000
000
000
600
000
000
000
000
000
000
600
100
Volatile
Solids2
ft/day
849, 100
145,000
597,000
230,000
30,900
320,000
410,000
96,250
32,000
134,000
37,000
-------
TABLE 4 (Continued)
Company Division
Ethyl Corporation
Freeport Minerals Co.
Georgia Pacific Corp.
Getty Oil Co.
Gulf Oil Co., U.S.
J^Gulf Oil Company
Hooker Chem. Corp.
Humble Oil & Ref. Co.
Kaiser Alum. & Chem. Corp.
Chemicals
Location
Baton Rouge
Date
Sampled
1-14-70
4-27/28-71
Total
Solids2.
#/day
651,500
739,900
Volatile
Solids2
#/day
51,500
Freeport Chem.Div. Uncle Sam
Crossett Div. Port Hudson
Baton Rouge
Chalmette
Gramercy
10-5-70 938,000 144,000
5-4-70 281,300 110,000
Venice
Venice
Welcome
Hahnville
Baton Rouge
6-1-71
*6-15-71
8-31-70
2-24-70
*5-25/26-71
1-5-70
*6-8-71
120,200
141,000
120,000
706,500
341,200
722,000
663,800
32,000
32,500
78,500
182,000
195,600
1-19-70 9,070,000 1,530,000
*8-30/31-71 5,084,500 4,802,9003
*8-31/9-1-71 4,435,000 4,144,2003
*11-30-70 416,100 116,100
3-31-70 496,400 69,000
9-28/29-71 206,600 8,2003
9-29/30-71 208,800 11,7003
-------
TABLE 4 (Continued)
Company
Division
OJ
Kaiser Alum. & Chem. Corp. Metals Div.
(Continued)
Monochem, Inc.
Monsanto Company
Occidental Chemical Co.
Rubicon Chemicals, Inc.
Shell Chemical Co.
Stauffer Chemical Co.
Tenneco Oil Co.
Texaco, Inc.
Union Carbide Corp.
UniRoyal, Inc.
Ind. Chemical
UniRoyal Chem.
Location
Gramercy
Geismar
Luling
Hahnville
Geismar
Norco
St. Gabriel
Chalmette
Convent
Hahnville
Geismar
Date
Sampled
Total
Solids'
tt/day
Volatile
Solids2
#/dav
9_7/8-71 5,049,500 4,990,000;
9-8/9-71 4,097,400 4,041,400;
*6-22/23-71 74,300
2-9-70
2-24-70
1-21-70
2-16-70
*2-8-71
1-11-71
8-17-70
1-22-70
*6-29/30-71 107,100
106,000
712,000
58,000
482,500
147,500
147,400
67,600
1,850,000 299,000
52,400
82,500
134,000
103,000
26,300
The industries listed have total solids loads of 50,000 pounds per day or more and volatile
solids loads of 25,000 pounds per day or more. These lower limits were arbitrarily selected
for screening purposes and do not imply that lesser quantities of solids are acceptable.
2 See Appendix, Exhibit E for additional data.
3 Total suspended, solids
* Net loads (see explanation page 132)
-------
TRACE HEAVY METALS IN PHOSPHATE ROCK WASTES
There are three companies along the lower Mississippi
River producing phosphoric acid by digesting phosphate rock
with sulfuric acid. These companies are Allied Chemical
at Geismar, Freeport Chemical at Uncle Sam and Occidental
at Taft. The Freeport plant is the largest plant of this
type in the United States. The rock as mined is a combina-
tion calcium phosphate-calcium fluoride compound. As with
most minerals there is a large number of impurities including
heavy metals associated with the rocks in small concentrations,
The basic process converts the calcium ion to calcium sulfate
which is filtered from the phosphoric acid. The resulting
calcium sulfate containing many of the impurities is slurried
and discharged into the river. These discharges contain
substantial amounts of fluorides as well as arsenic, cadmium,
chromium, copper, nickel and lead. Generally all of the
metal impurities can be removed by settling of the gypsum.
At present under state permits Occidental and Allied
must impound the gypsum when the river flow is below 200,000
cfs. Freeport must impound when the sulfate content of
their intake water is above 75 ppm.
The Refuse Act Permit Program will require total im-
poundment of the suspended solid gypsum by mid 1974 and a
reduction of the total sulfates to the river by 90% by the
end of 1975.
38
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ORGANIC CHEMICALS
The presence of organic chemicals in the water of
the Lower Mississippi River are objectionable for two
reasons; they are believed to be the primary cause of the
taste and odors in the finished water supplies and con-
tribute to the tainting of the fish flesh. Further, these
compounds are objectionable from a public health stand-
point because of their toxic nature. (See discussion on
toxicities later in the report.)
It should be emphasized that quantification of the
organics were not attempted in this investigation. In the
concentrations in the river they are usually referred to
as "trace" organics and are estimated to be in the "parts
per billion" to "parts per million" range.
Forty-eight organic chemicals have been found in raw
or finished water from three water plants - The U. S. Public
Health Service Hospital at Carville, Louisiana, the Jefferson
Parish #2 Water Plant at Marrero, Louisiana, and the
Carrollton Water Plant at New Orleans. Of these, thirteen
have been found in wastes from seven industrial plants. An
additional forty organic chemials have been found in wastes
from eleven industrial plants, including the seven mentioned
above, which have not yet been found in the raw or finished
waters of the three municipal plants. A complete list of
88 organic chemicals ranging from acetone to xylene which
have been isolated and identified by June 30, 1971, and the
streams in which they were found, appears in Table 16.
For the convenience of the reader, Tables 5 through 10
which follow present data on each of the three water plants
and industries whose wastes contain organics found in the
respective water plant's raw or finished waters. The total
number of compounds found in the different water supplies
varies from plant to plant. No significance should be
attached to these numbers. Different laboratories and
differing amounts of time were spent in isolating these com-
pounds from the extracts. Many additional compounds were
indicated on the GLC chromatograms, but time limitations
prevented their identification.
39
-------
Three organic compounds have been found in the
finished water supply of the U. S. Public Health Service
Hospital at Carville and in effluents from three indus-
tries as shown in Table 5. A total of eleven organic
compounds have been found at Carville as shown in Table 6.
TABLE 5
ORGANIC- COMPOUNDS IN THE FINISHED WATER AT THE
PUBLIC HEALTH SERVICE HOSPITAL AT CARVILLE, LA.
AND IDENTIFIED IN WASTES OF SPECIFIED INDUSTRIES
COMPANY ORGANIC COMPOUND
Enjay Chemical Co. ethyl benzene
(Baton Rouge)
vinyl benzene
toluene
Foster Grant Co., Inc. vinyl benzene
UniRoyal, Inc. vinyl benzene
40
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TABLE 6
LIST OF ALL ORGANIC COMPOUNDS
FOUND IN THE U. S. PUBLIC HEALTH
SERVICE HOSPITAL FINISHED WATER
acetylene dichloride
benzene
carbon tetrachloride
chloroform
1,2-dichloroethane
dimethyl sulfoxide
ethyl benzene
methyl chloride
propyl benzene
toluene
vinyl benzene
Twelve organic compounds have been found in the
finished water supply of the Carrollton Water Plant of the
City of New Orleans and in effluents from seven industries
as shown in Table 7- A total of thirty-six organic com-
pounds have been found at New Orleans as shown in Table 8.
41
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TABLE 7
ORGANIC COMPOUNDS FOUND IN THE CARROLLTON
WATER PLANT (NEW ORLEANS) FINISHED WATER AND
IDENTIFIED IN WASTES OF SPECIFIED INDUSTRIES
COMPANY
Copolymer Rubber & Chem. Corp,
(Baton Rouge)
Crown Zellerbach Corp.
Georgia Pacific Corp.
Enjay Chemical Co.
(Baton Rouge)
UniRoyal, Inc.
Foster Grant Co., Inc.
Rubicon Chemicals, Inc.
ORGANIC COMPOUND
acetophenone
vinyl benzene
a-camphanone
dimethoxy benzene
endo-2-camphanol
exo-2-camphanol
o-methoxy phenol
p-menth-en-l-8-ol
a-camphanone
dimethoxy benzene
endo-2-camphanol
exo-2-camphanol
o-methoxy phenol
p-menth-en-l-8-ol
ethylbenzene
toluene
vinyl benzene
isopropyl benzene
vinyl benzene
vinyl benzene
nitrobenzene
42
-------
acetone
acetophenone
benzene
bromobenzene
TABLE 8
LIST OF ALL ORGANIC COMPOUNDS
FOUND IN THE CARROLLTON WATER
PLANT (NEW- ORLEANS) FINISHED WATER
dichloroethyl ether
dimethoxy benzene
2,6-dinitro toluene
bromochlorobenzene
bromoform
bromophenyl phenyl ether
(positional isomer?)
butyl benzene
a-camphanone
chlorobenzene
chloroethyl ether
chloromethyl ether
chloroform
chloronitrobenzene
chloropyridine
dibromobenzene
dichlorobenzene
(positional isomer)
1,2-dichloro-ethane
endo-2-camphanol
ethyl benzene
exo-2-camphanol
hexachlorobenzene
l-isobrobenyl-4-isopropyl
benzene (1,2 isomer)
isocyanic acid
methyl biphenyl
methyl chloride
nitrobenzene
o-methoxy phenol
p-menth-en-l-8-ol
tetrachloroethylene
toluene
1,1,2-trichloroethane
vinyl benzene
43
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Four organic compounds have been found in the raw
water supply of the Jefferson Parish #2 Water Plant at
Marrero and in the effluents of four industries as shown
in Table 9. A total of fifteen organic compounds have
been found in the Jefferson Parish raw water supply as
shown in Table 10.
TABLE 9
ORGANIC COMPOUNDS IN THE RAW WATER AT THE
JEFFERSON PARISH #2 WATER PLANT AND
IDENTIFIED IN WASTES OF SPECIFIED INDUSTRIES
COMPANY ORGANIC COMPOUND
tf-t
Copolymer Rubber & Chem. Corp. acetophenone
(Baton Rouge)
Crown Zellerbach Corp. a-camphanone
p-menth-en-l-8-ol
Georgia Pacific Corp. a-camphanone
p-menth-en-l-8-ol
Rubicon Chemicals, Inc. nitrobenzene
44
-------
TABLE 10
LIST OF ALL ORGANIC COMPOUNDS FOUND IN THE
JEFFERSON PARISH #2 WATER PLANT - RAW WATER
a-camphanone
biphenyl
bis-chloroisopropyl ether
bromophenyl phenyl ether
bis-chloroethyl ether
bis-chloroisopropyl ether
dichlorobutene
2-methyl biphenyl
methyl-b-tolyl ketone
nitroanisol
nitrobenzene
0-phenyl anisole
p-menth-en-l-8-ol
l-propyl-2-methylnaphthalene
triethylene glycol dimethyl
ether
Table 11 is a listing of those industries which were
found to have high organic waste discharges as measured by
their COD (chemical oxygen demand) and TOC (total organic
carbon) loads. Both the TOC and COD are a measure of some
inorganic compounds. Thirteen industries listed are dis-
charging 40,000 pounds per day or more of COD and ten are
discharging 20,000 pounds per day or more to TOC. These
industries are considered to be discharging excessive organic
loads. All have been requested by the State to provide
secondary treatment or its equivalent by December 31, 1972.
45
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TABLE 11
INDUSTRIES WITH HIGH ORGANIC WASTE LOADS
CHEMICAL OXYGEN DEMAND 40,000 POUNDS PER DAY OR MORE
TOTAL ORGANIC CARBON 20,000 POUNDS PER DAY OR MORE
Company
Plant or Division
Borden, Inc.
Borden Chem. Div.
The Celotex Corp.
Chevron Chemical Co.
^ Ornite Additives Div.
n
Copolymer Rub. & Chem. Co,
Crown Zellerbach Corp.
Dow Chemical Co.
Enjay Chemical Co.
Chemical Plant
Ethyl Corp.
Freeport Minerals Co.
Freeport Chem. Co. Div.
Location
Geismar
Marrero.
Belle Chasse
Baton Rouge
St. Francisville
Plaguemine
Baton Rouge
Baton Rouge
Uncle Sam
Date Chemical
p
of Oxygen Demand
Sample (#/day)
*6-28-71
9-21-70
*8-10-71
1-4-70
11-2-70
1-20-70
*6-21/22-71
1-15-70
*4-6-71
6-9-71
1-14-70
11-3-70
74,900
88,000
45,300
76,400
170,000
380,000
57,750
553,600
206,800
111,700
42,400
60,000
Total Organic
Carbon
(#/day)
28,700
84,000
120,000
233,000
47,400
-------
TABLE 11 (Continued)
Company
Plant or Division
Georgia Pacific Corp.
Crossett Div.
Location
Port Hudson
Date Chemical
2
of Oxygen Demand
Sample (#/day)
5-4-70 101,000
Total Organic
Carbon2
(ft/day)
25,200
Humble Oil & Ref. Co.
Baton Rouge
Kaiser Alum. & Chem. Corp. Baton Rouge
Metals Div.
Shell Chemical Co.
Union Carbide Corp.
Gramercy
Norco
Hahnville
1-15-70
*6-8-71
1-19-70
8-30/31-71
8-31/9-1-71
9-7/8-71
9-8/9-71
2-16-70
1-22-70
M-21-71
213,000
61,300
173,000
80,400
87,500
80,100
70,600
82,200
342,000
149,900
**
7,700
27,000
67,600
76,400
48,200
27,000
24,000
120,000
46,100
The industries listed have COD loads equal to or greater than 40,000 pounds per day
and/or TOG loads equal to or greater than 20,000 pounds per day. These lower limits
were arbitrarily selected for screening purposes and do not imply that lesser quantities
of organics are acceptable.
2See Appendix, Exhibit F for additional data.
