INDUSTRIAL LIQUID WASTE SURVEYS
TRAINING MANUAL
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER PROGRAMS
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INDUSTRIAL LIQUID WASTE SURVEYS
This course is designed for engineers, chemists,
or other professional personnel who will be
responsible for planning and conducting industrial
liquid wastes surveys.
It is intended that, at the conclusion, the partic-
ipants will be able to plan, supervise, and evaluate
an industrial waste survey which measures or
characterizes wastes at outfalls or in-plant locations,
or both.
ENVIRONMENTAL PROTECTION AGENCY
Water Programs Operations
TRAINING PROGRAM
January 1973
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TRAINING PROGRAM
Through the Water Programs Operations Office, Environmental
Protection Agency conducts programs of research, technical
assistance, enforcement, and technical training for water
polh:tion control.
The objectives of the Training Program are to provide specialized
training in the field of water pollution control which will lead to
rapid application of new research findings through updating of
skills of technical and professional personnel, and to train
new employees recruited from other professional or technical
areas in the special skills required. Increasing attention is
being given to development of special courses providing an
overview of the nature, causes, prevention, and control of
water pollution.
Scientists, engineers, and recognized authorities from other
Agency programs, from other government agencies, universities,
and industry supplement the training staff by serving as guest
lecturers. Most training is conducted in the form of short-term
courses of one or two weeks' duration. Subject matter includes
selected practical features of plant operation and design, and
water quality evaluation in field and laboratory. Specialized
aspects and recent developments of sanitary engineering, chemistry,
aquatic biology, microbiology, and field and laboratory techniques
not generally available elsewhere, are included.
The primary role and the responsibility of the states in the
training of wastewater treatment plant operators are recognized.
Technical support of operator-training programs of the states is
available through technical consultations in the planning and
development of operator-training courses. Guest appearances
of instructors from the Environmental Protectim Agency, and
the loan of instructional materials such as lesson plans and
visual training aids, may be available through special arrangement.
These training aids, including reference training manuals, may
be reproduced freely by the states for their own training programs.
Special categories of training for personnel engaged in treatment
plant operations may be developed and made available to the states
for their own further production and presentation.
A bulletin of courses is prepared and distributed periodically
by the National Training Center. The bulletin includes descriptions
of courses, schedules, application blanks, and other appropriate
information. Organizations and interested individuals not on
the mailing list should request a copy from The National Training
Center.
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FOREWORD
These manuals are prepared for reference use of students enrolled in
scheduled training courses of the Office of Water Programs, Environmental
Protection Agency.
Vue to the limited availability 06 the manual6,
it i6 not app~op~iate to eite them a6 teehnieal
~e6e~enee6 in bibliog~aphie6 o~ othe~ 60~m6 06
publieation.
Re6e~enee6 to p~oduet6 and manu6aetu~e~6 a~e 60~
illu6t~ation only; 6ueh ~e6e~enee6 do not imply
p~oduet endo~6ement by the 066iee 06 Wate~ P~og~am6,
Envi~onmental P~oteetion Ageney.
The reference outlines in this manual have been selected and developed with
a goal of providing the student with a fund of the best available current
information pertinent to the subject matter of the course. Individual
instructors may provide additional material to cover special aspects of
their own presentations.
This manual will be useful to anyone who has need for information on the
subjects covered. However, it should be understood that the manual will
have its greatest value as an adjunct to classroom presentations. The
inherent advantages of classroom presentation is in the give-and-take
discussions and exchange of information between and among students and
the instructional staff.
Constructive suggestions for improvement in the coverage, content, and
format of the manual are solicited and will be given full consideration.
11-'r a
~i
4~~vU/ c:
Joseph Bahnick
Acting Chief
Direct Technical Training Branch
Division of Manpower and Training
Office of Water Programs
Environmental Protection Agency
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u.s. Environmental Protection Agency
OFFICE OF WATER PROGRAMS
MANPOWER DEVELOPMENT STAFF
R. F. Guay, Director
Academic Training Branch
State and Local Operator Training
Programs
Office of Environmental Activities
Direct Technical Training Branch
National Training Center
Cincinnati, OH 45268
REGIONAL MANPOWER OFFICES
REGION I
REGION VI
Manpower Development Branch
Division of Air and Water Programs
424 Trapelo Road
Waltham, MA 02514
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Air and Water Programs Division
1600 Patterson
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REGION II
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Air and Water Programs
26 Federal Plaza
New York, NY 10007
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Air and Water Programs
1 735 Baltimore
Kansas City, MO 64!08
REGION III
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Curtis Building
6th and Walnut Streets.
Philadelphia, PA 19106
Manpower Development Branch
Air and Water Division
1860 Lincoln Street - 9th Floor
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REGION IX
REGION IV
Manpower Development Branch
Division of Air and Water Programs
1421 Peachtree Street, NE, Fourth Floor
Atlanta, GA 30309
Manpower Development Branch
Air and Water Division
100 California Street
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REGION X
REGION V
Manpower Development Branch
Office of Air and Water Programs
1 N. Wacker Drive
Chicago, IL 60606
Manpower and Training Branch
Division of Air and Water Programs
1200 Sixth Avenue-Mail Stop 345
Seattle, WA 98101
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CONTENTS
Title or Description
Industrial Water Uses
Outline Number
Sources and Effects of Industrial Wastes
Physical and Chemical Effects of Water Temperature
Effects of Thermal Pollution on Fish Life
1
2
Effects of Pollution on Aquatic Life
Industrial Waste Surveys
3
4
5
Industrial Liquid Waste Surveys
Statistical Considerations in Survey Planning
6
7
8
9
10
Acidity, Alkalinity, pH and Buffers
Laboratory Procedure for Total Alkalinity
Laboratory Procedure for Total Acidity
The Specific Conductance Measurement
Specific Conductivity Laboratory
Chemical Oxygen Demand and COD/BOD Relationships
Solids Relations in Polluted Water
11
12
Determination of Suspended Solids
Laboratory Procedure for Total Solids
Laboratory Procedure for NonFilterable (Suspended) Solids
Laboratory Procedure for Filterable (Dissolved) Solids
Laboratory Procedure for Volatile Solids
Bioassay and Biomonitoring
13
14
15
16
17
18
Special Applications and Procedures for Bioassay
The Use of Bio-Assays: Case Histories
19
20
21
22
Sampling in Water Quality Studies
Sample Handling - Field Through Laboratory
Flow Measurement
23
24
25
Tracing Natural Waters
Preparation of Survey Reports
Pre'sentation of Data
26
27
28
Case Preparation and Courtroom Procedure
29
30
161.4.1. 73
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I SOURCES AND EFFECTS
Industrial Water Uses
Sources and Effects of Industrial Wastes
Physical and Chemical Effects of Water
Temperature
Effects of Thermal Pollution on Fish Life
Effects of Pollution on Aquatic Life
Outline Number
1
2
3
4
5
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INDUSTRIAL WATER USES
I
INTRODUCTION
A A successful industrial waste engineer has
a nearly instinctive ability to detect potent-
ial sources of liquid waste. This ability
develops with experience in analyzing
industrial processeS and operational
procedures.
B This skill is largely based upon intimate
familiarity with industrial uses of water
and proves valuable in many phases of
survey operations -- from selection of
sampling points to o::!valuation of final
results.
C This outline is intended to focus attention
upon specific industrial water uses. In
particular, the information cO:1tained
herein should expedite selection of sampling
locations:
II
COOLING WATER
A The bulk of the water withdrawn by all
industry is used for cooling -- over 900/c
of its total supply. The largest portion
of this water is used to condense steam
in thermal electric power stations. Ex-
clusive of electric utilities, industry
employs twice as much water for co::>ling
as for process and other purposes.
B Both conditioning practices and the quantity
of water required will depend upon the type
of cooling system employed.
1 A once-througH system
2 An open recirculating system
3 A closed recirculating system
C Although most water used for cooling does
not suffer any significant deterioration,
contaminants may be introduced by:
1 Addition of treatment chemicals
2 The use of direct contact condensers
3 Leakage of process and other equipment
w. Q. in. 4. 10. 69
D Blowdown from open recirculating systems
may contain considerable hexavalent chrom-
ium or other compounds. Chromates and
phosphates are used to control corrosion,
whereas bromines, chlorine, copper and
mercury salts, and quaternary amines are
used to inhibit biological growths. Blow-
down usually amounts to only O. 5-2. Oo/c of
the total amO'.lnt of water recirculating in
the system.
E On the other hand, once-through co.::>ling
waters may cause thermal pollution since
all of the heat absorbed in the system is
discharged to the receiving water.
F In addition to cooling water, steam gener-
ating facilities discharge a number of other
wastes such as boiler blowoff, chemicals
used for cleaning of boilers and other
equipment, and exhausted regenerent
solutions from demineralizeI' operations.
m
PROCESS WATER
Nearly all industries produce some kind or
quantity of liquid waste. However, the myriad
wastes produced are all derived from a few
specific uses:
A Reactant
A portion of water used as a reactant
actually enters a chemical reaction and
becomes part of the product. Examples
of such use include:
1 Production of acetylene from calcium
carbide
2 Manufacture of phosphoric acid
B Reaction Medium
Water may be used as a reaction medium
to facilitate mixing and contact of all
components. Although a reaction takes
place, the water may not be an active agent
and may not be included in the product.
Examples of this use include:
1
Suspension or emu.lsion polymerization
2 Chemical pulping as in the Kraft or
sulfite processes
3 Metal finishing baths
1-1
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Industrial Water Uses
C Solvent
Industrial use bears witness to water's
reputation as the "universal solvent".
Water is used as a solvent in a wide
variety of applications including:
1 Extraction of sugar from sliced sugar
beets
2 Ho~ water extraction of glues and gela-
tine from skins and bones after pre-
treatment
3
Leaching of metallic ores by acid,
alkaline, and other aqueous solutions
4 Extraction or removal of inorganic salts
from crude oils (referred to as crude
oil desalting)
D Cleaning or Washing of Products, Raw
Materials, or Intermediates
Batch or continuous washing of raw mat-
erials or product at intermediate or final
stages of manufacture is common.
Examples include:
1 Preliminary washing of fruit and
vegetables after harvesting to remove
soil and organic materials
2 Washing 01 sugar beets prior to slicing
into thin strips for use in the diffusion
battery
3 Pulp washing after digestion to remove
spent liquor
4 Pulp washing after bleaching
5 Washing and soaking of salted or cured
hides at tanneries to remove dirt, salts,
blood, and non-fibrous proteins and
restore moisture lost during preserva-
tion and storage
E Intermediate and Final Rinsing of Parts
Rinsing is a high volume application of
washing, which may occur in a single
step. Rinsing is characterized by continu-
ous use, p::>ssibly several steps, discharge
01 considerable effluent to waste, and high
volume.. Examples include:
I Water rinsing of parts after plating
2 Water rinsing of parts after pickling
1-2
3 Water rinsing of parts after alkaline
cleaning, anodizing, bright dipping,
and other metal finishing operations.