*Net loads (see explanation page 132;
**Interfering substances made determination invalid and/or questionable.
-------
TASTE AND ODOR*
Early in the study it became evident that, although
objectionable tastes and odors were occurring in treated
water from plants using the Mississippi River as their
source of raw water, the compounds believed to cause
tastes and odors were present in amounts too small to be
identified directly in the water. Since experience else-
where had demonstrated the feasability of adsorbing trace
organics on activated carbon to be later removed by ex-
traction with suitable solvents and concentrated until
measurable quantities were available for analysis, it was
decided that this approach would be used.
A program of threshold odor testing was initiated at
six plants, listed in Table 12; in January, 1969 and con-
tinued through March, 1971 at the Crown Zellerbach and
Carrollton Water Plants, and for one year at the remaining
four plants. Samples were collected once each week from
each plant and the threshold odor number (T.O.) was deter-
mined by the Environmental Protection Agency odor panel.
Operators at each of these plants were trained in the odor
test and panels were established. Daily odor testing was
performed and results were returned to the Baton Rouge
office. These results, though not as conclusive as those
of the larger Environmental Protection Agency panel, also,
indicated that odor problems were more severe below the
industrial complexes.
* The determination of threshold odor involves the comparison
of varying concentrations of odor bearing water with a sample
of odor free water until a concentration is reached that is
of the least definitely perceptible odor. The resulting
ratio by which the sample has been diluted is called the
"Threshold Odor Number" (T.O.). The presence, or absence,
of odors is determined by smelling, or "sniffing," a sample
that has been allowed to stabilize at room temperature. A
"panel" or group of five or more testers is preferred. For
most purposes the threshold of a group can be expressed as
the geometric mean (GM) of the individual threshold.
48
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The "average" threshold numbers in Table 12 are not
as significant as the maximum numbers. From January, 1969
through November, 1970 the T.O. was equal to or greater
than 13 in the raw water at the Carrollton Water Plant.
Six times during that period the T.O. was 20 or larger and
in January, 1969 a maximum of 45 was reached.
TABLE 12
RAW RIVER WATER
1969 THRESHOLD ODORS
River Average Threshold
Station Mile Odor Numbers
Crown Zellerbach, 260 7.3
St. Francisville
USPS Hospital, 191 12.8
Carville
Colonial Sugar Co., 146 10.0
Gramercy
St. Charles Plant No. 1, 125 11.3
New Sarpy
Carrollton Plant, 105 11.3
New Orleans
Jefferson Parish Water 99 12.0
Works #2, Marrero
Although not apparent in the tabular T.O. results, there
was a distinct qualitative difference in the odor of the
water at St. Francisville and that collected at the down-
stream sites. The description of the odor at the former
was predominantly "earthy" or "musty", while at the latter
sampling points it was usually described as "chemical" or
"petrochemical."
49
-------
In addition to the determination of tastes and odors
as just described> wastes from sixty industrial plants
were examined. All were found to have discernible tastes
and odors. In order to evaluate the odor potential of each
plant's waste discharge, the threshold odor number of the
fresh raw waste was multiplied by the daily average dis-
charge (in gallons). This value called "Odor Contribution"
gives an estimate of the rate (in gallons per day) of river
water to which a "threshold" or detectable odor would be
imparted.
Detailed results will be found in the Appendix, Exhibit
H which lists plants in order of decreasing odor contri-
bution. It will be seen that plant discharges having the
same characteristics as the samples analyzed will contri-
bute detectable odors at a rate ranging from 758 billion
gallons per day (the Crown Zellerbach Corporation at St.
Francisville) to as low as fifty thousand gallons (Argus
Chemical Company at Hahnville). Since 323 billion gallons
per day is considered the average flow at New Orleans, it
can readily be seen that if the wastes from the Crown
Zellerbach Corporation at St. Francisville were the only
ones discharged to the Mississippi River, more than double
the average river flow would be required to dilute them to
a point of no detectable odor. And this assumes that no
part of water treatment, such as chlorination, would in-
crease the taste and odor producing characteristics as in
the case of phenolics. Wastes from Enjay Chemical Company
at Baton Rouge, with an odor contribution ranging from 345
to 744 billion gallons per day, or those from the Hooker
Chemical Corporation at Hahnville, with an odor contribu-
tion ranging from 38 to 449 billion gallons per day, or
those from Humble Oil and Refining Company at Baton Rouge,
with an odor contribution of 135 to 331 billion gallons
per day, are capable of producing detectable tastes and
odors in the Mississippi River under average flow conditions,
Under minimum stream flow conditions of 129 billion gallons
per day the odor intensity will be increased about two and
a half times. The interpretation of these results must be
qualified, however, because the threshold odor test as per-
formed does not evaluate the "persistency" of the odors
with time and in contact with the aquatic environment.
50
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It is apparent that the strength of many of the
odors in the waste streams are partially dissipated in
the river - either thru biological degradation and/or
physical dispersion or evaporation. Many of the com-
pounds, however, do persist and find their way into the
finished water supplies and contribute to the higher
threshold odor numbers at the downstream location. Nor-
mal water treatment processes do not remove the low-level,
soluble organics. Continuous use of activated carbon
would probably be required to remove the trace organics
in the water supplies.
51
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TAINTING OF FISH FLESH
In addition to trouble with tastes and odors in
potable water supplies, it had been reported that objec-
tionable odors are present in the flesh of fish caught
in the lower Mississippi River in Louisiana to such an
extent that they cannot be sold. In November, 1969
commercial fishermen and wholesale and retail fish dealers
in the Simmesport (near R.M. 302) and New Orleans areas
reported that no fish taken from the Mississippi River
could be sold because of bad tastes. The dealers would
not buy, hence the fishermen fished elsewhere. ;
In June, 1971 the same dealers and fishermen in the
Simmesport and New Orleans areas were interviewed and had
the same answers - a kerosene, oily taste so strong that
the fish could not be sold. This condition was reported
to exist the year 'round. Most retailers refuse to attempt
to market fish taken from the Mississippi River because of
oily tastes of their flesh.
These two1 surveys indicated that water quality cri-
teria established by the State of Louisiana were being
violated, i.e. taste and odors must be "below levels of
detection following normal water treatment and below levels
that will produce objectionable odor in food fish and
seafood." (Emphasis added)
In order to obtain more direct, scientific evidence
of this fish tainting problem, on October 18, 1971, a fish
flesh tainting study was undertaken on the lower Mississippi
River to determine if taste and odor criteria were being
violated and which areas were out of compliance. Seven
stations were established between St. Francisville, Louisiana,
and Belle Chasse,, Louisiana (Tables 13 and 14). At each
station, a fish trap consisting of a hoop net with the
throat laced shut was placed near each bank in approximately
five feet of water. In each net were placed from four to
six channel catfish, Ictalurus punctatus, weighing between
three quarters and one and one half pounds. The fish were
obtained from a local market which in turn was supplied by
Mississippi delta fish farmers. This insured that the fish
were of high taste quality and not tainted with industrial
52
-------
or municipal waste. The test fish were placed in a one
thousand gallon tank at the laboratory for several days
before introduction into the river so that weak or diseased
individuals could be detected and eliminated. This screen-
ing process was later discontinued when market fish in good
condition became available. With the purchase of each
group of fish, five were dressed, wrapped in aluminum foil,
and frozen as a control to be later shipped with the test
fish for analysis.
The test fish were transported to the stations in a
live box with aeration. After a seventy-two hour exposure
in the river, they were removed from the nets and dressed
immediately. Each fish was individually wrapped in aluminum
foil and placed in a plastic bag on wet ice. The samples
were then returned to the laboratory on the same day and
frozen.
All samples were shipped frozen on dry ice to Oregon
State University, Department of Food Science and Technology
for a flavor evaluation. The frozen samples were received
at the Flavorium and stored in a freezer at -10°F until
tested. For testing, each frozen sample was enclosed in
aluminum foil, placed on a broiler type pan and cooked in
a large commercial style gas oven at 400°F for approximately
ninety minutes until the flesh flaked from the bone.
The cooked fish in each sample were boned, lightly
mixed to insure uniform serving samples, then placed in
the top of a double boiler over hot water to keep warm for
serving.
The samples were served in paper cups coded with three
digit random numbers except for one cup which was labeled
"ref" and contained the control sample. A duplicate con-
trol sample was included with the coded samples for scoring.
The judges scored the intensity of off-flavor on the follow-
ing scale: 7 (no off-flavor), 6 (slight off-flavor), 5
(moderate off-flavor), 4 (strong off-flavor), 3 (very strong
off-flavor), 2 (extremely strong off-flavor), 1 (totally
unacceptable). Scores of 6 and below were interpreted as
in violation of Louisiana stream water quality standards
on taste and odor for fcodfish.
53
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During each exposure period, water samples were
collected for odor analyses. The samples were taken at
a depth of one foot near each fish trap and placed on
wet ice for transport to the Baton Rouge laboratory for
taste and odor analysis.
DISCUSSION
Flavor scores were highest at St. Francisville, the
uppermost station (MR-01). Only small industrial and
municipal waste discharges into the River are located on
this stretch of the river. There was no appreciable
difference in flavor scores between the right (west) and
left (east) bank (Figure 1). The slight decrease in
flavor scores from the control was probably the result
of the natural background conditions in the River. The
taste panel judged the test fish at this station as having
a slight off-flavor.
Threshold odors in the water were also the lowest
(inverse scale from flavor scores) at St. Francisville
(Figure 2). Odors on the left bank were slightly higher
than the right bank.
Immediately below station MR-01 and fifteen to twenty
miles above the next downstream station MR-02, are two
large paper mills discharging into the river. It was
anticipated that these discharges would degrade flavors
at station MR-02. However, no decrease in flavor scores
occurred (Table III). The taste panel judged the test
fish as having a slight off-flavor. As paper mill waste
is well known for its ability to taint fish flesh, the
station was apparently far enough downstream to allow
sufficient dilution to eliminate any problem. Nevertheless,
threshold odors in the water were higher, especially along
the right bank.
At station MR-03, located immediately below the Baton
Rouge industrial complex, were found the lowest off-flavor
scores of the sutdy. This station was also unique in that
the greatest variation between left and right bank scores
was found. Practically all the Baton Rouge industry is
located on the left bank. The river along this area is
54
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straight for five miles followed by a gradual bend to
the right. Fish in the trap along the left bank exhib-
ited the worst flavor of any during the survey whereas
those along the right bank had scores only slightly lower
than station MR-02 above the Baton Rouge industry. The
panel judged test fish on the left bank as having an ex-
tremely strong off-flavor and those on the right only
slightly off-flavor.
Threshold odors in the water followed the same
pattern, with the left bank station having the strongest
odors of any station sampled. The only exception was
the right bank with less of an odor than its counterpart
at the adjacent upstream station.
Station MR-04 was located thirty-five miles below
MR-03 and immediately above the Geismar industrial area.
At this point, off-flavor scores along the left bank had
increased dramatically over the previous station. Scores
along the opposite bank, however, decreased by an almost
equal amount making left and right bank scores nearly
identical. The taste panel judged the test fish on both
sides of the river as containing a strong off-flavor.
Threshold odors in the water on the left bank had
decreased to near the pre-Baton Rouge levels. Right bank
levels were slightly lower than at the previous station
with the overall result being that both banks recorded
similar threshold odors. The upstream waste load had
apparently, by this time, become uniformly mixed.
As in the Baton Rouge area, the Geismar industry is
located on the left bank of the river. This fact was
evident by the data obtained at station MR-05 located just
below Geismar. Left bank flavor scores decreased, the
result of off-flavor producing waste in the Geismar area
being discharged along that shore. This waste was, how-
ever, quite restricted to the left bank as right bank scores
were slightly higher than the previous upstream station.
The panel judged the test fish on the left bank as con-
taining a very strong off-flavor with the right bank having
a strong off-flavor.
55
-------
Threshold odor levels for the wastes generally
followed the same pattern as the fish with higher thres-
hold levels along the left bank. However, levels also
increased, to a lesser extent, along the right bank.
Between Geismar and the next downstream station MR-06,
is a moderately industrialized sixty mile stretch of river.
Off-flavor scores increased significantly at this station.
For the first time, left bank scores were noticeably
higher than the right bank. Right bank scores were appar-
ently suppressed by a four-industry complex on that shore
five miles upstream. The panel judged the test fish on
both banks as containing a moderate off-flavor.
This increase in water quality was not evident in
the threshold odor scores. Except for a slight decrease
in the left bank and slight increase in the right bank,
levels varied little from the adjacent upstream station.
The last station, MR-07, was located approximately
thirty miles below New Orleans, and downstream of all
major industry in that area. Contrary to expectations,
the New Orleans area had little effect on the flavor of
the test fish. Scores on both banks were similar to those
found above New Orleans. A municipal treatment plant dis-
charge was discovered immediately above the right bank
fish trap on the day the nets were picked up. This, in
addition to an oil refinery two miles above the station,
probably prevented the right bank scores from approaching
the level of those on the left bank. The panel judged
the test fish on both banks as moderately off-flavor.
Threshold odors decreased on the left bank while the
right bank showed a slight increase. This resulted in
stronger water odors on the right bank than the left which
had occurred only once before at MR-02.
56
-------
All stations below Baton Rouge were found out of
compliance with Louisiana stream standards in regard to
objectionable taste and odor in food fish.
CONCLUSIONS
Industrial discharges into the Mississippi River
significantly taint the flesh of test fish placed down-
river of these discharges. These discharges are undoubt-
edly the primary cause of the off-flavor in native fish
in this reach of the river.
57
-------
TABLE 13
STATION LOCATIONS
LOWER MISSISSIPPI RIVER FISH TAINTING STUDY
OCTOBER - NOVEMBER 1971
Station Location
MR-01 Four miles below St. Francisville, Louisiana.