F Washing of Equipment
In many industries washing of equipment
and facilities may produce the majority
of the liquid waste. This use is especially
common in the food industry. Examples
include:
1 Water washing of cans, vats, tanks,
process equipment, and facilities in
dairies
2 Water washing of pans after each baking
to remove grease, flour, and sugar
3 Water washing of equipment, tables,
and floors at the end of each day of
operation in canneries
G Quenching
Water is commonly used in the metals
industries to rapidly cool hot metals and
other products to desired temperature.
Examples of this use include:
1 Quenching of hot coke
2 Quenching of blast furnace slag
3 Quenching of hot metals
H Scrubbing of Gases
Scrubbers are commonly employed to
reduce hazard and air pollution by water
absorption. Unfortunately, the absorbed
compound may prove equally or more
objectionable in liquid form than in the
gaseous state. Examples include:
1 Water scrubbing or washing of blast
furnace flue gases and exit gases from
open hearth and basic oxygen furnaces
to remove particles
2 Water scrubbing of off-gases produced
during electrolytic smelting of alumina-
fluorine salt mixtures
3 Water scrubbing of stack gases from
thermal-electric generating plants
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Industrial Water Uses
I
Buoyant Transporting Medium
Use of water to transport reactants,
products, and wastes is inherent to most
industries. Most large manufacturing
plants are equipped with an elaborate net-
work of channels and ditched for this
purpose. Examples include:
1 Transporting fibers and chemical
additives (sizes, fillers, and pigments)
to paper machines
2 Transporting washed raw fruit or
vegetables in canneries
J Processing Medium
Use of water as a processing medium does
not involve a chemical reaction, as does
its use as a reaction medium. Processing
is a purely physical action. Examples
include:
1 Wet clas sification
2 Froth flotation 0: ores
3 Wet grinding
4 Debarking logs or cleaning metal parts
with high pressure water jets
5 Use of high pressure water sprays to
remove skin and excess caustic from
potatoes withdrawn from lye peelers
K Heat Transfer Medium
Water is commonly used to control temp-
erature of critical stages of many industrial
processes. Temperature control may be
accomplished by either heating or cooling
in jacketed kettles or coil heat exchangers.
Water is commonly converted to steam for
this use. Examples include:
1 Temperature control during nitration
of toluene to produce TNT
2 Air conditioning of assembly rooms in
electronics plants
IV
SUMMARY
The ability to detect potential or actual waste
sources expedites all phases of industrial
waste surveys, especially selection of sampling
points. This ability is largely related to indi-
vidual familiarity with industrial uses of water.
Industry uses water for cooling and a number
of process applications including reactant,
reaction medium, solvent, cleaning or 'washing,
rinsing, washing of equipment, quenching,
scrubbing of gases, and as a transporting,
processing, ot' heat transfer medium.
This outline was prepared by John Ciancia,
Industrial Waste Engineer, and F. P. Nixon,
Acting Regional Training Officer, Northeast
Regional Training Center, FWQA, Edison
Water Quality Laboratory, Edison, NJ 08817.
1-3
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SOURCES AND EFFECTS OF INDUSTRIAL WASTES
I
INTRODUCTION
As a result of manufacturing every industry
produces some kinds and quantities of liquid-
borne wastes. These may be detrimental to
quality of the receiving waters in many ways:
toxicity, oxygen demands, sludge deposits,
surface films, thermal effects, etc. Since
agriculture is a form of production, the
effects of drainage from the land will be con-
sidered among the industrial wastes.
II
CLASSIFICATION SCHEMES
Classification is one of the most important
steps in any water pollution control investi-
gation involving industrial waste discharges.
A There are essentially two approaches to
industrial waste classification:
1
Classification according to industry.
2 Classification according to the effects
the waste produces in the receiving
stream.
B By Industry
Unaer this scheme industrial wastes are
classified as those from the paper and
pulp industry. or antibiotic industry, or
citrus concentrate industry, etc.
1 As a whole, the manufacture of a
specific product will result in similar
liquid waste materials. Classifying
wastewater by specific industries is
very valuable in that it allows for an
evaluation of the pollutionalload being
discharged to a stream no matter where
the industry is located. In this regard,
calculated .waste loadings should be
related to plant production, e. g., pounds
of BOD per ton of finished product.
WP. SUR. 21d. 3. 71
2 This classification scheme is based on
. the assumption that although manufac-
turing plants within an industry will
produce different quantities of waste,
the chemical constituents of the wastes
will be fairly uniform. Wastewaters
from various plants within the same
industry will have different effects on
water quality when discharged to
specific, unique receiving streams.
3 This classification gives no indication
of interaction type effects produced by
more than one industry within a
specified area.
C By Effect
There are many classification schemes
for industrial wastes based upon their
effects in the receiving water body. This
type of classification has more advantages
for water quality studies than the previous
type,' i. e., by industry. Many of the
analytical procedures record the effects
of the industrial waste (BOD, Bioassay,
etc.), rather than the components.
III
CLASSIFICATION BY EFFECTS
Classification by effects is based on the
supposition that an industrial waste may be
characterized by a single predominant effect.
In some cases, this may be true, but most
industrial wastes exhibit multiple effects.
Classification according to one effect may be
unduly restrictive. Notwithstanding this
problem, classification by effect appears to
be the more popular scheme because it is
more related to stream conditions and is
easily applied.
2~1
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Sources and Effects of Industrial Wastes
A Oxygen Depleting Wastes
1
Effect: Low DO levels, due to oxygen
demand, may alter the whole balance
of the biota of the receiving stream.
The natural process of self-purification
may be delayed significantly because
of the lack of adequate oxygen resources.
The demand exerted may be either
chemical or biochemical.
2
Typical Wastes: Examples of industrial
wastes having significant oxygen demand
are:
a Sulfite waste liquors from pulp mills
b Canning plant wash effluents
c
Meat packing wastes
d Textile scouring and dyeing effluents
e
Milk products wastes
f
Fermentation wastes
3
Measurement: Since the primary effect
of these materials is a reduction in dis-
solved oxygen, the BOD test is commonly
used to determine the deoxygenation
potential of the waste. In conjunction
with the BOD, the COD test wIll yield
valuable information.
4
Treatment: All of the methods for the
treatment of oxygen depleting wastes
involve satisfying all or part of the
oxygen demand before discharge to the
stream. This usually involves some
type of secondary treatment either
chemical or biological.
B Toxic Wastes
1
Effects: For the purpose of classifica-
tion, toxicity is considered as a direct
lethal effect on biological forms, as
contrasted to the indirect effects of
oxygen deficiency or smothering.
2
Typical Wastes: Among the many
wastes having toxic effects on
stream biota are:
202
a Spent plating solutions containing
heavy metals and cyanides.
b Acid wastes from pickling operations,
chemical manufacture, and mine
drainage.
c Organic materials such as strong
phenolics, antibiotics, pharmaceu-
ticals and petro-chemical wastes,
and pesticides.
d Textile dyes
3
Measurement: Traditionally, toxic
wastes are evaluated by chemical
analysis of the waste to determine the
concentration of the offending compound.
Unfortunately, suitable analytical
methods are not available for some of
the newer, more complex materials.
The bioassay is rapidly assuming a
key place in the evaluation of toxic
wastes.
4 Treatment: Removal of the toxic agent
is essential to adequate treatment.
Heavy metals are precipitated from
plating solutions, cyanide is oxidized
by chlorination, acids are neutralized,
and organic compounds are oxidized
biochemically by the use of acclimatized
flora.
C Wastes Caus"ing Physical Damage
1
Effects: Certain industrial wastes
cause damage to the stream by physical
actions rather than chemical or bio-
chemical reaction. These materials
create an unfavorable environment
because of the specific physical proper-
ties which they possess.
2
Typical Wastes: Physical damage
may be associated with the following:
a Wastes from lumbering and mining
operations, which contribute large
amounts of silt, sawdust, and other
insoluble deposits.
b Power plant discharges, raising
the temperature of the stream in
the vicinity of the outfall.
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c Petroleum refinery wastes, which
contribute oils and other immiscible
liquids, color, and sludge.
d Dyeing operations, which might
possibly contribute large amounts
of color to receiving streams.
3
Measurement: Wastes which create
insoluble deposits in the stream are
evaluated in terms of the settleable
and total solids tests. Special tech-
niques are required for other wastes,
e. g. , thermal, oil, and industrial
color.
4 Treatment: As in the case of the other
types of wastes, changing the properties
which cause damage is the accepted
method of treatment. Settling basins
and ponds, cooling systems, oil sep-
arators, and similar devices satisfac-
torily remove the objectionable property.
D Wastes Producing Tastes and Odors
1
Effects: Many industrial effluents
contain substances which are capable
of imparting disagreeable tastes to
water supplies. Even very minute
amounts of these materials may cause
public reaction. Often the undesirable
tastes are increased by chlorination.
2 Typical Wastes: The following con-
tribute tastes and odors to water
.supplies.
a Petroleum and petro- chemical
wastes, even when present in ex-
tremely small concentrations.
b By-product coke plants discharges
(phenolics) which are rendered very
objectionable by chlorination.
c
Liquid wastes from the manufacture
of synthetic rubber are often impli-
cated where offensive odors are
present.
3
Measurement: Because of the small
amounts of materials involved, special
concentrating techniques, such as the
Sources and Effects of Industrial Wastes
I
carbon filter, are required. Identifica-
tion of the cO;J;Ilpounds by means of infra-
red spectroscopy and gas chromatograpQY
are utilized. Threshold odor testing
also yields valuable information.
4
Treatment: Most of the compounds
whicQ produce tastes and odors are
organic and lend themselves to bio-
logical treatment. Certain wastes
(those from synthetic rubber manufac-
turer for example) are resistant to
attack and require special treatment
processes.
E Waste Containing -rnor gaoic Dissolved
Solids
1
Many industrial effluents contribute
large amounts of cations (Na, K, Ca,
Mg, Fe) which may cause some dis-
tress to the stream biota.
2
Typical wastes: Tannery wastes and
irrigation waters.
3
Measurement: These wastes are
usually evaluated by chemical analysis
for the specific cation.
4 Treatment: chemical treatment, co-
agulation and ion exchange. Irrigation
waters pose a special problem as far
as treatment is concerned and no ade-
quate treatment technique has been
developed.
F Radioactive Waste
1
Effects: Contamination of water en-
vironment, destruction of aquatic life.
2
Typical Wastes: nuclear reactor
cooling water, uranium ore mining
and refining.
3
Measurement and Treatment: Special
techniques due to the nature of the con-
taminant. Types of treatment, ion
exchange, storage, coagulation and
storage.
2-3
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Sources and Effects of Industrial Wastes
G Corrosive Wastes
d
1 Effects: Highly acidic or basic wastes,
although also toxic, deserve special
attention as corrosive wastes. Such
wastes seriously damage piping systems
and may even corrode ships' hulls and
bridge piers.
2 Typical Wastes: Examples of corrosive
wastes are:
a Spent pickling solutions
b Alkali discharges produced during
manufacture of soap.
H Pathogenic Wastes
1 These wastes may contain organisms
pathogenic to man or plants.
2 Typical Wastes
a Livestock production (cattle, poultry,
swine, laboratory animals)
b Tanneries
c Pharmaceutical manufacture
d Food processing
3 Treatment: Disinfection with chlorine
or other active agent.
IV
C~IMA TOLOGICAL CONDITIONS
Many effects of industrial wastes may be
diminished or enhanced by climatological
conditions. Some of these to be evaluated
are:
A Amount and Frequency of Rainfall
B Amount and Pattern of Run-off
C Stages and Pattern of Stream Flow
D Temperature Patterns - Stream and Air
E Sunlight Patterns
F Wind Patterns
2-4
V
MISCELLANEOUS FEATURES OF
RECEIVING STREAM
A Physical features of stream - cross-
sections, profiles, turbulence, etc.
B Past pollution history of stream most im-
portant in evaluating present effect of any
new industrial waste.
VI SUMMARY
Before any industrial waste can be adequately
treated, some idea of the wastes character-
istics must be known. The most common
procedure is to evaluate the wastewater in
light of the condition of the receiving water
and the uses to which the receiving water will
be put by downstream users. Therefore,
approaching the problem based upon the detri-
mental effects the wastewater produces in the
stream and eliminating the causitive agent is
the most logical method of attack.
REFERENCES:
1 Eckenfelder, W. W., and O'Connor, D. J.
Biological Waste 1'reatment. Per-
gamon Press, London. 1961.
2 Gurnham. C. F. Principles of Industrial
Waste Treatment. Wiley Publishing
Co., Naw York. 1955.
3 Nemerow, N. L. Theories and Practices
of Industrial Waste Treatment. Addison-
Wesley Publishing Co. Reading, Mass.
1963.
4 Rudolf, W. Industrial Wastes, Their
Disposal and Treatment. Reinhold
Publishing Co. New York. 1953. (Out
of Print)
This outline was prepared by P. F.
Atkins, Jr., Sanitary Engineer, formerly
with FWPCA Training Activities.
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PHYSICAL AND CHEMICAL EFFECTS OF WATER TEMPERATURE
I
INTRODUCTION
A With but a few exceptions, the physical
and chemical effects of temperature
change on water quality are more subtle
than, or subordinate to, the more direct
and dramatic biological effects. The
important direct effects, moreover,
usually are not significant in themselves
to water use, but, rather, as they affect
in secondary or tertiary sequence some
other water property or phenomena.
B The more important primary and secondary
effects are:
1 Density on stratification and density
currents, and the whole array of impacts
stratification and density currents have
on water quality and its management.
2 Density and viscosity on sediment
transport and the array of impacts
this sediment transport mechanism
. has on movement and deposition of
particulate matter.
3 Vapor pressure on evaporation rate
and its impact on cooling processes
and wate~ loss.
4 Partial pressure of ~ses on gas
solubility (particularly oxygen) and
its impact on reaeration.
5 Microbial reaction rate on
deoxygenation by organic matter and
its impact on the oxygen sag.
II
PHYSICAL EFFECTS OF WATER
TEMPERA TURE
A Temperature affects many physical
properties of water. Of these, the most
significant to water quality are density,
viscosity, vapor pressure and solubility
of dissolved gases. Table 1 shows the
effect of incremental changes in temper-
ature on these properties for fresh water.
W .Q.ph. 6.8.70
B Very slight differences in density are
sufficient to cause thermal stratifi~ation
in quiescent water bodies, but stra;-
ification stability also depends on water
movement and depth.
1 While the stratification process in
reservoirs and lakes is well known,
the resulting changes in water quality
are not. The changes are becoming
increasingly important because of the
growth of complex water resource
systems.
2 At the end of a winter season, the
impounded water is usually of a fairly
uniform quality and has a relatively
low temperature. A t the onset of
higher atmospheric temperatures,
the surface water and the incoming
water temperatures are raised and
this lighter water tends to "float" on
the colder and denser water already
in the lake.
3 Three definite strata may be formed,
the surface stratum or epilimnion, the
lower stratum or hypolimnion, and a
transition zone called the thermocline,
where the maximum rate of change of
temperature with depth occurs.
4 Stratification may exist until autumn,
when the lake begins to lose heat more
quickly than it is absorbed. As the
water becomes cooler and more dense,
the thermocline sinks, unstable con-
ditions occur and the reservoir mixes
or overturns. In climates where the
water temperature goes below 40 C,
two turnovers may occur per year.
5 Many impounded waters circulate com-
pletely but some circulate only partially,
these lakes being called meromictic by
limnologists. This stable, lower layer
can be caused by either an accumulation
of dissolved or suspended solids in the
water and may render this lower portion
of the lake unsuitable for a water supply.
3-1
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Physical and Chemical Effects of Water Temperature
TABLE 1
WATER PROPERTIES
Dissolved Oxygen
Temperature Density Abs. Viscosity Pressure Saturation
(0 C) (OF) (gmf cm3) (centipoises) (mm Hg) (m~fl)
o 32 0.99987 1. 7921 4.58 14.6
4 39.2 1.00000
5 41 0.99999 1. 5188 6.54 12.8
10 50 0.99973 1. 3077 9.21 11. 3
15 59 0.99913 1. 1404 12.8 10.2
20 68 0.99823 1. 0050 17.5 9.2
25 77 0.99707 0.8937 23.8 8.4
30 86 0.99567 0.8007 31.8 7.6
35 95 0.99406 0.7225 42.2 7.1
40 104 0.99224 0.6560 55.3 6.6
6 Stable stratification is common in lakes
and reservoirs where there is a specific
gravity difference of about. 001 or .002
between waters of the upper layer
(epilimnion) and lower layer (hypolimnion).
Such stratification inhibits vertical
mixing and oxygen transfer to lower
waters.
7 In stratified reservoirs, cool, incoming
waters may travel almost directly to
.the dam outlet in a density current at
a depth of compatible specific gravity.
This reservoir characteristic is
important in predetermining release
temperatures and in selecting optimum
discharge elevation.
C Water temperature affects velocity and
sediment transport through changes in
density and viscosity.
1 Stokes' law describes the velocity of
settling particles in a non-turbulent
medium according to the following
equation.
V =
~
18 (p s - p w)
3-2
where V = settling velocity, cmf sec
p = density of settling particle,
s gmf cm3
Pw = density of water, gmfcm3
J.I = viscosity of liquid, poises
d = diameter of particle, cm
g = acceleration of gravity =
980 cmf sec2
As indicated, settling velocity is inversely
proportional to the water viscosity and
density.
2 Both properties contribute to increased
settling rates at elevated temperatures.
These increased settling rates may
promote better water treatment pJant
operation, though probably to no
measurable degree.
3 A difference in settling velocities can
have a significant effect on the
location and amount of sediment and
sludge deposition in sluggish rivers,
reservoirs and estuaries.
D Evaporation rate increases as water
temperature rises and elevates water
vapor pressure.
-------
Physical and Chemical Effects of Water Temperature
1 Evaporation is caused by the wind ane!
the difference in water vapor pressure
between the air and the water. Since
vapor pressure is a driving force in
evaporation, an ir.crease in tem-
perature will cause an increase in
evaporation, assuming other factors
to be constant.
2 Evaporation is one of the key mech-
anisms in cooling water bodies.
E Water temperature affects gas solubility
and its resultant impact on reaeration.
1 Most living organisms depend on oxygen
in one form or another to maintain their
life and reproductive processes; thus
an adequate supply of oxygen must be
available for any healthy aquatic environ-
ment. Hence, the relation of water
temperature to gas solubility is a very
important aspect of thermal pollution.
2 Oxygen does not react chemically with
water. Therefore, its solubility is
directly proportional to its partial
pressure at any given temperature under
equilibrium conditions with the atmos-
phere. The effect of temperature on the
solubility of oxygen in fresh water under
one atmosphere of pressure is shown
in Table 1.
3 Temperature changes cause complicated
a.djustments in the dynamic oxygen
balance in waters and compound the
difficulty of relating dissolved oxygen
and other factors to oxygen demand,
atmospheric reaeration, photosynthetic
production, diffusion, mixing, etc.
General temperature rises, which
decrease the oxygen holding capacity,
may limit oxygen quantities which are
already less than optimum.
4 Atmospheric nitrogen, with a solubility
about one-half that of oxygen, is usually
not considered an important control
parameter for water quality. However,
recent evidence on the Columbia River
indicates that fish may be seriously
affected in waters which have become
super-saturated with nitrogen through
rapid warming or pressure reduction
after dam discharge.
III
CHEMICAL EFFECTS OF WATER
TEMPERATURE
A Many factors affect chemical reactions,
including the nature and concentration
of reacting substances. catalytic influence
and temperature. The last named is
important because chemical changes
speed up as the temperature rises. In
general, the speed of a chemical change
is approximately doubled for each 100 C
(180F) rise in temperature.
B In an irreversible reaction, higher tem-
peratures will decrease the time required
to produce the final products. In a
reversible reaction, the process is
complete when the reactants reach a
point of dynamic stability. 1. e.. when
the rate of forward reaction equals the
rate of reverse reaction. In this case,
temperature influences both the length
of time required to reach equilibrium and
the proportion of reactants and products
at equilibrium conditions.
. C Most of the chemical effects on water
quality. which are influenced by tem-
perature. center around microbial
activity. Any chemical reaction or
change that results from a life process
is properly termed a biochemical reaction.
1 The majority of chemical reactions
that organisms bring about occur
through catalytic action at far lower
temperatures than would be needed
in the absence of catalysts. Such
catalysts are known as enzymes, and
are themselves temperature-sensitive.