MR-02 Four miles above Baton Rouge, Louisiana.
MR-03 Six miles below Baton Rouge, Louisiana.
MR-04 Six miles above Geismar, Louisiana.
MR-05 Three miles below Geismar, Louisiana.
MR-06 Two miles above Luling, Louisiana.
MR-07 Twenty four miles below Greater New Orleans
bridge.
58
-------
TABLE 14
STATION DATA
LOWER MISSISSIPPI RIVER FISH TAINTING STUDY
Station Date
MR-01R
MR-OIL
MR-02R
ui
MR-02L
MR-03R
MR-03L
MR-04R
10-19-71
11-1-71
R.M.
261
10-19-71 261.5
10-27-71 236.5
10-27-71 236.5
10-27-71 225.3
10-27-71 225.8
191.3
Stage
6.4
6.4
-6.0
6.0
6.0
6.0
5.3
Air
Temp.
22.0
22.0
24.0
24.0
27.0
27.5
23.5
Station Sample Water
Depth*
10
71
Depth
I1
8'
I1
9'
I1
3'
I1
4'
I1
3'
I1
3'
1'
6'
Temp.
21
22
21
22
21
22
21
22
22
23
21
23
21
22
.5
.0
.5
.0
.5
.0
.5
.0
.5
.5
.5
.5
.5
.5
D
8
8
8
7
8
7
8
8
8
8
7
7
7
7
.0.
.5
.4
.0
.8
.1
.7
.2
.8
.5
.5
.4
.4
.3
.3
ŁH
7.8
7.8
7.8
7.7
7.5
7.6
7.4
7.3
7.6
7.7
7.6
7.6
7.6
7.6
-------
TABLE 14 (Continued)
Air Station Sample
Station Date R.M. Stage Temp. Depth* Depth
MR-04L 11-1-71 191.3 5.3 23.5 14' 1'
13V
MR-05R 11-1-71 182.2 5.3 26.0 10' 1'
91
MR-05L 11-1-71 182.2 5.3 22.5 8' I1
71
-------
TABLE 15
FLAVOR (FISH) AND THRESHOLD ODOR (WATER) DATA
LOWER MISSISSIPPI RIVER FISH TAINTING STUDY
OCTOBER - NOVEMBER 1971
Station
Control
MR-OIL
MR-OlR
**LSD (05)
Control
MR-02R
MR-03L
MR-03R
**LSD (05)
Control
MR-04L
MR-04R
MR-05L
MR-05R
MR-06L
MR-06R
**LSD (05)
Control
MR-02L
MR-07L
MR-07R
**LSD (05)
Water
Threshold
Odor
2.4
1.7
4.8
26.9
3.7
3.6
3.0
9.0
6.3
8.7
7.3
3.7
6.3
8.0
Off-flavor
(Raw Data)
6.1
5.5
5.4
0.4
6.5
5.8
1.9
5.7
0.6
5.6
3.4
3.6
3.2
3.6
4.9
4.4
0.8
6.0
5.4
5.1
4.5
0.5
Off-flavor*
(Corrected Data)
7.0
6.2
6.1
7.0
6.2
2.0
6.1
7.0
4.1
4.3
3.9
4.4
5.9
5.3
7.0
6.1
5.9
5.1
* Data Normalized, to a Perfect Control Score of 7.O.
Panel's Evaluation
Off-flavor
Slight
Slight
Slight
Extremely Strong
Slight
Strong
Strong
Very Strong
Strong
Moderate
Moderate
Slight
Moderate
Moderate
-------
FISH FLAVOR SCORES, NORMALIZED WITH A MAXIMUM CONTROL SCORE OF 7
7 ^Ťť
RIGHT BANK
LEFT BANK
ACCEPTABLE
UNACCEPTABLE
O)
o
O
2)
m
UJ
O
cc
o
en
UJ
_l
IT
O
UJ
UJ
_)
J
>
CO
o
z
or
50
100
150
RIVER MILE
200
250
-------
LEFT AND RIGHT BANK RIVER WATER THRESHOLD ODOR SCORES
m
I
m
o
o
o
33
o
o
3}
m
en
30
25
20
o
o
o
x !!!
(O f%
C3 5 "
x ť O
O - I
15
llJ
cr
x
10
RIGHT BANK
LEFT BANK
5O
IOO
ISO
RIVER MIUE
2OO
25O
-------
TOXICITY OF SELECTED ORGANIC CHEMICALS
The effects of low-level organics, such as were found
in the drinking water supplies along the Mississippi River
in Louisiana, on the health of people consuming the water
is not easily determined. These chemicals may be harmless
or toxic in a very short period, or their effects may not
be evidenced for several years.
Because some of the compounds found in the water sup-
plies are suspected toxicants under special experimental
conditions, and because of the dearth of knowledge regarding
their low-level effects, it is important that all identified
sources of these compounds be controlled as rapidly as the
technology for their control becomes available.
A general discussion of some known toxic and/or carcin-
ogenic effects of the chemical found either in the finished
'water supplies or in industrial discharges follows. Details
of toxicity studies are presented in Tables 17 thru 19, with
references included for each study. Table 16 lists the
identified organics and identifies water supplies in which
they were found as well as the individual effluent discharges
which were their sources to the river.
Table 17 contains available chronic toxicological
information on chemicals found in the finished water supplies.
Large gaps of information exist for chronic toxicity and the
greatest proportion of chronic toxicological data available
on organic chemicals is contained in the Russian literature.
The doses presented for chronic toxicity are those which
elicited an effect and where this was not available, the
doses used are presented. (45) All doses are oral unless
otherwise indicated.
Table 18 contains acute toxicological information on
chemicals found in water. LDso in mammals form the highest
proportion of acute toxicity information available. Data
on non-mammalian species were included when available. All
64
-------
doses are oral unless otherwise indicated. LDso is the dose
at which 50% of the animals die. TLm designates the median
tolerance limit which is the concentration which kills 50%
of fish for the indicated time in hours. LC is the con-
centration in the gaseous form which will kill the test
animals in a given time period. The acute toxicity data
is useful for determining relative toxicity and for chronic
toxicity.
Table 19 contains information regarding the carcin-
ogenic (cancer causing) properties of some of the organic
chemicals found in the water supplies.
The references following this chapter are selected
to represent literature in this field.
65
-------
DISCUSSION
There is growing evidence that a significant propor-
tion of malignancies may be initiated or promoted by
environmental factors (6, 8, 9, 13, 17, 21, 52, 64,).
Unlike the great epidemic diseases of the past, present
diseases associated with development and aging of the
human organism are of complex etiology; multiple factors
are involved.
In view of these observations, The Food and Drug
Administration has become very cognizant of the importance
of carcinogenic (cancer causing), teratogenic (malformation
causing)/ and mutagenic (capable of causing inheritable
mutations) of pharmaceutical agents and chemicals used as
food additives. As a result, food additives with carcin-
ogenic properties are barred from use regardless of how
carcinogenicity was demonstrated on animals. In contrast,
these types of data have not been used as limiting indices
in water quality criteria. Yet, because of physiological
requirements, danger from the presence of these agents in
water is greatly increased.
In terms of human health, total exposure of a human
being to a given substance from all parts of his environ-
ment - air, watery and food - must be considered, and the
interaction of these substances both within and outside
the body must be evaluated.
A tremendous number of synthetic organic chemicals
have been introduced into our water supplies (45, 52, 58).
As previously stated, 88 have been isolated and identified
either in industrial waste discharges or in water supplies
in the Lower Mississippi River in Louisiana (see Table 20).
Some of these compounds have been shown to be carcinogenic
in experimental animals. A smaller number have been singled
out as capable of causing cancer in humans. Infrequently,
others have been identified as teratogenic or mutagenic.
66
-------
Six chemicals found in either the finished water
supplies of the New Orleans Carrollton Plant or U. S.
Public Health Service Hospital, or both, induce histo-
pathological changes in chronic animal studies (see
Table 17).
Only three of the chemicals, benzene, carbon tetra-
chloride and chloroform, found in the finished waters
have been indicated as being carcinogenic and may be con-
sidered chronic toxicants (see Table 19).
Equally significant, chronic toxicological data was
not available for most of the organic chemicals found
so far in these water supplies. Furthermore, there may
be a myriad of organic chemicals, not yet isolated and
identified, such as the pesticides, that could be present
in these water supplies which are carcinogenic, teratogenic,
or mutagenic.
It is clear that society must weigh carefully the
expenditures for corrective action, both industrial and
municipal against the costs it may have to pay in terms
of present or future health impairment of its people
stemming from man-made hazards.
In examining this dilemma, thought must be given to
questions like the following which were posed to the
Gross Committee (44):
How are the long-term effects of chronic exposure
to low concentrations of toxic agents acting singly or
in concert with other chemical or physical agents
assessed?
How are susceptible subgroups within the popu-
lation which may be at special risk because of age,
sex, genetic background, or pre-existing physical
impairments identified?
To what extent are diseases of unknown etiology,
such as chronic degenerative diseases affecting the
cardiovascular and respiratory systems aggravated by
exposure to environmental agents?
67
-------
There are no quick and easy solutions. The effects
of toxic substances on man vary according to the nature
of the substance, the quantity of the substance to which
a person is exposed, the duration of exposure, the consti-
tution of the person, including age, sex, health, and
genetic makeup.
Because of the number of variables involved, chronic
animal toxicity studies used in establishing limiting
indices for Water Quality Criteria can only be used as
a starting point.
All of the toxicity studies referenced in this report
were initiated with healthy animals. The various toler-
ances set by governmental agencies based on these animal
studies and extrapolated for humans are for healthy indi-
viduals; as health conditions deteriorate, the environmental
stresses from the toxic chemicals are magnified.
The water consumers at the U. S. Public Health Service
Hospital at Carville and at private and local governmental
hospitals in New Orleans are not healthy people, but are
patients with debilitating impairment of vital organs,
i.e., the liver, kidneys, urinary bladder, lungs, heart
and blood vessels. These organs compose the body's detoxi-
cation system. This system has evolved to protect the
individual from the toxic effects of naturally-occurring
foreign compounds of the diet by rapid metabolic transforma-
tion and excretion.
Since the hospital patients are suffering from various
vital organ impairments, their protection is diminished,
and the insult of the various heavy metals and toxic chemi-
cals on their health is therefore much greater than it is
on the general population.
Another grave situation involves the potential chronic
effect of these contaminants on the health of the young
children of the New Orleans area, not because of any organ
disorder, but resulting from underdevelopment of certain
enzyme systems needed for metabolizing foreign compounds.
68
-------
These two groups of people, plus the senior citizens,
are the most susceptible to the detrimental effects of
these drinking water contaminants, because of their inherent
biochemical conditions.
It is mandatory to single out potentially harmful
substances and prevent them from entering those bodies of
waters that will be used for drinking or food sources until
it is clearly demonstrated that they pose no threat to
human health or aquatic life. Determination of additional
substances that might be harmful in long-term, low level
exposures will require improved knowledge of the specific
compounds that are entering receiving waters. It will also
require considerable more research in epidemiology, in
addition to laboratory animal studies. Priorities will
have to set, attacking first those chemicals having an
oral LD5Q value of less than 100 mg/kg or TLm value of less
than 20 mg/1 (LDsg - lethal dose that will kill 50 percent
of test animals over a given time period. TLm - median
tolerance limit - concentration that will kill 50 percent
of test animals over a given time period.)
69
-------
TABLE 16
ORGANIC CHEMICALS ISOLATED FROM RAW & FINISHED WATERS AND INDUSTRIAL WASTES
ORGANIC COMPOUND
acetone
acetophenone
acetylene dichloride
*^]
o alkylated benzene (C14.H20)
benzaldehyde
benzene
biphenyl
bromobenzene
bromochlorobenzene
bromoform
bromophenylphenyl ether
(positional isomer?)
butyl benzene
a-camphanone
carbon tetrachloride
chlorobenzene
bis-chloroethyl ether
chloromethyl ether
chloroform
PS
W rs>
EH #
<
gPS PS
Q ^ W
i-3 W ft EH
J a
H a
ft fa U
X
X
X
X
a
u
<
m
PS
w
PS J W
w w a
S N U
1-1 s ^
o ^ ^
ft O b
O PS 121
u u w
X
X
X
fa
u w
H PS
fa
EH H t3
13 U
fjj <] ij jgj
PS ft H H
o o a
< u
PS H W
W O iJ J
EH PS eg J
CO O g W
Sw 5 a
o a co
X
X
W
O EH
g S5 EH
WHO
a Q
o s
J 5<
^J rtj bn
O ^ ^
U 0
H PS fa
pq H co
PS D OQ
X
-------
TABLE 16 (Continued)
ORGANIC COMPOUND
m-chloronitrobenzene
bis-chloroisopropyl ether
3-chloropyridine
&
w
EH
<
13 IS
§°
J H
( 1 rt
O c/3
PS H
PS Ł5
O S s
W DJ o I"
JTH f \ QX ^
U U U P
U
H
PM
EH H
ť* H IS
t 1 C_) O
J H PS Pq
ffi IT!) !2 rf^
CO PH & PQ
cresol, probably o-cresol
n-decane
1 dibromobenzene X
4,4'dibutenyl disulfide
dichlorobenzene
(positional isomer?) X
dichlorobutene
1,2-dich.loroethane X
dichloroethyl ether X
dicyclopentadiene
diisopropyl benzene
(probably 1,3 isomer)
1,2-dimethoxy benzene X
1,3-dimethyl naphthalene X
2,3-dimethyl naphthalene
2,3-dimethyloctane
dimethyl sulfoxide
X
X
X
X
X
X
X
X
X
X
X
X
X
X
-------
TABLE 16 (Continued)
ORGANIC COMPOUND
2 , 6-dinitrotoluene
m-divinylbenzene
n-dodecane
n-eicosane
H
EH
0 ^
EH Q
i 1 W
t 1 X
O CO
O3 H
< H
U fe
X
CM EH PL)
# H EH
ft <
CO 12
On O3 O
< W a Q
ft EH W
<; i [rj
& co co
PL, . H
PLJ |2 33 tt
W < H
r"^ fy (i( r*Ti
s
1 0!