2 The rate of microbial activity increases,
to a point, with the rates of chemical
reactions. The majority of organisms
affecting chemical water quality are in
the mesophylic classification and thrive
in a temperature range of 10 to 400 C
(18 to 1040F). For this group. activity
usually reaches a maximum between
30 and 370 C (86 and 990 F). then falls
off as enzymes become less active.
3-3
-------
;Physical and Chemical Effects of Water Temperature
D Temperature affects not only the rate at
which a reaction occurs, but the extent
to which the reaction occurs, but the
extent to which the reaction takes place.
1 When considering temperature changes
in a receiving water, one must con-
template changes in ionic strength,
conductivity, dissociation, solubility
and corrosion.
2 With an increase in temperature, these
changes might very well result in
differing chemical requirements in the
water treatment plant.
E Taste and odor problems induced by
temperature-accelerated chemical or
biochemical action are accentuated when
oxygen is depleted.
1 Substances which may accumulate
include hydrogen sulfide, sulfur
dioxide, methane, partially oxidized
organic matter. iron compounds,
carbonates, sulfates, and phenols.
2 In addition to greater amounts of
accumulating substances, tastes and
odors are usually more noticeable in
warmer water due to decreased
solubility of gases.
F Biodegradable organic material entering
water exerts a biochemical oxygen demand
(BOD) which must be satisfied before
assimilation of the material is completed.
1 When the temperature of a receiving
water rises, the intensified action of
microorganisms causes the BOD to be
satisfied in a shorter distance from
the discharge than would be accomplished
at a lower temperature. Figure 1
depicts oxygen sag curves for a stream
in which all conditions, i. e., stream-
flow, wasteflow, BOD of the waste,
and initial percent DO saturation, were
held constant, except temperature.
3-4
It is apparent from the curves that the
deoxygenation effect caused by waste
assimilation is exerted over a shorter
stream distance at higher temperatures;
also that oxygen depletion occurs to a
greater extent, since the sag point is
lower at elevated temperature. Hence,
it is possible that the discharge of an
organic waste that previously had not
caused excessive oxygen depletion
could pose problems at an elevated
temperature.
G Chemical effects of slightly increased
temperatures may have minor beneficial
influences on water treatment.
1 Disinfectant action is generally more
rapid at higher temperatures. For
example, for a given dose of free
chlorine, the period required to
disinfect water at 460 F is more than
nine times greater than at 104oF.
2 Reports on coagulant dosages are
contradictory, although reports
indicate a savings of 30 to 509 per
million gallons per each 100 F rise
in temperature.
3
The potential beneiicial effects must
be weighed against the undesirable
effects such as induced slime or algae
growth, taste and odor problems, or
unpalatable drinking water temperatures.
IV
SUMMARY
A The physical and chemical effects of
temperature change on water quality
usually are not significant in themselves
to water use but rather as they affect in
secondary or tertiary sequence some
other water property or phenomenon.
-------
10
.9
"
0,8
E
z 7
w
~ 6
X
o 5
a
w
~ 4
o.
.~ 3
a 2
Physical and Chemical Effects of Water Temperature
FIGURE 1
RELATION BETWEEN TEMPERATURE AND OXYGEN PROFILE
(After La Berge). .
I WASTE
r .
I
I
OUTLET
o
o
10 20 30.
Miles from Outlet Discharging Organic Waste
B The more important effects relate to:
A CIrn"OW LEDGMENT:
1 Stratification and density currents
Material for this outline was taken from
"Thermal Pollution: Status of the Art, "
by Frank L. Parker and Peter A. Krenkel
and "Industrial Waste Guide on Thermal
Pollution, "FWPCA, September 1968
(revised).
3 Evaporation
2 Sediment transport and deposition
4 Saturation with gases
5 Microbial activity
6 Taste and odor
7 Deoxygenation and reaeration
This outline was prepared by D. S. May,
Former Microbiologist, Manpower and
Training, PNWL, Corvallis, OR.
3-5
-------
EFFECTS OF THERMAL POLLUTION ON FISH UFE
I
INTRODUCTION
A The physiology of fishes is directly
affected by temperature.
1 Fishes are classed as Poikilothermic
animals, i. e., their body temperatures
follow changes in environmental tem-
peratures rapidly and precisely.
2 In such animals, the factors favoring
heat loss tend to equal the factors
producing body heat, and thus the body
approaches environmental temperatures.
3 In a majority of fishes, the body tem-
perature differs by only O. 5 to 1. 00 C
(0.9 to 1. 80F) from that of the
surrounding water.
4 A fundamental requirement of fishes is
that the external temperature be well
suited to internal tissue functionality.
B The single most important point in
analyzing or predicting the effects of
temperature change on a fishery is to
look at the individual species important
to the specific water body under study.
II
GENERA L
A Metabolism--Rates of metabolism and
activity increase with increasing tem-
perature.
1 According to Van't Hoff's law,
metabolic activity can double or even
triple over a 100 C (180F) rise in
temperature.
2
This increase in metabolic rate and
activity will occur over most of the
tolerated temperature range and then
often cease suddenly near the upper
lethal temperature.
3 The rates of increased activity vary
with different species, metabolic
processes, and temperature ranges or
leve Is .
BI. ECO. he. 6.8.70
4 The rates may also be modified by
salinity and oxygen factors.
5 Changes in metabolic rates caused
by temperature changes may be
signaling factors for spawning or
migra tion.
6
Chemical reactions within the fish 's
body cells may be accelerated by
temperature increases.
7 Temperature induced changes in cell
chemistry are associated with four
possible death mechanisms.
a Enzyme inactivity caused by the
acceleration of the enzyme
reaction to such a state that the
enzyme is no longer effective.
b The coagulation of cell proteins.
c The melting of cell fats.
d The reduction in the permeability
of cell membranes.
8 Cells may also be killed by the toxic
action of the products of metabolism.
B Reproduction - the temperature range
within which many fishes reproduce is
narrower than that required by the
majority of functions.
1 Fishes generally spawn when a certain
temperature level is reached. Of
course, this level varies from species.
to species.
2 Some fish spawn on a drop in tem-
perature, while others respond to a
rise in temperature.
3
Even though the temperature require-
ments for breeding are narrow, fishes
may populate a heated area by con-
tinued migration from the outside.
4-1
-------
Effects of Thermal Pollution on Fish Life
C Development - temperature changes affect
fish development in several ways.
1 Abnormal temperatures can affect
embryonic development.
2
Low temperatures may slow down
development, but in some cases, fish
attain a larger final size because of
their slow, long continued growth
rather than the rapid growth expe-
rienced at higher temperatures.
D Distribution - temperature is one of the
more important factors governing the
occurrence and behavior of fish life; it
affects the general location of a given
species and may also modify the species
composition of a community or an
ecosystem.
1 Tropical and subtropical fishes are
more stenothermal than those found
in fresh water.
2
Some cold water stenothermal forms
may be eliminated by heated discharges.
while the effect on some eurythermal
(tolerant of a wide temperature range)
species may be to increase the popu-
lation.
3 In tropical areas, species live close to
their upper thermal limits. thus the
effect of a thermal discharge can be
quite severe.
4 In northern areas, species may live in
temperatures as much as 160 C
(28. 80F) below their upper lethal
temperature and will not be as
severely affected.
5
Laboratory tests have shown that a
slow rate of decrease in environmental
temperature is more important for
maintaining life than a slow rate of
increase.
6
Lethal cold can be more important than
lethal heat as a factor limiting the
distribution of marine fish and as a
hazard to some in their native habitats.
4-2
E Synergistic Action - synergism is defined
as the simultaneous action of separate
agents which together, have a greater
total effect than the sum of their individual
effects.
1 In reference to water temperatures,
synergistic action refers to the fact
that temperature rises increase the
lethal effect of toxic substances to
fish and may also increase the sus-
ceptibility of the fish to many diseases.
2 A 100 C (180 F) rise in temperature
doubles the toxic effect of potassium
cyanide, and an 80 C (14. 40F) rise
triples the toxic effect of o-xylene.
3 The temperature effect on toxicity
varies with each substance and with
concentrations of any specific
material; no hard and quick rule may
be formulated to determine this
temperature effect.
4 Since domestic and industrial wastes
are numerous in our nation's waters.
the synergistic action between tem-
perature and toxicity is a relatively
common occurrence.
a Fish kills have accompanied small
temperature rises which might have
been relatively harmless in an
unpolluted stream free of toxic
substances.
b The concentration of a substance
may be harmless at one temperature
but may contribute to fish mortalities
when combined with the stress
imposed by higher temperatures.
5 The virulence of fish pathogens may be
increased by higher temperatures.
a The myxobacteria Chondrococcus
columnaris. which can cause death
through tissue destruction, becomes
more virulent as temperature is
increased.
-------
Effects of Thermal Pollution on Fish Life
F Dissolved Oxygen - two factors associated
with rising water temperature are
decreases in available oxygen and
increases in metabolic rates.
1 These factors combine to render the
aquatic environment less compatible
to fish life at higher water temperatures.
2 At low water temperatures in the range
of 0 to 40C (32 to 39.20F) a dissolved
oxygen level of 1 to 2 mg/l is sufficient
for survival of many freshwater fish
species. When the temperature reaches
15 to 200 C (59 to 680 F), less than 3 mg/l
of dissolved oxygen is often lethal.
3 At these temperatures, oxygen levels
as high as 5 mg/l are sometimes
required to support normal activity
beyond that of merely staying alive.
G Acclimation - the temperature to which
fish become adjusted over an extended
period of time, i. e., the thermal history,
is important because of its influence on
lethal temperature levels.
1 The capacity to acclimate depends on
the genetic background, environmental
history, physiological conditions, and
age of the organism involved.
a The resistance of animals to cold is
much more variable than resistance
to heat.
b The resistance to cold varies with
size, smaller fish resisting best.
2 Acclimation to different temperatures
may involve changes in orientation,
migration, and other behavioral aspects
such as territorialism and biological
rhythms.
a Gradual temperature changes are
tolerated much better than rapid
changes.
b Brief or intermittent exposure to
high temperature can result in
markedly increased resistance to
heat which is not readily lost on
subsequent exposure to low temperature.
c It is the rapid onset of low tem-
peratures that probably causes
death, outstripping the ability of
fish to acclimate and resulting in
greater mortality.
d Deaths resulting from the inability
of fish to rapidly acclimate to
lowering temperatures have been
reported.