H
a 1^4
O ?H
Pi iJ
t> o
H ft
ffi O
U U
a
u
CQ
H
w
N
*z
O
03
O
S
w
ffl
0
>H
s
w
EH
1
O
O3
H
EH
CO
o
fe
U
H
fo
H
U
ft
pj]
H
O
o
w
0
1
tjj
H
o
w
I_II
i
^
a
X
X
s
a
u
j
w
a
co
g
U
a
o
u
H
m
J^3
03
U
H
lJ
rij
JH
O
03
H
13
D
X
H
EH
EH
|
f-C
^
^
CO
^
ffl
^4-ethenyl-l-cyclohexane X
wethyl benzene XX X
ethyl heptane (positional
isqmer?) X
ethyl hexyl phthalate X
4-ethyl pyridine X
4-ethyl styre-ne X
endo-2-camphanbl X X
exo-2-camphanol X XX
n-heptadecane X
hexachlorobenzene X
n-hexadecane X
isocyanic acid X
l-isopropenyl-4-isopropyl-
benzene (or 1,2 isomer) X X
l-isopropenyl-3-isopropyl-
benzene X
o-methoxyphenol X XX
-------
TABLE 16 (Continued)
ORGANIC COMPOUND
2-methylbiphenyl
methyl chloride
c-11^24 a me"thyl decane
l-methyl-2-ethylbenzene
l-methyl-4-ethylbenzene
C13H28 (probably 5-methyl-
5-ethyldecane)
1-methylnaphthalene
2-methylnaphthalene
methyl-b-tolyl ketone
naphthalene
nitroanisole
nitrobenzene
n-nonadecane
n-octadecane
n-pentadecane
phenols
o-phenyl anisole
phenyl cyclohexane
propyl benzene
CARROLLTON
FINISHED WATER
JEFF. PAR. #2
RAW WATER
X X
X
X
X
X X
X
P.H.S. HOSPITAL
FINISHED WATER
X
X
CHEVRON CHEM.
COPOLYMER
CROWN ZELLERBACH
X
X
X
X
X
EN JAY CHEM.
FOSTER GRANT
X
X
X
X
GEORGIA PACIFIC
HUMBLE OIL & REF
X
X
X
X
X
X
X
X
X
SHELL CHEM.
RUBICON CHEM.
X
X
UNI ROYAL, INC.
X
BASF WYANDOTTE
-------
TABLE 16 (Continued)
ORGANIC COMPOUND
l-propyl-2-methylnaphthalene
p-menth-l-en-8-ol
tetrachloroethylene
tetradecane
n-tetradecane
^toluene
1, 1, 2-trichloro ethane
PS
H
EH
<
X Ł
0
.En Q
i 1 fa"
i-3 K
O CO
PS H
PH ^1
< H
U fa
X
X
X
X
CM
*
PS PS
H M
O-i fa O
X
PS
w
p
l_3
o
04
o
u
X
ffl
u
<
ffl
PS
w
J S
J W
w ffi
N U
g3 [ť
S H
O
PS
H
g
w
EH
EH
O
P
13
SH
^
fa
CO
-------
TABLE 17
MAMMALIAN CHRONIC TOXICITY OF ORGANIC POLLUTANTS FOUND IN FINISHED
WATER FROM CARROLLTON AND U. S. PUBLIC HEALTH SERVICE HOSPITAL
Ref Organic Compound
45 Chloroform
Species
Dose
Chronic Toxicity
Effect
Guinea
Pig
-j
Ul
Albino
Rat
0.4 mg/Kg
35 mg/Kg
0.4 mg/Kg
125 mg/Kg
12.5 mg/Kg
Increase in Vitamin_C in adrenals.
Decrease in blood catalase; decrease
in phagocytic capacity of leucocytes;
structural lesions in liver, heart
muscle and stomach wall; fatty infil-
tration, necrobiosis, and cirrhosis
of liver parenchyma, lipoid degenera-
tion and proliferation of insterstitial
cells in myocardium, and acute edema
of the submucous and muscular layers
of the stomach.
No effect.
Decrease in conditioned reflex; de-
crease in cholinergic-activity;
histological changes.
Affects conditioned reflexes by
fourth month.
-------
-J
CTi
Ref
45
45
45
45
45
Organic Compound
Dichlorobenzene
Methylethyl Ketone
Hexachlorobenzene
Xylene
TABLE 17 (Continued)
Chronic Toxicity
Species
Rat
Warm
Blooded
Animals
Rats
Rat
Ethyl Benzene
Rabbit
Dose
0.003 mg/Kg
daily for
5 months
0.005 mg/Kg
daily for
4 months
4 and 48
mg/Kg daily
for 5 1/2
months
48 mg/Kg
daily for
5 1/2
months
5 mg/Kg
in drink-
ing water
Effect
No significant effect.
No significant effects.
Changes in conditioned reflexes,
Occasional variation in hemoglobin,
erythrocytes, and leucocytes;
marked eosinophilia; change in
reticulocyte number.
Lymphopenia
Effect on: CNS, growth, morpholog-
ical composition of blood,
pathological and histological
changes in organs.
-------
Ref
45
Organic Compound
Toluene
TABLE 17 (Continued)
Chronic Toxicity
Species
Rabbit
45
Dimethylsulfoxide
Fish
Dose
Effect
0.25, 1.0,
and 10 mg/Kg
for 9 1/2 and
5 months
High cone.
or over long
period of
time
No significant effects,
Change in number of various blood
components; histopathological
changes in liver, kidney, brain,
gills, and spleen.
-------
TABLE 18
ACUTE TOXICITY OF ORGANIC POLLUTANTS
Ref
-j
00
45
Organic Chemical
Acetone
Acetophenone
Acetylene
dichloride
Benzaldehyde
Benzene
Biphenyl
Borneol
Bromoform
Camphor
Species
rabbits
rats
mice
rats
rats
sunfish
rats
Oral LD5Q
mg/Kg
5300
3000
S.C. 5000
5700
2200
rabbits 2000
rabbits S.C. 1000
96 hr
TLm mg/1 ppm
35-37
15,000
Toxic Effect
Chronic: bone marrow de-
pression & aplasia, rarely
leukemia. CNS depression,
paralysis, convulsions have
been observed in experimental
animals.
rats
S.C. 2200*
1. Subcutaneously injected.
-------
TABLE 18 (Continued)
Ref
Organic Chemical
Carbon
Tetrachloride
45
Chloroform
Cresol
Species
man
mosquito
fish
Oral
mg/Kg
mice
rat
rabbit
guinea
pig
rat
5700
5700
5700
1900
96 hr LC5Q
TLm mg/1 ppm
10-24
Toxic Effect
10,000 Liver and kidney damage
Chronic poisoning from
oral or percutaneous absorp-
tion may produce nervous
disorders, mental changes,
skin eruptions, jaundice,
oliguria, & uremia.
p-Dichlorobenzene rats
B, B x-Dichloroethyl-
ether rats
I.P.-1- 2560
105,000
Continuous exposure, may
cause portal cirrhosis,
subacute yellow atrophy
of liver. May cause liver
& kidney damage.
1. Injected inter-peritoneally.
-------
TABLE 18 (Continued)
Ref
45
00
o
45
Organic Chemical
Dimethyl Sulfoxide rats
Ethylbenzene mice
Ethylene Bichloride rats
Guaiacol rats
Oral LD50 96 hr
Species mg/Kg TLm mg/1 ppm Toxic Effect
Isocyanic Acid
Isopropenyl
Methyl Chloride
Naphthalene
Nitrobenzene
Phenol
rabbits
perch
rats
mice
rat
sunfish
rats
rats
20000
770,000
S.C. 900,000
10,400
I.V. 3700
3000
2000
700,000**
530,000
70-80 (48 hrs)
3150
4-5
Liver and kidney injury
Chronic exposure may
cause fatigue and
weakness.
Injury to liver & kidneys,
2. Injected intravenously.
-------
TABLE 18 (Continued)
Ref
45
CD
Organic Chemical
Styrene
Tetrachloro-
ethylene
Toluene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Xylene
45
Species
catfish
rats
mice
rats
sunfish
rats
rats
rats
sunfish
Oral
mq/Kg
8850
S.C. 5000
2960
820,000
4000**
96 hr
TLm mq/1 ppm
16.7
Toxic Effect
2000
6000
6000
61-65 (lethal in 1 hour)
6000
47-48 (lethal in 1 hour)
54 All data were obtained from the Eighth Edition of Merck Index, except where indicated.
* M.L.D.
** LD which is essentially the LD 100.
-------
TABLE 19
CARCINOGENICITY IN MAMMALS OF ORGANIC POLLUTANTS IN WATER SUPPLIES
This Table presents available information on Carcinogenicity of Chemicals which are
pollutants of New Orleans water supplies.
Ref
31
Organic Compound
P-Cresol
Routes
Skin
Skin
oo
to
31
Carbon Tetrachloride Oral
Oral
Dose
3% in
alcohol
3 times
weekly
3% in
alcohol
3 times
weekly
0.125-0.5
ml/Kg
3x wk in
al:l soln
& corn oil
0.2 ml of
2% olive
oil soln
2x wk
interval
Species
Mouse
Rat
Dog
Mouse
Tumor Results
Negative
Negative
0/8 Out of eight animals
no tumors.
+/37 Tumors showed - number
not own
3% soln
given
weekly
for 17 wks
-------
TABLE 19 (Continued)
Ref Organic Compound
Routes
31
Carbon Tetrachloride Oral
(Cont'd)
31
Chloroform
Oral
oo
u>
56
Tetrachloroethylene Oral
jDose
0.1 ml of
40% soln
in olive
oil, 3x wk
for 45-66
doses/ 13
1/2 wks
8 x 10~4
and
4 x 10~4
ml dose
in olive oil
every 4
days, 30
times
2% in diet/
13 months
0.33 mg/Kg,
8 doses
at 4d.
intervals
Species
Mouse
Tumor Results
Positive
Mouse
7/20
Rat
0/40
0/18
-------
TABLE 19 (Continued)
Ref Organic Compound
57
Naphthalene
Routes
Oral
57
p-Dichlorobenzene
Oral
oo
57
Toluene
Oral
Dose
In oil
(in syn-
thetic diet)
6 times a
wk, 10-20
mg until
dose of 10g/
rat in food
500 mg/Kg
fed 5d/wk
for total
of 263
doses
118,354,
or 590
mg/Kg/d.
in 2-3 ml
olive oil
soln
emulsified
& 5-10%
aqueous
soln of
acacia for
138; feed-
ings.
Species
Rat
Tumor Results
Negative
Cataracts induced
Rabbit
0/7
Rat
Negative
-------
TABLE 19 (Continued)
Ref Organic Compound
57 Acetone
Routes
Dose
Species
Tumor Results
31 Acetophenone
57 Benzene
56 Guaiacol
CO
31 Xylene
Skin
S.C. or
I.V.
Skin
S.C.
Skin
0.2 ml Mouse
of 100%
2x wk
for 1 yr
Daily/ Rabbit
40 day
Twice Mouse
weekly
1-4% in Rat
olive oil,
26 inj
(S.C.)
Weekly Mouse
applica-
tion
Negative
Negative
+/21
Negative
Negative
-------
CHAPTER III
WATER QUALITY STANDARDS VIOLATIONS
The water quality standards of the State of Louisiana
and the Federal government relating to taste and odor pro-
ducing substances are being violated by industrial waste
discharges to the Lower Mississippi River in Louisiana. On
February 12, 1968, The Honorable Stewart Udall, then Secre-
tary of the Interior, advised Governor John McKeithen of
Louisiana by letter that the water quality standards of
Louisiana had been approved. SPECIFIC CRITERIA (b) Taste
and Odor - of these standards reads as follows:
Taste and odor producing substances
shall be limited to concentrations in
the waters of the state that will not
interfere with production of potable
water by reasonable water treatment
methods, or impart unpalatable flavor
to food fish, including shellfish, or
result in offensive odors arising from
the stream or other wise interfere with
reasonable use of the water.
Municipal water plants using the Lower Mississippi
River as their source of raw water include those of New
Orleans, Jefferson Parish, the U. S. Public Health Service
Hospital at Carville, Louisiana, and others. As shown
earlier in Tables 5 through 10, thirty-six organic compounds
have been isolated from the treated water from the Carrollton
Water Plant serving New Orleans, fifteen in the raw water of
the Jefferson Parish Marrero Plant and twelve in the finished
water at the U. S. Public Health Service Hospital. Allowing
for duplication, or finding the same compound in more than
one water supply, a total of forty-eight compounds have been
identified in the water supplies of these three plants.
86
-------
Twelve of the compounds listed above Have been
identified in waste discharges from seven industries.
These compounds, and industrial plants in whose wastes
they have been found, are listed in Tables 5 through 10
pages 40 through 45 of this report.
These compounds and many others not identified are
believed to be the primary cause of the taste and odors
of these water supplies and in the fish caught in this
reach of the river.
87
-------
CHAPTER IV
INDUSTRIAL WASTE TREATMENT
The following information in Table 20 was compiled
to reflect the current status of industrial waste treat-
ment on the lower Mississippi River in Louisiana as well
as the proposed treatment as presented to the Louisiana
Stream Control Commission in a series of permit review
meetings as authorized by P.L. 89-234 during the latter
part of 1970 through early 1971. Many of these facil-
ities are presently under construction and a few have
been completed. In addition, some industries have had
later meetings with the Louisiana Stream Control Commis-
sion and modifications and improvements to the proposed
treatment facilities shown in Table 20 were accepted by
the Commission. Current status of the state's approved
waste abatement plans can be obtained from the Executive
Secretary of the Louisiana Stream Control Commission,
P. 0. Drawer FC, Louisiana State University, Baton Rouge,
Louisiana, 70803.