3 Acclimation to low temperature usually
tends to shift the lower thermal limit
downward, and acclimation to high
temperatures tends to shift the upper
limits upward.
a The ability to acclimate affects the
temperature range that a fish can
tolerate.
b Fish acclimated to cold winter
temperatures are often subjected
to lethal temperatures in the spring
as warmer water is encountered.
III
FRESHWATER FISHES
A Maximum Temperatures - maximum,
temperatures have been determined for
numerous species of freshwater fish.
1 These temperatures indicate the highest
temperature at which a fish can survive,
but they are often higher than the
maximum temperature at which a species
can survive for long periods.
2 Maintaining water temperature at these
maximums does not insure the main-
tenance of a fish population.
3 Table 1 shows maximum and minimum
temperatures for various species and
acclimation temperatures.
a Values shown are LD50 temperatures,
i. e. temperature survived by 50%
of the test animals.
b These figures are based on specific
test conditions, so care must be
taken in interpreting the data.
4-3
-------
Effects of Thermal Pollution on Fish Life
TABLE 1
MINIMUM AND MAXIMUM TEMPERATURES FOR CERTAIN FRESHWATER FISHES
Acclimated To Minimum Temperature~' Maximum Temperature*
Fish 0C of 0C of Time, Hr. 0C of Time. Hr.
Bass, largem0';lth 20.0 68.0 5.0 41. 0 24 32.0 89.6 72
30.0 86.0 11.0 51.8 24 34.0 93.2 72
Bluegill (Lepomis 15.0 59.0 3.0 37.4 24 31.0 87.8 60
macrochirus purpurescens) 30.0 86.0 11. 0 51. 8 24 34.0 93.2 60
Catfish, channel 15.0 59.0 0.0 32.0 24 30.0 86.0 24
25.0 77.0 6.0 42.8 24 34.0 93.2 24
Perch, yellow 5.0 41. 0 21. 0 69.8 96
(winter) 25.0 77.0 4.0 39.2 24 30.0 86.0 96
(summer) 25.0 77.0 9.0 48.2 24 32.0 89.6 96
Shad, gizzard 25.0 77.0 11.0 51.8 24 34.0 93.2 48
35.0 95.0 20.0 68.0 24 37.0 98.6 48
Shiner, common 5.0 41. 0 27.0 80.6 133
(Notropis cornutus 25.0 77.0 4.0 39.2 24 31. 0 87.8 133
frontalis) 30.0 86.0 8.0 46.4 24 31.0 87.8 133
Trout, brook 3.0 37.4 23.0 73.4 133
20.0 68.0 25.0 77.0 133
'~Values are LD50 temperature tolerance limits. i. e.. water temperatures survived by 50 percent
of the test fish.
c Temperature limits for a given species
will vary slightly depending on the
fish's rate of heating, size, and
physiological condition.
B Preferred Temperatures - most biologists
agree that fish can live for short periods
in waters 0:11 abnormally high temperatures,
but at these high temperatures the fish
cannot perpetuate their population.
4 A temperature need not kill a fish
directly for it to be lethal.
1 Fish seek out the temperature that is
. best suited for their survival.
a Brook trout were found to be com-
paratively slow in catching food
minnows at 17.20 C (630 F) and
virtually incapable of catching
minnows at 210C (700F).
2 This "preferred temperature" is given
in Table 2 for several species of
yearling fish based upon laboratory
experiments.
b Even though their lethal limit is 23
to 250 C (73.4 to 770 F) the fish
could not survive in this temperature
due to a lack of food (Table 1).
3 Table 3 shows the temperature at which
fish in the natural environment seem to
congregate, thus indicating their
"preferred temperature. "
4-4
-------
Effects of Thermal Pollution on Fish Life
TABLE 2
THE FINAL PREFERRED TEMPERATURE FOR VARIOUS SPECIES
OF FISH AS DETERMINED BY LABORATORY EXPERIMENTS
Final
Preferred Temperature
Species °C of Authority
Bass, largemouth 30.0-32.0 86.0-89.6 Fry, 1950
Bass, smallmouth 28.0 82.4 Fry, 1950
Bluegill 32.3 90.1 Fry & Pearson, 1952
Carp 32.0 89.6 Pitt, Garside & Hepburn,
1956
Muskellunge 24.0 75.2 Jackson & Price, 1949
Perch, yellow 24.2 75.6 Ferguson, 1958
Perch, yellow 21. 0 69.8 McCracken & Starkma,
1948
Trout, brook 14.0-16.0 57.2-60.8 Graham, 1948
Trout, brown 12.4-17.6 54.3-63.7 Tait, 1958
Trout, lake 12.0 53.6 McCauley & Tait, 1956
Trout, rainbow 13.6 56.5 Garside & Tait, 1958
4 The level of thermal acclimation
influences the range of temperatures
preferred.
In general, the difference between the
acclimation temperature and the pre-
ferred temperature decreases as the
acclimation temperature increases.
5 Competition between species is also
important to distribution and survival
since different species have different
species have different preferred tem-
peratures.
Temperatures higher than optimum may
not kill trout, but they may produce
environmental conditions favorable for
the production of coarse fish and reduce
the trout I s food supply.
IV
MARINE, ESTUARINE, AND
ANADROMOUS FISHES
A Spawning - limits of temperature require-
ments for spawning are usually much more
stringent than for adult fish survival.
1 The normal spawning temperature for
sockeye salmon is between 7. 2 and
12.80 C (45-550F); lower and upper
lethal limits are 00 C (320 F) and about
250 C (770F), respectively.
2 Pink salmon spawn best near 100 C
(500F).
3 During migration salmon do not feed,
so high water temperatures which
increase their metabolic rate may
result in fuel depletion before spawning
can occur.
4-5
-------
TABLE 3
PREFERRED TEMPERATURES FOR VARIOUS SPECIES OF FRESHWATER FISH
BASED ON FIELD OBSERVATIONS .
tI:!
.....
.....
C1)
n
....
00
o
.....
>-3
::T
C1)
Ii
S
ID
.....
~
I
0'>
Preferred Temperature
Species uC uF Water Body Location Authority
Alewife 4.4- 8.8 39.9-47.8 Cayuga Lake New York Galligan, 1951
Bass, largemouth 26.6-27.7 80.0-81.9 Norris Res. Tennessee Dendy, 1948
Bass, rock 14.7-21.3 58.5-70.3 Lakes Wisconsin Hile & Juday, 1941
" ;0 20.7 69.3 Streams S. Ontario Hallam, 1958
Bass, smalimouth 20.3-21.3 68.5-70.3 Nebish Lake ~/i scons in Hi le & Juday, 1941
.. 21.4 70.5 Streams S. Ontario Ha 11 am, 1958
Bass, spotted 23.5-24.4 74.1-75.9 Norri s Res. Tennessee Dendy
Perch, yellow (small) 12.2 54.0 Muskellunge Lake Wisconsin Hile 1/, Juday, 1941
Perch, yellow (large) 20.2-21.0' 68.4-69.8 Lakes Wisconsin Hile & Juday, 1941
Shad, gizzard 22.5-23.0 72.5-73.4 Norris Res. Tennessee Dendy
Trout, brook 14.2-20.3 57.6-68.5 t.1oosehead Lake Maine Coooer t. Fuller
" " 15.7 /60.3 Streams S. Ontario Hallam, 1958
" 12.0-20.0 53.,6-68.0 Redrock Lake Ontario Baldwin, 1948
Trout, 1 ake 10.0-15.0 50:0-59.0 Cayuga Lake New York Galli9an, 1951
" " 14.0 57.2 White lake Ontario Kennedy, 1941
" 11.0-11.5 51.8-52.7 Moosehead Lake Maine Cooper & Fuller, 1945
" 8.0-.10.0 46.4-50.0 Louisa & Redrock Ontario r-iartin, 1952
Lakes
Wa 11 eye 20.6 69.1 Trout Lake Wisconsin' Hile & Juday, 1941
" 22.7-23.2 72.9-73.8 Norri s Res. Tennessee Dendy, 1948
'1j
o
.....
~
....
,....
o
~
o
~
I:rj
,....
00
::T
t"
t::;
C1)
-------
Effects of Thermal Pollution on Fish Life
4 Fish migration is hampered by
unfavorable temperature conditions.
5 A thermal block of 21.10C (700F)
at the mouth of the Okanogan River,
Washington, prevented migration into
the stream from the Columbia River.
6 Generally for salmon, upstream
migration and reproduction occur best
at temperatures between 7.2 and 15.60 C
(45 and 600F).
BEggs - the incubation of eggs and develop-
ment of fry generally have more critical
temperature requirements than either
fingerling or adult fish.
1 Table 4 shows the minimum and
maximum temperatures reported for
the successful hatching of various
species of marine, estuarine, and
anadromous fish eggs.
2 Care must be taken not to equate
successful hatching with fry survival;
Chinook salmon eggs incubated at
16.10 C (610F) hatched successfully,
but suffered severe mortality in the
late fry stage.
C Young Fish - Table 5 shows the tem-
perature limits for the survival of
various species of young marine,
estuarine, and anadromous fishes at
several acclimation temperatures.
1 This information is based on laboratory
tests which often produce data not
directly transferable to the natural
environment.
2 Laboratory tests on striped bass
fingerlings showed an upper lethal
temperature of 350C (950F), but
studies in the Atlantic Ocean indicated
striped bass fish kills occurring at
temperatures of 25 to 270 C (77.0 to
80.60F).
3 Fish in the estuarine environment are
more susceptible to temperature
changes than those in fresh water.
However, wider ranges of tolerance
between species exist in estuarine
waters.
4 Decreases in temperature seem to have
more of an effect on estuarine fishes
than on freshwater fishes.
TABLE 4
TEMPERATURE RANGES FOR SUCCESSFUL EGG HATCHING OF VARIOUS
MARINE, ESTUARINE, AND ANADROMOUS FISHES
Lower Limit Upper Limi t
Species 0C UF 0C uF Authority
Bass, strirJed 12.8 55.0 23.9 75.0 A 1 bercht, 1964
California ki 11 ifish 16.6 61. 9 28.5 83.1 Hubbs, 1965
California grunion 14.8 58.6 26.8 80.1 Hubbs, 1965
Salmon, Chinook 5.8 42.4 14.2 57.6 Combs & Burrows, 1957
9.4 48.9 14.4 57.9 Seymour, 1956
5.6 42.1 14.4 57.9 Leitritz, 1962
Salmon, sockeye 4.4-5.8 39.9-42.4 12.8-14.2 55.0-57.6 Combs, 1965
Sea lamprey 15.0 59.0 25.0 77.0 McCauley, 1963
15.6 60.1 21. 1 70.0 Piavis, 1961
4-7
-------
Effects of Thermal Pollution on Fish Life
TA BLE 5 ..