Further, the Environmental Protection Agency in
conjunction with the U. S. Army Corps of Engineers has
initiated the Refuse Act Permit Program under Section 13
of the River and Harbor Act of 1899 and Executive Order
No. 11574. This has resulted in the development of waste
abatement programs by industry which in some instances
go beyond what was required by the State of Louisiana.
Information regarding the current status of these permit
applications and implementation plans for waste abatement
can be obtained from the U. S. Army Corps of Engineers'
District Office in New Orleans whose address is P. 0.
Box 60267, New Orleans, Louisiana, 70160 or the Environmental
Protection Agency, Region VI office in Dallas Texas, whose
address is Enforcement Division, Permits Branch, 1600 Pat-
terson Street, Suite 1100, Dallas, Texas 75201.
88
-------
TABLE 20
PROPOSED OR EXISTING INDUSTRIAL WASTE TREATMENT
TREATMENT
COMPANY
Allied Chem. Corp.
Ind. Chem. Div.
(Baton Rouge)
Allied Chem. Corp,
Spec. Chem. Div.
(Baton Rouge)
oo
Allied Chem. Corp.
Plastics Div.
(Scotlandville)
Allied Chem. Corp.
Geismar Complex
(Geismar)
TYPE OF WASTE
Chemical and
Petrochemical
EXISTING
Chemical (Chlo-
rides, Sulfates,
Fluorides,Chro-
mates)
Petrochemical
Agri-chemical and
Petrochemical
In-process recovery systems,
lime neutralization pond,
organic recovery system,
impounding basin to treat
lead and chrome.
HCl discharged to Mississippi
River, all other wastes dis-
charged to batture for
settling.
Suspended solids removed in
settling chamber with
mechanical skimmer.
Impound Gypsum-
bioxidation pond.
PROPOSED TO STATE OF LA.
Meet best practical treat-
ment for organics by
January 1, 1973.
Separation and treatment of
sanitary wastes, construct
compounding basin for
calcium sulfate residue.
Reduce chromates by 40%
and eliminate excessive
uses of recirculated
cooling water.
Conversion of oxidation
and settling ponds for
ethylene and nitrogen
plants to biological
systems. Maximum recycling
of water from HF and phos-
phoric acid plant. (Comple-
tion Dec. 1972)
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Allied Chem. Corp.
Ind. Chem. Div.
(Marrero)
American Cyanamid
Co. (Avondale)
TYPE OF WASTE
Chemical
Argus Chem. Corp.
I (Hahnville)
Petrochemical
Avondale Shipyards, Barge cleanings
Inc. (Avondale)
BASF Wyandotte
Corp. (Geismar)
Petrochemical
EXISTING
Inorganic Chemical None
Three deep well disposal
systems - Organic recovery
system (Completion 6-1-71);
Sanitary waste treatment
(Completion 5-1-71); Chromate
reduction (Completion 6-1-71).
Separators and skimmers.
Dilution, Rated aeration
sewage treatment plant -
Capacity 11,000 gpd, oil-
water separator, steam
stripping of water solubles.
Organic wastes separated,
neutralized, or incinerated,
PROPOSED TO STATE OF LA.
None
Surface water collection
system (Completion 10-1-71)
None-Considered equivalent
of secondary.
Neutralization, activated
carbon filtration, con-
trolled release of non-
volatile, non-toxic chemicals.
Incineration of organics;
recycling for recovery of
chlorides; stabilization
pond; oil skimmer.
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Borden, Inc.
Borden Chem. Div.
(Geismar)
TYPE OF WASTE
Petrochemical
EXISTING
The Celotex Corp.
(Marrero)
Bagasse
-"C-F. Industries
(DonaIdsonvilie)
Chevron Chem. Co.
Oronite Add. Div.
Oak Point Plant
(Belle Chasse)
Chemical
Organic Chem.
Waste handling system
(central collection system),
stabilization lagoon.
Diversion of sewage to
Jefferson Parish-Marrero
waste treatment process.
Neutralization pond,
aeration pond.
API oil-water separator,
mechanical belt oil skimmer.
PROPOSED TO STATE OF LA.
Separation of process and
uncontaminated surface run-
off, secondary treatment
(Completion 1972); deep
well disposal - chromates
(Completion 1971-72)
Recirculation and rinse
of cellulose fiber through
alterations in piping and
storage of used process
water (Completion 1972)
Add baffles to aeration
pond to correct short-
circuiting.
Holding tanks, air flotation,
coalescing units (1&2),
final settling, segregation
of process and storm water
drainage, deep well dis-
posal (Completion 1st
quarter 1972).
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
TYPE OF WASTE
EXISTING
Ciba-Geigy Chem. Agri-chemical
Corp. (St. Gabriel)
Copolymer Rubber & Petrochemical
Chem. Corp.
(Baton Rouge)
Copolymer Rubber & Petrochemical
Chem. Corp. (Addis)
Cos-Mar Plant, Mar- Petrochemical
bon Div. of Borg
Warner (Carville)
Deep well disposal, "Oxigest"
system for sanitary waste.
Oil and grease trap, steam
stripping of styrene, removal
of rubber particles by screens
and hydrocyclones, surge
system to handle plant upsets,
segregation of storm and
process water.
Precipitation basin,
oxidation
Aerated packaged plant for
sanitary wastes, chlorination
of intake water.
PROPOSED TO STATE OF LA.
Chromate removal, impound-
ing basin (Completion 1971),
in-plant improvements to
reduce effluent 50%.
Dissolved air flotation
(Completion 1971), coales-
cing system, activated sludge
bio-oxidation system.
None-Treatment incorporated
into plant design and con-
sidered equivalent of
secondary.
Contracted consultants to
determine concentrations
and substance in effluent
streams, possibility of
process modifications,
surface water run-off.
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Crown-Zellerbach
Corp. (St.
Francisville)
The Dow Chem. Co.
(Plaquemine)
TYPE OF WASTE
Paper Mill
Petrochemical
C. I. duPont de Petrochemical
Nemours & Co.,Inc.
(LaPlace)
EXISTING
Extended aeration, activated
sludge for sanitary waste,
fiber recovery equipment.
Enjay Chem. Co.
Chem. Plant
(Baton Rouge)
Enjay Chem. Co.
Plastics Plant
(Scotlandville)
Petrochemical
Petrochemical
API separator, coalescers,
in-plant changes.
Deep well disposal, clarifier,
oxidation pond for sanitary
wastes.
API separators, in-plant
changes.
API separator,
pellet removal
PROPOSED TO STATE OF LA.
Primary treatment consist-
ing of primary clarifier,
sludge storage lagoon
(Completion Dec. 1972).
Secondary treatment -
aerated stabilization basin
(Completion last quarter
1973).
Deep well disposal and
incineration of chlori-
nated hydrocarbons.
None
River water replacement
project, stabilization
tank, trickling filters
(Completion mid 1973).
None-Considered equivalent
of secondary.
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Ethyl Corp.
(Baton Rouge)
TYPE OF WASTE
Petrochemical
Foster Grant Co., Petrochemical
Inc. (Baton Rouge)
Freeport Chem. Co. Chemical
Div. of Freeport
> Minerals Co.
(Uncle Sam)
Freeport Sulphur Carbon-sulphur
Co. (Port Sulphur) compound (carsul)
Georgis Pacific
Corp.,Port Hudson
Pulp Plant
(Port Hudson)
Paper Mill
EXISTING
Filtration from T.E.L. process
for lead reduction, settling
basins, lead impounding basin,
oil :and solids traps.
Skimmer ponds, API separator
Impound CaSo4 when sulfate
in Mississippi River is
over 75 ppm.
None
None
PROPOSED TO STATE OF LA.
None
Collection lines and sumps
to collect tank car heels
and wash waters, retention
basin for non-process
surface waters.
Study to reduce flouride
discharges to the
Mississippi River.
None
Primary treatment (Com-
pletion end 1972) . Sec-
ondary treatment
(Completion Oct. 1973).
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Getty Oil Co.
(Venice)
Goodyear Tire &
Rubber Co.
(Plaquemine)
Gulf Oil Co., U.S.
(Venice)
TYPE OF WASTE
Ship Ballast
Petrochemical
Oil refinery
Gulf Oil Chem. Co. Agri-chemical,
(Welcome) Petrochemical
Ul
Hercules, Inc.
Allemania Plant
(Plaquemine)
Hooker Chem. Corp.
(Hahnville)
Organic Chemical
Chemical
EXISTING
Oil skimmers
Collection pit with
skimmer.
PROPOSED TO STATE OF LA.
None
Waste is handled by Dow
Chemical Company.
Packaged disposal plant for Air flotation.
sanitary wastes, API separator,
retention pond and skimming.
In-plant controls resulting
in secondary treatment
(Agri-chemical plant).
Secondary treatment.
Primary settling tanks and
secondary air flotation
(Styrene Monomer plant
1970-71).
None
Process design to avoid con- Recycling and equipment
tamination of effluent, changes to eliminate lead,
neutralization, chromate further organics removal,
reduction, recovery and absorption of HCl.
recycling of organic materials.
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Humble Oil &
Refining Co.
(Baton Rouge)
TYPE OF WASTE
Oil refinery
Jackson Brewing Co. Brewery
(New Orleans)
ID
CTi
Kaiser Alum. &
Chem. Corp.
(Baton Rouge)
Kaiser Alum.
Chem. Corp.
(Chalmette)
Spent Bauxite
Primary Metal
EXISTING
In-plant controls, oil-water
separators.
None (Only discharge is once
through cooling water from
Mississippi River and wells.)
Brewery and washing waste dis-
charged to city sanitary
system.
None (for spent bauxite).
Condenser water-none.
Surface runoff-oil booms.
Scrubber water-none.
PROPOSED TO STATE OF LA.
90% reduction of intake
water use, expand aerated
lagoon, in-plant control
(Completion 1972). Based
on pilot studies, determine
secondary treatment (acti-
vated carbon or biological
oxidation (Completion 1974-
75).
None
Impoundment or steel pro-
duction (Completion 1975-76)
for spent bauxite. Other
waste streams - removal of
settleable solids.
Condenser water-none.
Surface runoff-none
Scrubber water-eliminate
or treat.
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Kaiser Alum. &
Chem. Corp.
(Gramercy)
TYPE OF WASTE
Spent Bauxite and
chemical
Melamine Chem. Inc. Ammonia
(DonaIdsonvilie)
Monochem, Inc.
(Geismar)
Monsanto Co.
j (Luling)
Murphy Oil Co.
(Meraux)
Occidental Chem.
Co. (Hahnville)
Petrochemical
Chemical
Oil refinery
EXISTING
None (for spent bauxite).
Settling pond, impoundment
of gypsum.
None
Phenols-Activated carbon,
decantation, filtration,
oxidation, aeration.
Carbon-Filtration.
Segregation and Concentra-
tion of organics.
Segregation of non-contami-
nated storm water.
Inorganic chemical Retention pond.
Rollins-Purle, Inc. Pollution abatement Thermal, biological,
(Baton Rouge) plant chemical
PROPOSED TO STATE OF LA._
Activated sludge, impound-
ment or steel production
(Completion 1975-76).
Settling ponds, aerators.
None
Secondary by 1972.
Reduce BOD 70%, reduce
phenols 90% (Completion
Dec. 1972).
None
None
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
TYPE OF WASTE
Rubicon Chem., Inc. Petrochemical
(Geismar)
Schuykill. Metals
Corp. (Baton
Rouge)
Shell Chem. Co.
(Geismar)
Shell Chem. Co.
(Norco)
CO
Stauffer Chem. Co,
(Baton Rouge)
Stauffex Chem. Co,
(St. Gabriel)
Tenneco Oil Co.
(Chalmette)
Secondary lead
smelter
Petrochemical
Pet rochemi ca1
Petrochemical
Chemical
Oil refinery
EXISTING
Deep well disposal,
Settling ponds.
Incineration, deep well
disposal, recycling
Incineration, deep well
disposal, process unit
recovery facilities, segre-
gation, neutralization.
Control by process design-
stripping towers.
Two sludge settling ponds,
two sulfide treatment ponds,
pH control, two sand filters.
Deep well disposal, API sep-
arators, biological oxidation.
PROPOSED TO STATE OF LA.
Additional pretreatment
prior to deep well disposal
None
Secondary HCl disposal
well.
None
None
None
None
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Texaco, Inc.
(Convent)
TYPE OF WASTE
Oil refinery
EXISTING
Triad Chemicals Ammonia, urea
(Donaldsonville)
Union Carbide Corp. Petrochemical
(Hahnville)
UniRoyal, Inc.
g (Scotlandville)
UniRoyal, Inc.
(Baton Rouge)
UniRoyal, Inc.
UniRoyal Chem.
Div. (Geismar)
Plastic resins
Petrochemical
Synthetic rubber
Deep well disposal, API sep-
arators, oxidation ponds,
settling ponds.
Aeration pond, neutralization
pond.
Neutralization, clarifiers,
retention pond, skimmers,
storm water collection
lagoon.
Lime-alum clarification
API separator
Settling pond,
neutralization
PROPOSED TO STATE OF LA.
None
In-plant process
modifications.
In-process modifications,
deep well disposal, sec-
ondary biological treatment
(Completion Dec. 1973).
Bio-oxidation (Completion
mid 1972).
None-Effluent is incorpo-
rated into Enjay's waste
lines and will be treated
by their treatment facilities.
Deep well disposal
(Completion 1972).