LETHAL TEMPERATURE RANGES FOR YOUNG MARINE, ESTUARINE, AND ANADROMOUS FISHES
Acclimation Temperature Lower Lethal Temperature Upper Lethal Temperature
Species uC OF 0C . uF 0C UF Authority
Greenfish. 12.0-28.0 53.6-82.4 4.1-13.0 39.2-55.4 28.7-31. 5 83.7-88.7 Doudoroff, 1942.
HetTing 7.5~15.5 45.5-59.9 -1. 8 to -0.75 28.8-30.7 22.0-24.9 71.6-75.2 Bl axter, 1960
Salmon, Chinook 5 41 21.5 70.7' Brett, 1956
" " 10 50 0.8 33.4 24.1 75.7' "
15 59 2.5 36.5 25.0 77.0
20 68 4.5 40 :1 . 25.1 77.2
23 73.4 7.4 4513 ---- Brett, 1952
,,' 26.7 80.0 Kerr, 1953
Salmon, chum 5 41 21.8 71. 2 Brett, 1956
" 10 50 0.5 32.9 22.6 72.7 "
15 59 4.7 40.5 23.1 73.6
20 68 6.5 43.7 23.7 74.7
23 73.4 7.3 45.2 ---- Brett, 1952
Salmon, pink 5 41 21.3 70.3 Brett. 1956
" " 10 50 22.5 72.5
15 59 23.1 73.6
20 68 23.9 75.0
Salmon, silver 5 41 0.2 32.4 22.9 73.2 Brett, 1956
" " 10 50 1.8 35.1 23.7 74.7 " "
15 59 3.5 38.3 24.1 75.7
20 68 4.5 40.1 25.0 77.0
23 73.4 6.4 . 43.5 ---- Brett, 1952
Sall1t)n, sockeye 5 41 0.0 32.0 22.2 . 72.0 Brett, 1956
" " 10 50 3.1 37.6 ' 23.4 74.1 " "
15 59 4.1 39.4 24.4 75.9
20 68 4.7 40.5 24.8 76.6
23 73.4 6.7 44.1 ---- Brett, 1952
Topsmelt 20 68 10.1 50.2 31.8 89.2 Doudoroff, 1942
a In studies of young greenfish to
determine the resistance and
acclimation of marine fishes to
temperature changes, Doudoroff
found that heat resistance was gained
rapidly and lost slowly.
b Acclimation to decreasing temper-
atures was slower than acclimation
to increasing temperatures.
c Transposed to the practical case,
this fact implies that the shutdown
of a power generating plant may be
more detrimental than its normal
discharge of heat.
5 Anadromous fingerlings have maximum
growth in the temperature range of 10
to 15.60 C (50 to 600F).
4-8
6 Research on the effects of temperature
on swimming speed indicates that for
young sockeye salmon optimum
cruising speed occurred at 150 C
(590F), and for young silver salmon
at 200 C (680 F); thus, the fish I s
mobility for protection and feeding is
affected by temperature changes.
D Adult Fish - Table 6 shows the lethal
temperature limits for several species
of adult marine, estuarine, and
ana dromous fishe s .
1 Adult fish are usually able to select
their preferred temperatures, unless
trapped in shallow water or forced to
migrate through thermal blocks.
-------
Effects of Thermal Pollution on Fish Life
TABLE 6
,LETHAL TEMPERATURE LIMITS FOR ADULT MARINE, ESTUARINE, AND ANADROMOUS FISHES
Species
Alewife
Bass, striped
California killifish
Common si1verside
Flounder, winter
Herring
Northern swellfish
Perch, whi te
Salmon (general)
Acc11mation Temperature Lower Lethal Temperature Upper Lethal Temperature
uc UF 0c UF uc OF
2&.7-32.2
6.0- 7.5 42.8-4.5.5 25.0-27.0
14.0-28.0 57.2-82.4 32.3-36.5
7.0-28.0 44.6-82.4 1.5- 8.7 34.8-47.8 22.5-32.5
21.0-28.0 69.8-82.4 1.0- 5:4 33.8-41.6
7.0-28.0 44.6-82.4 22.0-29.0
-1.0 30.2 19.5-21.2
14.0-28.0 57.2-82.4 8.4-13.0 47.1-55.4
10.0-28.0 50.0-82.4 28.2-33.0
4.4 40.0 27.8
0.0 32.0 26.7
Authority
80.0-90.0 Trembley, 1960
77.0-80.0 Talbot, 1966
90.1-97.7 Doudoroff, 1942
73.3-90.3 Hoff & Westman, 1966
71. 6-84.2
67.1-70.1
Brawn, ~ 960
Hoff & Westman, 1966
82.9-90.4
82.0 Trembley, 1960
80.0 Columbia Basin Inter-
agency Camm., 1966
ACKNOWLEDGMENTS:
Material for this outline was taken from the
"Industrial Waste Guide on Thermal Pollution, "
Alden G. Christianson and Bruce A. Tichenor,
principal authors.
REFERENCES
1 Brett, J.R. Some Principles in the
Thermal Requirements of Fishes.
Quarterly Review of Biology. 31(2):
75-87. 1956.
2 Brett, J.R. Thermal Requirements of
Fish--Three Decades of Study, 1940-
1970. Biological problems in Water
Pollution. Transactions, 1959
Seminar. . Robert A. Taft Engineering
Center, Cincizmati, Ohio. Technical
Report W60-3, 110-117. 1960.
3 Brett, J.R., Hollands, M. and Alderdice,
D. F. The Effect of Temperature on
the Cruising Speed of Young Sockeye
and Coho Sahnon. Journal of the Fish.
Research Bd. of Canada. 15(4): 587-
605. 1958.
4 Burrows, R. E. Water Temperature
Requirements for Maximum Pro-
ductivity of Sahnon. Water Temperature
Influences, Effects, and Control.
Twelfth Pacific Northwest Symposium
on Water Pollution Research, Pacific
Northwest Symposium on Water
Pollution Research, Pacific Northwest
Water Laboratory, Corvallis, Oregon.
29-38. 1963.
5 Doudoroff, P. The Resistance and
Acclimation of Marine Fishes to Tem-
perature Changes: 1. Experiments with
Girella nigricans (Ayres). Biological
Bulletin. 83 :219-244. 1942.
4-9
-------
Effects of Thermal Pollution on Fish Life
6 Doudoroff, P. Water Quality Requirements
of Fishes and Effects of Toxic Substances.
In The Physiology of Fishes. M. E.
Brown, Ed. Academic Press, Inc.,
New York. 403-430. 1957.
7 Ellis, M. M. Temperature and Fishes.
Fhh Leaflet No. 221, U. S. Fish and
Wildlife Service. 1947.
8 Ferguson, R. G. The Preferred Tem-
perature of Fish and Their Midsummer
Distribution in Temperate Lakes and
Streams. Journal of the Fish.
Research Bd. of Canada. 15:607-624.
1958.
9 Fish. Bd. of Canada.
1961-62. 206 pp.
Annual Report
1962.
10 Gunter, G. Temperature, Chapter 8,
Treatise on Marine Ecology and
Palaeoecology. 1. J. W. Hedgepeth,
Ed. Geology Society American
Memoirs. 67:159-184. 1957.
11 Kinne, O. The Effects of Temperature
and Salinity on Marine and Brackish
Water Animals. 1. Temperature.
Oceano-Marine Biological Annual
Review. 1:301-340. 1963.
12
Laberge. R. H. Thermal Discharges.
Water and Sewage Works. pp. 536-
540. 1959.
13 Major. R. L. and Mighell, J. L.
Influence of Rocky Reach Dam and the
Temperature of the Okanogan River on
the Upstream Migration of Sockeye
Salmon. Fisheries Bulletin. U. S.
Fish and Wildlife Service. 66(1):131-
147. 1966.
14 Naylor, E. Effects of Heated Effluents
on Marine and Estuarine Organisms.
In Advances in Marine Biology.
Sir Fredrick S. Russell. Ed. Academic
Press. 63-103. 1965.
15 Nikolsky, G. V. TheEcology of Fishes.
Academic Press, New York. 352 pp.
1963.
4-10
16 Olson, P.A. and Foster, R.F.
Temperature Tolerance of Eggs and
young of Columbia River Chinook
Salmon. Trans. of American Fish.
Soc., 58th Annual Meeting. pp: 203-
207. 1957.
17 Pennsylvania Department of Health.
Heated Discharges--Their Effect on
Streams. Report by the Advisory
Committee for the Control of Stream
Temperatures to the Pennsylvania
Water Board. Harrisburg, Pennsylvania.
Pennsylvania Department of Health
Publication No.3. 108 pp. 1962.
18 Prosser. C. L. Physiological Variations
in Animals. Biological Review.
30(3):229-262. 1955.
19 Prosser. C. L., Brown, F. A., Bishop,
D. W., JOM, T. L., and Wulff, V. J.
Comparative Animal Physiology.
W. B. Saunders Co., Philadelphia. Pa.
1950.
20 Stanier. R. Y., Doudoroff, M. and
Adelburg. E.A. The Microbial World.
Prentice-Hall, Englewood Cliffs, N. J.
753 pp. 1963.
21 Talbot, G. B. Estuarine Environmental
Requirements and Limiting Factors
for Striped Bass. A Symposium on
Estuarine Fisheries. American Fish.
Soc. Special Publication No.3, pp. 37-
49. 1966.
22 Rarzwell, C. M. Water Quality Criteria
for Aquatic Life. Biological Problems
in Water Pollution. Robert A. Taft
Sanitary Engineering Center, Cincinnati.
Ohio. 246-272. 1957.
23 Technical Advisory and Investigations
Branch, FWPCA. Temperature and
Aquatic Life - Laboratory Investigations-
No.6, Cincinnati, Ohio. 151 pp. 1967.
24 Warinner, J. E. and Brehmer. M. L.
The Effects of Thermal Effluents on
Marine Organisms. International
Journal of Air and Water Pollution.
10(4):277-289.
This outline was prepared by John F. Wooley,
Former Biologist. Manpower & Training Branch.
Pacific Northwest Laboratory Lab.. EPA.
-------
- EFFECTS OF POLLUTION ON AQUATIC UFE
I
INTRODUCTION
A The effluent from any given industrial
plant may be combined with municipal
sewage, and/or wastes from other
industries. This may occur in the
sewerage system or in a natural body
of water.
1 Toxic wastes may inhibit biota of
treatment plant as well as life in
receiving stream.
2 Organic wastes may simply increase
sewage-type load on plant and stream.
3 The above effects may be reinforced
or neutralized by a complex of
industrial wastes.
B The general overall character of a body
of water may be subtly changed over a
period of time.
IT
The principle of limiting factors (see
Figure 1) deals with the response of
organisms to various factors in the
environment.
A Liebig's Law of the Minimum (Figure 1)
states that the distribution of a species
may be limited by one or more essential
environmental factors which occur in
minimal quantities.
B Shelford on the other hand pointed out in
his Law of Tolerance (Figure 1) that there
are also maximum values of most
environmental factors which can be
tolerated. In between these two extremes
there are ranges which may be called
"optimum" for factors useful to the
organism. Purely deleterious factors
on the other hand have a maximum tol-
erable value, but no optimum. The
range between the maximum concentration
(greater than zero) which kills no orga-
nism and the minimum concentration
BI. BIO.Uk. 5. 71
which kills all organisms is known as
the "critical range. "
C These principles apply to all aquatic life
whether in a stream, lake, estuary, or
treatment plant. They are the basis for
the control or regulation of biological
conditions.
III
INDIRECT TOXICITY: MODIFICATIONS
OF THE ENVIRONMENT WHICH AFFECT
AQUA TIC LIFE
A Deposition of inert precipitates and silt
tends to smother bottom organisms.
Contributing materials include silt or
sand from erosion due to poor agricul-
tural practices, rock flour or tailings
from mining or quarry operations, mica,
coal washings, sawdust and debris from
lumbering, insoluble precipitates or
complexes from chemical industries.
1 Vulnerable organisms include
important fish foods such as insect
larvae and snails; also fish eggs,
bottom -living algae such as diatoms,
and many others.
2 Physical injury to delicate membranes
of eyes, and gills may also result.
3 Inert suspended materials and dyes
reduce light penetration, suppress
photosynthesis and hence biological
productivity. They also prevent game
fish and other predators from seeing
their prey, thereby reducing the
efficiency of food utilization.
The word "stream" should be interpreted in
most cases to mean "river, " "lake, "
"estuary, " etc~. as applicable.
5-1
-------
Effects of Pollution on Aquatic Life
U)
a>
....
u
....
't:I ....
a b.O
~~
Liebig's Law
Shelfords Law
Extinction
Optimum
Range
Extinction
....
1ij
......
-------
c The absolute values of these thresh-
olds vary with the species and other
factors. Five mg 02 per liter is
often listed as a mimmum permissible
value to maintain a well-rounded
healthy population of fishes on a year-
round basis.
3
Low oxygen tensions may also increase
the toxicity of certain chemicals.
D pH
1
"pH" is a logarithmic expression of the
hydrogen ion concentration in a solution.
Hydrogen ions (H+) in certain concen-
trations are toxic to aquatic life
(as are also hydroxyl ions: OH-).
Aquatic life in relative abundance and
variety can be found in waters ranging
from approximately pH 5 to 9. Thriving
communities including algae, insects,
and fish have been studied in waters
with a pH of at least 11.
2 Many species of aquatic organisms can
adjust to pH values over a wide range.
Sudden change of any kind however can
be fatal.
3 Most metals and other toxic substances
in dilute solution tend to become less
toxic at high pH values. A notable
exception is ammonia.
IV
POLLUTION WHICH RENDERS FISH OR
SHELLFISH UNUSABLE OR INTERFERES
WITH THEIR CAPTURE
A Radioactivity at levels currently found in
our waters has not been observed to
adversely affect aquatic life itself. It may
however, be taken up with food materials
and render fish or fishery products unusable.
1 Radioactive nuclides (forms of chemicals)
are taken up by the plants (predominantly
algae) in the processes of photosynthesis
and other types of protoplasmic syn-
thesis. There is no selection between
nuclides on the basis of radioactivity.
Effects of Pollution on Aquatic Life
2 As the chemicals originally assimi-
lated by the algae are "eaten up the
food chain" (from algae to inverte-
brates to small fish to large fish to
man and other predators) their
radioactivity moves along with them.
3 Thus radioactivity is acquired by
fishes essentially through food, and
scarce1y at all by direct assimilation
or absorption.
4 Plankton -feeding organisms such as
herrings, oysters, and clams acquire
radioactivity directly from the algae
on which they feed. Since they con-
centrate this food from large volumes
of water, they may be much "hotter"
than the surrounding water itself.
B Fish may be repelled or driven out of an
area by obnoxious chemicals. This may
simply result in their scarcity or absence
from a given locale, or it may prevent
their swimming up a river to spawn. In
this case the species would soon disappear
and be lost to the community.
C Color, odor, oil, floating scum, bacterial
slimes, and other such materials tend to
discourage sport fishing and interfere
with gear used by commercial fisheries.
D Sublethal concentrations of chemicals
such as phenol, benzene,oil, 2-4-D, etc.,
may impart an unpleasant taste to fish
flesh, even when present in very dilute
concentrations. This is nearly as
detrimental to the fisheries as a complete
kill, and of course applies to shellfish
as well as fin fish.
E Minamata disease was first described
from Minamata, Japan, as a disorder
resulting from eating various seafoods
taken from Minamata Bay, Kyushu,
Japan. The disease results from
industrial toxicity, in this case an organic
mercury compound, transmitted to a wide
variety of local marine seafood species.
These organisms are not known to be
affected, but acting as "transvectors, "
5-3
-------
Effects of Pollution on Aquatic Life
pass the toxin along to predators or human
consumers. Over 300/0 mortality occurred
in Minamata among people eating local
seafood.
1 It may be important to note that a fish
kill was recently reported from a TV A
lake in this country resulting from
mercury leaching from corroded 50
gallon drums used as floats by
marinas.
2 Bird and fish kills have recently
occurred in Swedish lakes resulting
from mercury compounds from pulp
mills. Levels in pike exceed the WHO
standards for human consumption and
the local population has been advised
not to eat pike more than once a week!
Ca ses of high mercury levels are increasing.
V
DIRECT TOXICITY: AFFECTS THE
ORGANISM ITSELF
Fish kills are often the result of direct
toxicity. If this is sufficiently potent to kill
at once, or within a few days, it is called
"f' h kill"
acute, and is often observed as a 1S .
Action that may require weeks or months to
be effective may be referred to as low-level,
cumulative, or chronic toxicity, and is more
often observed as simply a reduction of
productivity: "Fishin' ain't what it used to
be." Examples of chemicals often believed
to be involved include: acids, alkalines,
ammonia, chlorine, cyanides, metals,
phenols, solvents, sulfides, synthetic organic
chemicals, oil field brines, pesticides,
herbicides, detergents and others.
A Acute toxicity may be so broadly effective
that many forms of life are affected at one
time, or it may be highly selective. It
may result from a low concentration of a
highly toxic material or a high concentration
of a relatively less toxic material.
"1 "
1 It is frequently encountered as a s ug
resulting from a dump or spill, followed
by normal, relatively non-toxic con-
ditions as the mass of water containing
the poison flows on downstream, or is
deflected by tidal movements.
5-4
2 Acute toxicity can be evaluated by
means of the toxicity bioassay
technique and various modifications
(Figure 2).
100
....
lIS
.~
t 50
;j
tIJ
...
c
(!j
o
1-0
(!j
0.
o
TL 5 0 t
C'
C
~
Increasing Concentration
Figure 2 - Critical Range
C: maximum concentration at which
no fish die, C': minimum concen-
tration at which all die. TL50 t,
50% tolerance limit (concentration
tolerable to 50% of the population)
for time t.
B Chronic or low-level toxicity may change
the entire population balance.
1
Susceptible species of either fish or
fish food organisms may die off,
thereby permitting tolerant species
to flouriSh for lack of competition.
2 If algae and/or invertebrate food
organisms are killed off fish may die
or move out of the area.
3 Weakened individuals are more
susceptible to attack by parasites and
disease, such as the aquatic fungus
Saproleenia.
4 Reproductive potential may be altered.
Eggs or fry mayor may not be more
susceptible to toxic substances than
adults.
5 Host fish for mussel (unionidae) life
cycle may not survive,
-------
6 The result may be a slow and subtle
alteration of the characteristics of a
stream over an extended period of time.
C The specific physiological mechanisms
involved are infinite in variety and but
little known. Included are such processes
as enzyme inhibition as in the case with
some of the pesticides, and over stimu-
lation of mucous membranes of the gills,
leading to death by suffocation.
D There are a number of excellent diagnostic
techniques for the examination of dying
fish, these include pathogenic bacteria,
parasites, some metals, and certain
pesticides. None are routine but require
specific handling and preservation tech-
niques .
E A recently developed procedure for
protecting aquatic life from deleterious
substances is biomonitoring. This is
the continuous monitoring or surVeillance
of an effluent for toxicity by means of a
system for exposing living organisms
(such as fish or invertebrates) to a con-
tinuously flowing stream in a dilution just
below the known danger point. Should the
toxicity of the substance increase the test
organisms respond in some recognizable
manner, thus giving warning that correc-
tive measures need to be initiated.
VI
MECHANISMS OF POLLUTION
TOLERANCE AND SENSITIVITY
The fact that some organisms are more
resistant to pollution than others needs no
emphasis. The matter of "why?" and "how?"
on the other hand, is quite another question.
In some cases the answer is obvious, in
others not. In general we can say that the
adaptations of certain species enable them
to resist certain types of natural conditions
such as organic deposits or sand bars. When
man artificially creates conditions such as
sludge banks, or sand bars, organisms which
can tolerate such conditions move in, survive,
and often thrive. Other forms are
eliminated.
Effects of Pollution on Aquatic Life
A Organic pollution is essentially non-toxic.
Its typical result as noted above is
oxygen depletion, physical turbidity, and
smothering blankets of sediment or sludge.
B Devices and mechanisms for living in
oxygen-poor or oxygen-free water include
the following:
1 Obtaining oxygen from the air by means
of periodic trips or access to the
surface.
a The snorkel tube of the rat-tailed
maggot.
b Periodic trips of the mosquito
larvae and Corixidae or water
boatmen. The mosquito takes air
directly into its respiratory system,
the water boatman into a trap or
space beneath the wing covers, as
well as into a layer of air held by
fine hairs or "pile" all over its body.
c Behavior of the air breathing snails
such as Physa which have an internal
lung cavity.
d Insects which tap into air tubes in
aquatic plants. .
e Fishes which gulp air at surface or
breathe surface water.