-------
TABLE 20 (Continued)
TREATMENT
COMPANY
Universal Foods
Corp., Red Star
(Belle Chasse)
Vulcan Materials
Co., Chem. Div.
(Geismar)
Witco Chem. Corp.
Sonneborn Div.
(Gretna)
TYPE OF WASTE
Yeast
Petrochemical
Oil additives
EXISTING
Pilot plant studies
Segregation of storm water
run-off, in-process modifi-
cation.
API separator, skimmer
PROPOSED TO STATE OF LA.
Present abatement schedule
following completion of
pilot plant studies.
Elimination of source of
waste stream.
Secondary or equivalent
by Dec. 1972.
o
o
-------
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30. Hall, G., "Benzene Leukemia," Deutsch Med. Wschr.,
94: 1665, 1969.
31. Hartwell, J. L., "Survey of Compounds Which Have Been
Tested for Carcinogenic Activity," Washington, D. C.,
U. S. Government Printing Office, PHS No. 149, 1951.
32. Henderson, C. and Tarzwell, C. M., "Industrial Wastes,
Bioassays for Control of Industrial Effluents," Sewage
and Industrial Wastes," 29: No. 9.
33. Houston, Chester W., "Biochamical Oxidation of Hydro-
carbons in Natural Waters," Report, Rhode Island Water
Resources Center, 1971.
34. Jernelov, A., "Conversion of Mercury Compounds," pp
58-74, in Miller, M. M. and Berg, G. G. (eds.) Chem-
ical Fallout: Current Research on Persistent Pesticides,
1969.
35. Johnels, A. G., Westermark, T., "Mercury Contamination
in Sweden," pp. 221-241, in Miller, M. M. and Berg,
G. G. (eds.) Chemical Fallout: Current Research on
Persistent Pesticides, 1969.
36. Klaassen, C. D. , Plaa, G. L., "Comparison of the Bio-
chemical Alterations Elicited in Livers from Rats
Treated with Carbon Tetrachloride, Chloroform, 1,1,2-
Trichloroethane and 1,1,1-Trichloroethane," Biochem
Pharmacol., 18: 2019-2027, 1969.
37. Klein, C. L., "Testimony Before the Senate Committee
on Commerce, Subcpmmittee on Energy, Natural Resources,
and Environment," July 30, 1970.
104
-------
38. Kleiner, A. M., Stolbun, B. M., Likhacheva, E. I., and
Belyaeva, L. N., "Some Figures Characterizing the Myo-
cardial Function and Hemodynamics in Chronic Occupational
Poisoning with Chromium Compounds," Gigieva Trueta i
Professionalny Zobolevaniia, 14: 10-12, Dec. 1970.
39. Kobayashi, J., "Relation Between the IYAI-IYAI Disease
and the Pollution of River Water by Cadmium from a
Mine," 5th International Water Pollution Research Con-
ference, pap 1-25, San Francisco, California, July-
August 1970.
40. Kolman, J. H., Noever De Brauw, M. C. Ten, Vos, R. H.
De, "Chlorinated Biphenyls in Fish, Mussels, and Birds
from the River Rhine and the Netherlands Coastal Area,"
Nature (London), 221: 1126-1128, March 22, 1969.
41. Kolmodin, B., Azornoff, D. L., Sjoqvist, F., "Effect
of Environmental Factors on Drug Metabolism - Decreased
Plasma Half-Life of Antipyrine in Workers exposed to
Chlorinated Hydrocarbon Insecticides," Clin. Pharmacol,
Ther., 10: 638-642, 1969.
42. Krantz, W. C. , Mulhern, B. M. , Bagley, G. E. , "Organo-
chlorine and Heavy Metal Residues in Bald Eagle Eggs,"
Pestic, Monit. J., 4: 136-140, December 1970.
43. Krasovitskaia, M. L., Maliarora, L. K., "On the Chronic
Effect of Small Concentrations of Ethylene and Trichloro-
ethylene on the Organism of New-born Animals." Gig Sanit.
33: 7-10, May 1968.
44. Lee, Douglas, K., Minard, David (Editors) "Physiology,
Environment, and Man," Based on a Symposium conducted
by the National Academy of Sciences - National Research
Council, August 1966.
45. Little, Arthur D., Inc.. "Water Quality Criteria Data
Book, Vol. I, Organic Pollution of Fresh water," pre-
pared for the Environmental Protection Agency, Water
Quality Office, December 1970.
105
-------
46. Louisiana State Department of Health, Engineering
Division, in cooperation with Water Works operators
and officials, the Louisiana Stream Control Commission
and Industries of Louisiana, "Water Works Warning
Network Plan", January 20, 1969.
47. Louisiana Stream Control Commission, "Water Quality
Criteria and Plan for Implementation - State of
Louisiana, Section of Mississippi River, General
Criteria," P-18, 1968.
48. McKee, J. E. and Wolf, H. W., "Water Quality Criteria,"
2nd Edition, Publication No. 3-A, The Resources Agency
of California, water Quality Control Board, 1963.
49. Merck Index,-An Encyclopedia of Chemicals and Drugs,
Eigth Edition, Paul G. Strecher, Editor; Merck & Co.,
Inc., Rahway, N. J. , 1968.
50. Middleton, F. M., Pettit, H. H., and Rosen, A. A.,
"The Mega Sampler for Extensive Investigation of
Organic Pollutants in Water," Proc. 17th. Purdue
Industrial Waste Conference, 1962.
51. Miner, S., "Preliminary Air Pollution Survey of Baruim
and its Compounds: A Literature Review.," Prepared by
Litton Systems, Inc., under Department of Health, Edu-
cation, and Welfare Public Health Service, Consumer
Protection and Environmental Health.
52. Nuller, E., Reichert, J. K., "Cancerogenic Substances
in Water and Soil," XXV "Animal Experimental Test of
Cancerbgenicity of Chlorinated Derivatives of 3,4-
Benzopyrene," Arch. Hyg Bakt., 153, 26-32, T-bb 69.
53. Schroeder, H. A., "Trace Elements in the Human Environ-
ment, " Entered into the record of the Senate Committee
on Commerce, Subcommittee on Energy, Natural Resources,
and Environment, August 27, 1970.
54. Schroeder, H. A., "Cadmium as a Factor in Hypertension,1
Journal of Chronic Diseases," 18: 647-656, 1965.
106
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55. Schroeder, H. A., "Cadmium Hypertension in Rats," Amer.
J. of Physiol., 207: 62-66, 1964.
56. Shubik, P-, "Survey of Compounds Which Have been Tested
for Carcinogenic Activity, Supplement 1, Washington,
D. C., U. S. Government Printing Office, PHS No. 149,
1957.
57. Shubik, P., Hartwell, J. L., "Survey of Compounds Which
Have Been Tested for Carcinogenic Activity, Supplement 2,
Washington, D. C., U. S. Government Printing Office, PHS
No. 149, 1957.
58. Suess, M. J., "The Occurrence of Polycyclic Aromatic
Carbohydrates in Coastal Waters and its Possible Effects
on Man's Health," Archiv Fuer Hygiene and Bakteriologie,
Vol 154, No. 1, pp 1-7, 1970.
59. Thorpe, E., Gopinath, C., Jones, R. S., "The Effect of
Chloroform on the Liver and the Activity of Serum
Enzymes in the Horse," J. Path, 97: 241-251, 1969.
60. Takeuchi, Tadao, "Biological Reactions and Pathological
Changes of Human Beings and Animals Under the Condition
of Organic Mercury Contamination," Presented at Inter-
national Conference on Environmental Mercury Contami-
nation, Ann Arbor, Michigan, 1970.
61. Underwood, E. J., "Trace Elements in Human and Animal
Nutrition," 2nd Edition, Academic Press, Inc., New
York, 1962.
62. U. S. Department of the Interior, Federal Water Pollution
Control Administration, The National Estuarine Pollution
Study, 1970.
63. U. S. Department of Health, Education, and Welfare,
Public Health Service Drinking Water Standards, 1962.
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Public Health Service, Morbidity from Cancer in the
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107
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65. U. S. Department of Health, Education, and Welfare,
"Conference in the Matter of Pollution of the Inter-
state Waters of the Lower Mississippi River, Proceedings,"
Vols. I-IV, May 5-6, 1964, New Orleans, Louisiana.
66. U. S. Department of Health, Education, and Welfare,
Public Health Service, EHS, B WH, Region VII, "Community
Water Supply Study," August 1970.
67- U. S. Department of Interior, "Endrin Pollution in the
Lower Mississippi River Basin," June 1969.
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Chemical Analysis of Waters and Wastes," November 1969.
69. U. S. Geological Survey, "Hydrologic and Quality Charac-
teristics of the Lower Mississippi River," 1971.
70. Vogin, E. E., Carson, T., Cannon, G., "Chronic Toxicity
of DMSO in Primates," Toxic, Appl. Pharmacol. 16: 606-
12, May 1970.
71. Weisburger, J. H., Weisburger, E. K., "Food Additives
and Chemical Carcinogens - On the Concept of Zero
Tolerance," Food Cosmet. Toxic., 6: 235-242, 1968.
72. Yamagoto, Norboru, Shigematou, Itsuzo, "Cadmium Pollution
in Perspective," International Symposium on Hydrogeo-
chemistry and Biochemistry, September 7-12, 1970.
108
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APPENDIX
109
-------
LIST OF FIGURES Page
D-l Flow Sheet, Fractionation of Lower Mississippi
Carbon Chloroform Extract 118
D-2 Flow Chart of Industrial Waste Water
Extraction 119
E-4 Odor-free Water Generator 125
110
-------
LIST OF TABLES Page
E-l Threshold Odor Number Corresponding
to Various Dilutions : 127
E-2 Dilutions for Various Odor Intensities 129
E-3 Sample Odor Series 130
111
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EXHIBIT A
STATE OF LOUISIANA
STREAM CONTROL COMMISSION
P . O , D M A W C R f C
UNIVERSITY STATION
OATON ROUGE, LOUISIANA 70003
March 23, 1967
Mr. James M. Quigley, Commissioner
Federal Water Pollution Control Administration
U.S. Department of Interior
633 Indiana Avenue, N.W.
Washington, B.C. 20242
Dear Mr. Commissioner:
For a number of years, Louisiana has been among the Nation's
leaders in the production and refining of petroleum. During the past
ten years, Louisiana has taken its place among the Nation's leaders
in the manufacture of basic petro-chemical and other chemical pro-
ducts. These manufacturing plants have located and are locating in
Louisiana because of the availability of vast mineral resources, an
apparent, inexhaustible supply of good quality water for process use,
and because of the benefits associated with water transportation, and
because of availability of plant sites.
Virtually all of these plants return cooling and other types of
process water to the streams. Many of these returned waters contain
small fractions of the complex chemicals being manufactured. These
fractions find their way to Louisiana's very rich estuaries. The
Mississippi River is the only available source of raw water for potable
supplies for more than 1,500,000 people.
Louisiana's Water Pollution Control Authority, the Louisiana Stream
Control Commission, inaugurated a permit system for industrial waste
discharge to public waters in 1940. Known toxins and other chemicals
that by calculated concentration in the receiving stream may be toxic or
otherwise harmful to humans and other forms of life are denied in the
permit to discharge. Despite the afore-mentioned, we have become
concerned about the degradation properties or lack therof of some of
these materials in the aquatic environment. There is also concern about
112
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Mr. James M. Quigley, Commissioner page 2 March 23, 1967
the possible combination of these materials in the ecosystem and the
effects produced by their synergism and/or antagonism. Possible accu-
mulation of these materials and their effects on the bioata, stream bed,
and other sites are unknown. A good case in point is the recent fish
kills in the Mississippi River. Such incidents have raised questions
about other organic and inorganic chemicals entering Louisiana via the
Mississippi River which drains approximately 40% of the continental United
States.
If there is to be continuing positive assurances given our water using
public that their waters will remain safe, potable supplies in light of the
ever increasing discharge of complex chemicals to our water resources, there
is need for more information than is presently available or, at the present
time, we are staffed and geared to obtain.
For the reasons and concerns cited, it is requested that technical
assistance as provided in Section 5 (b) of Public Law 84-660, as amended,
be made available to the State of Louisiana. Specifically this assistance
is requested in the fresh and estuarine waters of the Mississippi River in
Louisiana and the Calcasieu River, a watershed located entirely within this
state, but discharging to our coastal region. Specific information is
desirable and needed on the effects on water quality and aquatic life that
may be exhibited by the presence of organic chemicals in the above cited
aquatic environments. We feel the need to be advised of processes that
could be used in treating or removing specific chemicals from waste streams
and costs associated with their treatment and/or removal.
Very truly yours,
/ 1
Leslie L. Glasgow
Chairman
Louisiana Stream Control Commission
FMM
113
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MISSISSIPPI
"LbUFsiANA
SAINT iFRANCISVILLE
BATON ROUGE
PLAQUEMINE
DONALDSON VILLE
HAHNVILLE
-N-
SCALE IN MILES
VICINITY MAP
NEW ORLEAI*
PORT SULPHUR
VENICE
INDUSTRIAL POLLUTION OF THE
LOWER MISSISSIPPI RIVER IN LOUISIANA
LOCATION MAP
U. S. ENVIRONMENTAL PROTECTION AGENCY
REGION VI APRIL 1972 DALLAS, TEXAS
114
EXHIBIT B
-------
PAGE NOT
AVAILABLE
DIGITALLY
-------
EXHIBIT D
ANALYTICAL TECHNIQUES
1. RAW AND FINISHED WATER
Mega Sampling
The "Mega" sampler is used to extract trace organics
from large volumes of water. It is a portable unit com-
prising filters to remove suspended solids followed by beds
of granular activated carbon. These units are connected
in series, water entering the filters for removal of,
suspended solids and then flowing through the activated
carbon units where organic compounds are adsorbed on the
carbon surface and thus removed from solution.
Two'samplers were used during the study; one with
three rapid sand filters followed by eight stainless steel
containers for holding the carbon. The second, more com-
pact unit, comprised two sand filters followed by four
carbon units. Both units are capable of extracting organics
from water in quantities up to 300,000 gallons per run.
Carbon Drying
A carbon drying oven is basically a forced-air, low
temperature oven with a series of stainless steel trays
for holding the carbon. The oven has the capacity of
drying two mega cylinders of carbon in 4 days.
Mega Extraction
Organics adsorbed on the activated carbon from mega
samples of raw and finished water were removed by extraction,
The extractor is basically a large soxhlet extractor
made of stainless steel (Middleton, et. al.). Chloroform
was used as the extracting solvent. Samples were reduced
in volume by distillation to approximately 500 ml.
116
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Fractionation and Identification of Organics in
garbon-Chloroform Extract
The carbon chloroform extract (CCE) was first
fractionated by a combination of steam distillation
and silica gel column chromatography. Further separation
into compounds or groups of compounds was achieved by
preparative gas chromatography (GLC). This procedure is
shown schematically on the flow sheet in Figure D-l. Since
the project was initially designed to identify odor-causing
organics, each GLC fraction trapped in a cold trap-silica
gel U-tube was subjected to a threshold odor evaluation
(Exhibit E). The important odorous fractions were then
further purified by GLC preparative techniques and identified
by infrared (IR) spectrophotometry initially and, during
the latter part of the study, by mass spectroscopy.
2. INDUSTRIAL WASTES
Sampling Procedures
Industrial wastes were collected by grab sampling
techniques or, in some instances, were composited. Indi-
vidual waste streams were sampled and composited in
proportion to flow. All flow values were provided by the
industry- A total of thirty gallons of composite (later
twenty-five gallons when bioassays were discontinued) were
collected.
Organic Analyses
Twenty gallons of the composited waste was extracted
with immiscible solvents in a liquid-liquid procedure
showed schematically on the attached flow chart (Figure D-2) .
The concentrated fraction of this extract was used
for the identification of individual organic compounds.
Identification procedures parallel the techniques used in
the CCE extracts of the raw and finished water as previously
described. Emphasis in the early part of the study was on
the identification of the odorous fractions of the wastes.
117
-------
Figure D-l
Flow Sheet
Fractionation of Lower Mississippi
Carbon Chloroform Extract
CCE
Aliphatics
Steam distillation
Steam Distillate (60%) *
Silica gel column
Aromatics (55%)*
Preparative gas
chromatography
Oxys (18%)*
Fraction 1
60-81°
i I '
Fraction 2 Fraction 3 Fraction 4 Fraction 5
81-140° 140-160° 160-194° 192-260°
* Numbers in parentheses indicate percentage of total odor of
parent fraction contained in daughter fraction. These
percentages vary with different samples.
118
-------
Figure D-2
Flow Chart of Industrial Waste Water Extraction
Industrial Waste Water
20 gal.
Add 7.2 Liters Ethyl Ether
and 4 Ibs. of Sodium Sulfate
Stir for 30 mins.
Water Layer
Add 2 Liters of 1:1
Pet Ether-Hexane
Stir for 30 mins.
Ether Layer
Water Layer
Discard
Pet Ether-Hexane
Layer
Combine
Solvent Layers
Evaporate to Approx.
1 Liter and dry
Evaporate dried solvent extract
to 100 - 200 ml.
Retain for preparative gas
chromatography, odor evaluation
and identification of major odorous
compounds.
119
-------
Other Parameters
The waste of each industry sampled was subjected
to a detailed analysis. The following parameters were
determined on most samples: flow, temperature, pH,
conductivity, hardness, alkalinity and/or acidity,
chlorides, sulfates, solids (total and volatile), chemical
oxygen demand (COD), total organic carbon (TOG), phenols,
oil and grease, phosphorous, cyanide, sodium, potassium,
arsenic, lead, iron, cadmium, copper, chromium, mercury
and zinc and threshold odor number.
All of these analyses were performed by procedures
described in the FWQA methods manual.
Methodology Used in Organic Identification
The organic fractions separated from either the CCE's
of the river water or the solvent extracts of the indus-
trial wastes, were identified by several different procedures
including separations by preparative GLC; trapping in the
cold or in solvents, followed by identification by infrared
spectroscopy. Other laboratories used the newer, GLC-Mass
Spectroscopy approach. Certain low boiling compounds were
identified by a combination of differential thermal analysis
(DTA) followed by mass spectroscopy. Since each laboratory
used a unique approach, standard procedures are unavailable;
however, below is a list of the laboratories and senior
chemists who participated in these investigations. It is
suggested that these individuals be contacted directly for
details on the methodology.
Robert S. Kerr Water Research Center
U. S. Environmental Protection Agency
P. O. Box 1198
Ada, Oklahoma 74820
Dr. William Dunlap
Southeast Water Laboratory
U. S. Environmental Protection Agency
College Station Road
Athens, Georgia 30601
Dr. Ron Webb
120
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Robert A. Taft Engineering Center
4676 Columbia Parkway
Cincinnati, Ohio 45226
Mr. Charles Mashni
Baton Rouge Facility
U. S. Environmental Protection Agency
2695 N. Sherwood Forest Drive
Baton Rouge, Louisiana 70814
Mr. Mike Garza
Bureau of Sport Fisheries & Wildlife
Denver Federal Center, Building 16
Denver, Colorado 80225
Mr. R. E. White
The Dow Chemical Company
Waste Control
Midland, Michigan 48640
Mr. C. E. Hamilton
121
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EXHIBIT E
THRESHOLD ODOR*
STORET NO:
(Consistent Series Method) 60°C 00086
ROOM TEMP: 00085
1. Scope and Application
1.1 This method is applicable to the determination
of finished waters, surface waters, domestic
and industrial wastes, and saline waters.
1.2 Highly odorous samples are reduced in concen-
tration proportionately before being tested.
Thus, the method is applicable to samples ranging
from nearly odorless natural waters to industrial
wastes with threshold odor numbers in the thousands.
2. Summary of Method^ '
2.1 The sample of water is diluted with odor-free water
until a dilution that is of the least definitely
perceptible odor to each tester is found. The re-
sulting ratio by which the sample has been diluted
is called the "threshold odor number" (T.O.).
2.2 People vary widely as to odor sensitivity, and even
the same person will not be consistent in the con-
centrations he can detect from day to day- Therefore,
panels of not less than five persons, and preferably
10 or more, are recommended to overcome the varia-
bility of using one observer.'^)
2.2.1 As an absolute minimum, two persons are
necessary: One to make the sample dilutions
and one to determine the threshold odor.
3. Sample Handling and Preservation
3.1 Water samples must be collected in glass bottles
with glass or Teflon-lined closures.
* Methods of Chemical Analysis of Water and Wastes, "Threshold
Odor (Consistent Series Method)" Environmental Protection
Agency, Water Quality Office, Analytical Quality Control
Laboratory, Cincinnati, Ohio, 1971.
122
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3.1.1 Plastic containers are not reliable for
odor samples and must not be used.
3.2 Odor tests should be completed as soon as possible
after collection of the sample. If storage is
necessary, collect at least 1000 ml of sample in
a bottle filled to the top. Refrigerate, making
sure no extraneous odors can be drawn into the
sample as the water cools.
4. Interferences
4.1 Most tap waters and some waste waters are chlori-
nated. It is often desirable to determine the
odor of the chlorinated sample as well as of the
same sample after removal of chlorine. Dechlori-
nation is achieved using sodium thiosulfate in
exact stoichiometric quantity.
4.1.1 It is important to check a blank to which
a similar amount of dechlorinating agent
has been added to determine if any odor
has been imparted. Such odor usually disap-
pears upon standing if excess reagent has
not been added.
5. Apparatus
5.1 Odor-free glassware: Glassware must be freshly
cleaned shortly before use, with non-odorous soap
and acid cleaning solution followed by rinsing
with odor-free water. Glassware used in odor
testing should be reserved for that purpose only.
Rubber, cork, and plastic stoppers must not be used.
5.2 Constant temperature bath: A water bath or electric
hotplate capable of maintaining a temperature control
of +1°C for performing the odor test at 60°C. The
temperature bath must not contribute any odor to
the odor flasks.
5.3 Odor Flasks: Glass stoppered 500 ml (ST 32)
Erlenmeyer flasks, or wide-mouthed 500 ml Erlenmeyer
flasks equipped with Petri dishes as cover plates.
123
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NOTE: Narrow-mouth vessels are not suitable
for running odor tests. Potential positive
bias due to color and/or turbidity of water
sample under observation can be eliminated
by wrapping odor flasks in aluminum foil,
painting flasks with non-odorous paint, or
by using red actinic Erlenmeyer flasks.
5.4 Sample Bottles: Glass bottles with glass or Teflon-
lined closures.
5.5 Pipets, measuring: 10.0 and 1.0 ml graduated in
tenths.
5.6 Graduate cylinders: 250, 200, 100, 50, and 25 ml.
5.7 Thermometer: 0-110°C (+;1°C) , chemical or metal
stem dial type.
5.8 Odor free water generator: See Figure 1.
6. Reagents
6.1 Odor-free water: Odor-free dilution water must be
prepared as needed by filtration through a bed of
activated carbon. Most tap waters are suitable
for preparation of odor-free waters, except that
it is necessary to check the filtered water for
chlorine residual, unusual salt concentrations, or
unusually high or low pH. All these may affect
some odorous samples.
Where supplies are adequate, distilled water
avoids these problems as a source of odor-free
water. A convenient odor-free water generator may
be made as shown in Figure 1. Pass tap or dis-
tilled water through the odor-free water generator
at a rate of 0.1 liter/minute. When the generator
is first started, it should be flushed to remove
carbon fines before the odor-free water is used.
The carbon cartridge,' ' or a comparable assembly,
is also suitable.
124
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TWO HOLE RUBBER STOPPER
GLASS TUBING
TAP WATER
GLASS WOOL
ONE GAL. JUG
ODOR-FREE
WATER
GRANULAR
4x 10 MESH
ACTIVATED
CARBON
PEA SIZE
GRAVEL
FIG. E-l ODOR-FREE WATER GENERATOR
125
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6.1,1 The quality of water obtained from the
odor-free water generator should be chebked
daily at the temperature tests are to be
conducted (room temperature and/or 60°C).
The life of the carbon will vary with the
condition and amount of water filtered.
Subtle odors of.biological origin are often
found if moist carbon filters are permitted
to stand idle between test, periods. Detection
of door in the,water coming through the carbon
indicates a change of carbon is needed.
7. Procedure
7.1 Precautions; Selection of persons to make odor
tests should be carefully made. Extreme sensitivity
is not required, but insensitive persons should
not be used. A good observer has a sincere interest
in the test. Extraneous odor stimuli such as those
caused by smoking and eating prior to the test or
through the use of scented soaps, perfumes, and
shaving lotions must be avoided. The tester should
be free from colds or allergies that affect odor-
response. Frequency of tests must not be so great
as to induce fatigue. Frequent rests in an odor-
free atmosphere are recommended.
The room in which the tests are to be conducted
should be free from distractions, drafts, and other
odor. In certain industrial atmospheres, a special
odor-free room may be required, ventilated by air
filtered through activated carbon and maintained at
a constant comfortable temperature and humidity^'.
For precise.work a panel of five or more testers
should be used. The pers.ons making the odor measure-
ments should not prepare the samples and should not
know the dilution concentrations being evaluated.
These persons should have been made familiar with
the procedure before participating in a panel test.
Always start with the most dilute sample to avoid
tiring the senses with the concentrated sample. The
temperature of the samples during testing should be
kept within 1 degree of the specified temperature
for the test.
126
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7.2 Threshold Measurement; The ratio by which the
odor-bearing sample has to be diluted with odor-
free water for the odor to be just detectable by
the odor test is the "threshold odor number" (T.O.).
The total volume of sample and odor-free water used
in each test is 200 ml. The proper volume of odor-
free water is put into the flask first; the sample
is then added to the water. Table 1 gives the
dilutions and corresponding threshold numbers.
Table 1. Threshold Odor Number Corresponding
to Various Dilutions
Sample Volume (ml)
Diluted to 200 ml
Threshold Odor
Number
200
100
50
25
12.5
6.3
3.1
1.6
0.8
1
2
4
8
16
32
64
128
256
7.3 Determine the approximate range of the threshold
odor by:
7.3.1 Adding 200 ml, 50 ml, 12.5 ml, and 3.1 ml
of the sample to separate 500 ml glass-
stoppered Erlenmeyer flasks containing odor-
free water to make a total volume of 200 ml.
A separate flask containing only odor-free
water serves as the reference for comparison
If run at 60°C, heat the dilutions and the
reference in the constant temperature bath
to 60°C
127
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7.3.2 Shake the flask containing the odor-free
water, remove the stopper, and sniff the
vapors. Test the sample containing the
least amount of odor-bearing water in
the same way. If odor can be detected
in this solution, more dilute samples
must be prepared as described in 7.3.3.
If odor cannot be detected in the first
dilution, repeat the above procedure using
the sample containing the next higher
concentration of the odor-bearing water,
and continue this process until odor is
clearly detected.
7.3.3 If the sample being tested requires more
extensive dilution than is provided by
Table 1, an intermediate dilution is
prepared from 20 ml of sample diluted to
200 ml with odor-free water. Use this
dilution for the threshold determination.
Multiply the T.O. obtained by ten to
correct for the intermediate dilution.
In rare cases more than one tenfold inter-
mediate dilution step may be required.
7.4 Based on the results obtained in the preliminary
test, prepare a set of dilutions using Table 2
as a guide. One or more blanks are inserted in
the series, in the vicinity of the expected
threshold, but avoiding any repeated pattern.
The observer does not know which dilutions are
odorous and which are blanks. He smells each
flask in sequence, beginning with the least con-
centrated sample and comparing with a known flask
of odor-free water, until odor is detected with
utmost certainty.
128
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Table 2. Dilutions for Various Odor Intensities
Sample Volume in Which Odor First Noted
200 ml
50 ml
12.5 ml
3.1 ml
Volume (ml) of Sample to be Diluted to 200 ml
200
100
50
25
12.5
100
50
25
12.5
6.3
52
25
12.5
6.3
3.1
(Intermediate
Dilution,
See 7.3.3)
7.5 Record the observations of each tester by indicating
whether odor is noted (+ sign) in each test flask.
For example:
ml sample
diluted to 200 ml 12.5
0 25 0 50 100 200
Response - - + - + + +
8. Calculations
8.1 The threshold odor number is the dilution ratio
at which odor is just detectable. In the example
above (7.5), the first detectable odor occurred
when 25 ml sample was diluted to 200 ml. Thus,
the threshold is 200 divided by 25, equals 8.
Table 1 lists the threshold numbers that corre-
spond to common dilutions.
8.2 Anomalous responses sometimes occur; a low con-
centration may be called positive and a higher
concentration in the series may be called negative,
In such a case, the threshold is designated as
that point of detection after which no further
anomalies occur. For instance:
ml sample
diluted to 200 ml 6.3 12.5 0 25 50 100
Response + - - + + +
threshold
129
-------
8.3 Calculations of panel results to find the most
probable average threshold are best accomplished
by appropriate statistical methods. For most
purposes, the threshold of a group can be expressed
as the; geometric mean (G.M.) of the individual
thresholds. The geometric mean is calculated in
the following manner:
8.3.1 Obtain odor response as outlined in pro-
cedure and record results. For example:
Table 3. Sample Odor Series
ml of Odor- ml of
free water Sample
188 12.5
175 25
200 0
150 50
200 0
100 100
0 200
Observer R
1
-
-
ŁF)
-
+
+
2
e
-
+
-
+ ;
+
3
-
-
-
-
Š
+
psponse*
4
+
-
-
-
Š
+
5
Q
-
+
-
+
+
*Circled plus equals threshold level.
8.3.2 Obtain individual threshold odor numbers
from Table 1.
Observer
T.O.
1
2
3
4
5
4
8
2
2
8
130
-------
8.3.3 The geometric mean is equal to the nth root
of the product of n numbers. Therefore:
4x8x2x2x8= 1024,
and 1024 = log 1024 = 3.0103 = 0.6021,
5 5
and anti-log of 0.6021 = 4 = T.O.
9. Precision and Accuracy
9.1 Precision and accuracy data are not available at
this time.
9.2 A threshold number is not a precise value. In the
case of the single observer, it represents a judgment
at the time of testing. Panel results are more
meaningful because individual differences have less
influence on the result. One or two observers can
develop useful data if comparison with larger panels
has been made to check their sensitivity- Com-
parisons of data from time to time or place to
place should not be attempted unless all test con-
ditions have been carefully standardized and some
basis for comparison of observer intensities exists.
References
1. Standard Methods, 13th Edition, Amer. Public Health
Asso., New York, N.Y., p. 248, Method 136 (1971).
2. ASTM, Comm E-18, STP 433, Basic Principles of Sensory
Evaluation; STP 434, Manual on Sensory Testing Methods;
STP 440, Correlation of Subjective-Objective Methods
in the Study of Odors and Taste; Phil., Pennsylvania
(1968).
3. Standard Methods, 12th Ed., Amer. Public Health Asso.,
New York, N.Y., 1965, p. 213.
4. Baker, R. A., "Critical Evaluation of Olfactory Measure-
ment". Jour WPCF, 34, 582 (1962).
131
-------
ANALYTICAL RESULTS
INDUSTRIAL WASTE DISCHARGES
* An asterisk (*) by the date sampled indicates net load
contributions for all parameters on that date, while an
asterisk (*) by an individual value means that only that
parameter value is a net load calculation. These net
load values were obtained by substracting the concentration
of the intake water parameter from the comparable effluent
discharge parameter concentration and the net pounds per
day discharged were calculated on this difference. All
other load values were calculated by using only the con-
centrations found in the plant effluent and therefore
represent gross contribution of these plants.
132
-------
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AVAILABLE
DIGITALLY
-------
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AVAILABLE
DIGITALLY
-------
PAGE NOT
AVAILABLE
DIGITALLY
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AVAILABLE
DIGITALLY
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DETECTION LIMITS
The analytical method chosen for each parameter
has a minimum detection limit. Analytical results below
these limits are indicated in "Analytical Results, Indus-
trial Waste Discharges" with a 4- since they are considered
unreliable.
Detection limits for parameters reported in this
document are listed below:
PARAMETER
Conductivity
Solids - Total
Solids - Volatile
Chemical Oxygen Demand
Low (5-50 mg/1)
High (1000 mg/l+)
Total Organic Carbon
Phenol
Oil & Grease
Cyanide
Iron -
Fe
Sodium - Na
DETECTION LIMIT
10.0 Micromhos
9.X mg/1
9.X mg/1
5.X mg/1
250.X mg/1
l.X mg/1
0.001X mg/1
5.X mg/1
l.X mg/1 (titration)
0.005X mg/1 (colorimetric)
0.004X mg/1
0.00IX mg/1
137
-------
Potassium - K
Arsenic - As
Lead - Pb
Cadmium - cd
Copper - Cu
Chromium - Cr
Mercury - Hg
Zinc - Zn
0.005X mg/1
0.25X mg/1
0.0IX mg/1
O.OOlX mg/1
0.005X mg/1
0.0IX mg/1
0.0002X mg/1
0.005X mg/1
138
-------
EXHIBIT G
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS
Company and Location
Crown Zellerbach Corp.
St. Francisville
Enjay Chem. Co.
Baton Rouge
Hooker Chem. Corp.
Hahnville
Humble Oil & Ref. Co.
Baton Rouge
Union Carbide Corp.
Hahnville
Georgia Pacific Corp,
Port Hudson
Dow Chemical Co.
Plaquemine
BASF Wyandotte Chem.
Geismar
Odor
Plant or
Division
Chem. Plant
Chem. & Plas-
tics Div.
Crossett Div.
Date
Sampled
11-2-70
4-6-71
6-9-71
1-15-70
2-24-70
5-25/26-71
1-15-70
6-8-71
1-22-70
4-21-71
5-4-70
1-20-70
6-21/22-71
Discharge
(mgd)
33.5
29.25
10.08
25.63
21.60
20.74
190.0
83.63
325.0
345.1
18.5
540.0
576.0
Threshold
Odor Number
22,600
25,436
55,746
13,460
20,800
1,836
1,740
1,616
872
16
13,800
215
14
Contribution
(bgd)
758
744
562
345
449
38
331
135
283
6
255
116
8
4-7-70
3.74
13,730
51
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Company and Location
Copolymer Rubber &
Chem. Co.
Baton Rouge
Shell Chemical Co.
Geismar
Borderi, Inc.
Geismar
Ł The Celotex Corp.
0 Marrero
Rubicon Chemicals, Inc.
Geismar
Chevron Chem. Co.
Belle Chasse
Ethyl Corp.
Baton Rouge
Shell Chem. Co.
Norco
Plant or
Division
Geismar Plant
Borden Chem.
Div.
Oronite Addi-
tives Div.
Date
Sampled
5-3-71
1-14-70
7-13-70
6-28-71
9-21-70
1-21-70
4-14-71
3-1/2-71
1-25-71
8-10-71
1-14-70
4-27/28-71
Discharge
(mqd)
4.32
5.76
30.2
21.6
12.0
0.4
0.23
1.15
0.72
0.58
14.4
14.4
Threshold
Odor Number
9,555
1,710
742
928
1,250
33,600
2,249
8,100 ,
9,224
570
556
117
2-16-70
43.92
171
Odor
Cont r ibut ion
(bqd)
41
10
22
20
15
13
0.5
9.3
6.6
0.33
8.0
1.7
7.5
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Company and Location
Kaiser Alum. & Chem.
Chalmette
" ;'
Tenneco Oil Co.
Chalmette
Freeport Chem. Co.
Uncle Sam
Kaiser Alum. & Chem.
Baton Rouge
Cos-Mar Plant of
Borg Warner Corp.
Carville
Occidental Chem. Co.
Hahnville
American Cyanamid Co.
Avondale
UniRoyal, Inc.
Baker
Plant or
Division
Div. of Free-
port Minerals
Date
Sampled
11-30-70
1-11-71
10-5-70
1-19-70
7-6-70
5-19-71
2-24-70
2-2-70
7-26-71
7-6-71
1-19-70
Discharge
(mgd)
408.0
27.36
144.0
7.2
0.47
0.47
5.04
4.87
4.85
3.17
3.17
Threshold
Odor Number
18
249
35
476
7,125
4,778
454
452
80
631
354
Odor
Contribution
(bgd)
7.3
6.8
5.04
3.42
3.35
2.23
2.28
2.20
0.38
2.00
1.12
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Odor
Plant or
Company and Location Division
UniRoyal, Inc.
Baton Rouge
E.I. duPont de Nemours
& Co. , Inc.
LaPlace
Allied Chem. Corp. Ind. Chem.
Baton Rouge Div.
Gulf Oil Co. , U.S.
Venice
Texaco, Inc.
Convent
Hercules, Inc.
Plaquemine
Kaiser Alum. & Chem. Chem. Div.
Gramercy
C.F. Industries
Dona Idsonvi lie
Allied Chem. Corp. Geismar Com]
Date
Sampled
5-25-70
3-2-70
5-4-71
4-14-70
7-19-71
6-15-71
8-17-70
11-23-70
3-31-70
11-16-70
?lex 6-29-70
Discharge
(mgd)
0.86
36
28.8
43.0
46.51
129.6
2.62
0.6
27.07
2.02
4.1
Threshold
Odor Number
2,242
49
6
39
29
8
306
1,296
26
289
112
Contribution
(bqd)
1.
1.
0.
1.
1.
1.
0.
0.
0.
0.
0.
92
76
17
68
34
03
80
76
70
58
46
Geismar
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Odor
Company and Location
UniRoyal, Inc.
Geismar
Murphy Oil Corp.
Meraux
Foster Grant Co., Inc.
Baton Rouge
Universal Foods Corp.
Belle Chasse
Ciba-Geigy Chem. Corp.
St. Gabriel
Witco Chem. Corp.
Gretna
M6nsanto Company
Luling
Getty Oil Co.
Venice
En jay Chemical Co.
Baton Rouqe
Plant or Date
Division Sampled
UniRoyal Chem. 6-29/30-71
1-18-71
6-8-70
Red Star Yeast 5-24/25-71
Operations
8-25-70
Sonneborn Div. 3-30-71
2-9-70
6-1-71
Plastics Plant 8-24-71
6-15-70
Discharge
(mqd)
1.1
10.8
0.53
0.5
1.5
0.115
1.73
0.84
1.05
0.75
Threshold
Odor Number
387
32
584
549
176
215
114
215
167
174
Contribution
(bqd)
0.42
0.35
0.31
0.28
0.26
0.24
0.19
0.18
0.17
0.13
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Odor
Company and Location
Triad Chemicals
Dona Idsonvi lie
Melamine Chem., Inc.
Dona Idsonvi lie
Allied Chem. Corp.
Scotlandville
Vulcan Materials Co.
Geismar
Monochem, Inc.
Geismar
Allied Chem. Corp.
Baton Rouge
Copolymer Rubber &
Plant or Date
Division Sampled
9-8-70
6-16-71
Plastics Div. 4-28-70
7-12-71
Chem. Div. 10-26-70
6-22/23-71
Spec. Chem. 6-22-70
Div.
Addis Plant 10-12-70
Discharge
(mgd)
1.
0.
3.
1.
0.
1.
1.
1.
3
11
17
29
25
44
65
32
Threshold
Odor Number
116
951
32
25
279
48
40
38
Contri
bution
(bgd)
0.
0.
0.
0.
0.
0.
0.
0.
15
10
10
03
07
07
07
05
Chem. Co.
Addis
Gulf Oil Co.
Welcome
Stcluffer Chem. Co.
Baton Rouge
Chem. Dept.* 8-31-70
6-1-70
2.74
2.45
19
15
0.05
0.04
* Bought out by WillChemCo, Inc. July 1, 1971
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Odor
Plant or
Company and Location Division
SdhuyUdll Metals Corp.
Scot landvi lie
Union Tank Car Co.
Baton Rouge
Jackson Brewing Co.
New Orleans
Rollins-Purle, Inc.
Baton Rouge
Goodyear Tire & Chem. Plant
Date
Sampled
5-11-70
8-3-71
3-8-71
4-12-71
4-19-71
Discharge
(mgd)
0.18
0.183
2.16
0.32
6.48
Threshold
Odor Number
108
84
5.6
36
1.7
Contribution
(bgd)
0.02
0.015
0.01
0.01
0.01
Rubber Co.
Plaquemine
Avondale Shipyards 9-22-70 0.04 258 0.01
Avondale
Freeport Sulphur Co.
Port Sulphur 3-22-71 0.144 4,4 0.006
-------
INDUSTRIAL WASTE THRESHOLD ODOR NUMBERS AND ODOR CONTRIBUTIONS (Continued)
Plant or
Company and Location Division
Date
Sampled
Odor
Discharge Threshold Contribution
(mgd) Odor Number (bqd)
Stauffer Chem. Co.
St. Gabriel
Industrial
2-8-71
1.12
5.3
0.006
Allied Chem. Corp.
Marrero
Ind. Chem.
Div.
2-22-71
0.003
19
0.00006
Argus Chem. Corp.
Hahnville
3-15-71
0.031
1.6
0.00005
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