2
Special devices and behavior for
respiration of water
a Hind intestine respiratory
structures of dragonfly larvae
permits respiration in silt-laden
water.
b Movement of gill covers and
similar structures in isopods and
certain insect groups maintains a
current of water over respiratory
. organs.
c Body movements of chironomid
larvae create wafer current in
tibe. Sludge worms
5-5
-------
~ffects of Pollution on Aquatic Life
and other annelids also create water
movement by means of sinuous body
movements.
3 Physiological and behavioral adaptations
to endure low oxygen tensions.
a Forms possessing accessory
respiratory pigments such as
hemoglobin might be expected to
be able to be able to extract the
last vestige of dissolved oxygen from
the water. Two groups famous for
resisting low 00 do have hemoglobin:
the larvae of certain Chironomid
midge flies, and small annelid worms
such as sludge worms, (it should be
noted however, that the hemoglobin
in each case is simply dissolved in
the blood plasma, rather than being
concentrated in special corpuscles
as is the case in the more efficient
vertebrate system. )
b The mere possession of hemoglobin
however, does not seem to assure
tolerance of low DO (Walshe '47).
Larvae of the midge Tanvtarsus SPP.
have hemoglobin, but will not
tolerate oxygen-poor waters.
Hemoglobin -bearing Chironomus
bathopilus is moderately tolerant,
and Chironomus plumosus is highly
tolerant, however.
c During periods of low DO, Chironomus
plumosus apparently respires carbo-
hydrates as usual, but excretes
excess lactic acid instead of accu-
mulating it.
d Various species of Daphnia (micro-
crustacea) have been shown to
accumulate hemoglobin in oxygen-
poor waters but not in oxygen-rich
waters (Fox 147), No clear adaptive
significance has yet been proven
however.
C Advantageous Feeding Habits
All highly organic pollution tolerant orga-
nisms are scavengers, and hence find an
abundance of food. Most are relatively
5-6
defenseless and hence have normally high
reproductive rate. The result in a
polluted situation is thus usually an
extreme abundance.
D The reverse problem is why are intolerant
species intolerant?
1 A physiological requirement for higher
oxygen levels is probably most basic.
2 Turbidity would hamper any organisms
employing sight in any way.
3 Absence of light would suppress the
growth of green algae, and hence also
restrict the growth of algae feeders.
E Inert silts by themselves have many
damaging effects such as abrasive or
smothering action.
Biological mechanisms for enduring inert
silt or sand pollution are not numerous,
and consequently such locations are
usually known as biological deserts.
Since some life exists even in deserts
however, a few forms may occasionally
be found. In general they are typical sand
or mud dwellers. Since the available
food in such a substrate is at best of a
very low order, inhabitants of these
situations must either seek buried or
trapped food particles or capture food
from the passing waters.
1 If there is no BOD involved, and water
and oxygen circulate down into the
deposit, burrowing forms such as
certain mayflies, annelid worms,
ammocetes lamprey larvae, micro-
crustaceans, and others may burrow
down to depths of two feet or more.
Fish eggs normally deposited in gravel
and newly hatched larvae are also
dependent on circulating water. Such
a population can be killed overnight by
a layer of fine sediment or sludge which
seals the surface to water circulation.
2 Water or plankton feeders include
clams and mussels which can move
about freely in a soft, shifting bottom,
thus keeping on top of silt or sand as
-------
it accumuJates. If deposition is
actively taking pJace, however, there
will probably be so much turbidity in
the water that pJankton (food) organisms
are unable to live. Under such cir-
cumstances certain cJams and snails
have the ability to close the shell so
tightly by means of valves or an
operculum that all contact is lost with
the environment for extended periods.
during which C02 tends to lower the
rate of body metabolism. Organisms
of this type have been reported to be
dug up with sand and gravel and
incorporated into concrete products
while still alive. Emergence of a
population of asiatic clams (CorbicuJa)
for example, just as a big block of
concrete is setting is said to be rough
on contractors!
3 An interesting situation occasionally
develops in estuaries where mud of
moderate organic content is slowly
deposited over oyster beds. The
oysters are unable to move, but as
they grow, their shells tend to bend
upward above the accumuJating silt,
and may grow to several inches in
length while growing very little in
width. Crowding brings about a similar
reaction in the effort to avoid being
buried.
F Few generalizations can be offered
re1ative to toxic pollution except that
toxicity is relative, and all forms do not
respond equally to a given toxicant. .
1
Few mechanisms of toleration can be
listed. beyond the natural resistance
that certain forms may have for a given
condition. For example, some marine
species may survive a salt concentration
that is toxic to freshwater species.
Over a period of several generations,
some species may develop a genetic
resistance to some toxicant such as
insecticides in the same way that DDT-
resistant strains of houseflies have
developed. Copper sulfate, and chlorine-
resistant strains of algae such as
Cosmarium for example, may develop
in treated water supply reservoirs.
Effects of Pollution on Aauatic Life
2 Some bottom in-fauna organisms such
as annelid worms may retreat down
into burrows until a slug of undesirable
water passes.
3 Molluscs may close shells tightly for
the same purpose. The metabolic
rate is known to diminish with the
increase of C02 inside the closed
shell, thereby enabling them to
remain tightly sealed for extended
periods of time.
VII
EFFECTS OF UFE HISTORY STAGES
A In order to survive in a polluted area,
each life history stage of an indigenous
organism must be able to survive in turn.
B If some given life history stage cannot
tolerate conditions, and the species is
present:
1 Fortuitous changes may occur at the
proper time(s) to permit survival of
the more susceptible stages(s) or:
2 Recruitment from less polluted areas
may occur.
C Some examples of reproductive stages or
procedures which might affect pollution
sensitivity:
1 Egg or egg-like stages are often
enclosed in protective membranes,
jelly masses, or cases. May remain
dormant until favorable conditions
develop.
2
Eggs may be deposited in locations
where they are less exposed to polluted
water as:
buried in the gravel,
on the surface film,
on rocks over the water moistened
by spray,
on mud surface near water,
or in locations where maximum
water circulation is encountered
as at lip of waterfall.
5-7
-------
Effects of Pollution on Aquatic Life
3 Eggs may require minimal DO due to
low metabolic rate~
4 Eggs deposited on or in bottom may be
susceptible to smothering.
5 Newly hatched larvae often continue to
live on stored yolk material for a time.
On beginning to take natural food, they
may be killed by toxic content thereof,
such as organochlorines.
6 Some forms such as certain sludge
worms commonly reproduce by
(vegetative) fragmentation, hence
avoiding egg and larva stages.
VIII
NATURAL SELECTION AND
ACCUMATIZATION TO POLLUTION
A Known biological mechanisms for selective
breeding of pollution resistant strains
operate in nature among fishes as among
other organisms.
1
Studies of population genetics indicate
that after some finite number of gen-
erations of population stress (e. g.,
exposure to a given pollutant),
permanent heritable resistance may be
expected to develop.
2 If the environmental stress (or
pollutant) is removed prior to the time
that permanent resistance is developed
in the population, reversion to the
non-resistant condition may occur within
a relatively few generations.
3 Habitats harboring populations under
stress in this manner are often marked
with the dead bodies of the unsuccessful
individuals.
B Individual organisms on the other hand can
over a period of time (less than one life
cycle) develop a limited ability to tolerate
different conditions, e. g., pollutants:
1 With reference to all categories of
pollutants both relatively facultative
and obligate species are encountered
(e. g., euryhaline vs stenohaline,
eurythermal vs stenothermal).
5-8
2 This temporary somatic acclimatization
is not heritable.
C A given single-species collection or
sample of living fishes may therefore
represent one or more types of pollution
re sistance:
1 A sample of an original population
which has been acclimated to a given
stress in toto.
2 A sample of the surviving portion of
an originalpopulation, which has been
"selected" by the ability to endure the
stress. The dead fish in a partial fish
kill are that portion of the original
population unable to endure the stress.
3 A sample of a sub-population of the
original species in question which has
in toto over a period of several
generations developed a heritable
stress resistance.
D Any given multi -speCies field collection
will normally contain species illustrative
of one or more of the conditions outlined
above.
ACKNOWLEDGMENTS:
Certain portions of this outline contain
material from a prior outline by Croswell
Henderson and revisions by R. M. Sinclair.
REFERENCES
I
Cordone, A. J. and Kelley, D. W. The
Influence of Inorganic Sediment on the
Aquatic Life in Streams. Calif. Fish
and Game. 47:189-228. No.2. 1961.
2
Ellis, M. M. Detection and Measurement
of Stream Pollution. Bull. 22, U. S.
Bur. Fish: also, Bull. Burg. Fish 48:
356-437. 1937.
3
Foster, R.F. and Davis, J.J. The
Accumulation of Radioactive Sub-
stances in Aquatic Forms, No. A/Conf.
8/P /280. U. S.A. International Conf.
on Peaceful Uses of Atomic Energy.
pp. 1-7. 1955.
-------
4 Ingram, W.M. and Towne, W.W.
Stream Life Below Industrial Outfalls.
Public Health Reports. 74:1059-1070.
1959.
5 Kurland, Leonard. The Outbreak of a
Neurologic Disorder in Minimata,
Japan, and its Relationship to the
Ingestion of SE;afood Contaminated by
Mercuric CompOl.mds. Proc. Nat.
Shell. Sanit. Workshop. pp. 226-228.
1961.
6 Mackenthun, K. M. and Keup, L. E.
Assessing Temperature Effects with
Biology. Proc. Am. Power Conf.
Vol. 31. pp. 335-343. 1969.
7 Tarzwell, C. M. and Gaufin, R. R. Some
Important Biological Effects of Pollution
Often Disregarded in Stream Surveys.
Purdue Univ. Engr. Bull. Proceedings
8th Ind. Waste Conf. May 4,5, and 6,
1953.
8 Tarzwell, C. M. Hazards of Pesticides
to Fishes and the Aquatic Environment.
The Use and Effects of Pesticides.
Proc. of Symposium, Albany, N. Y.
Sept. 23, 1963. N. Y. State Joint
Legis. Comm. on Nat. Resources,
Albany, N. Y. pp. 30-40.
9 Vinson, S. B., Boyd, C. E. and Ferguson,
D. E. Resistance to DDT in the
Mosquito Fish Gambusia affinis Science.
139:217-218. January 18, 1963.
10 Walshe, Barbara M. On the Function of
. Hemoglobin in Chironomus after Oxygen
Lack. Jour. Exp. Bio!' Cambridge.
124:329-342. 1947.
SUPPLEMENTARY READING
1 Bullock, Glen L. A Schematic Outline for
the Presumptive Identification of
Bacterial Diseases of Fish. Prog. Fish
Cult. 23(4):147-151. 1961.
Effects of Pollution on Aquatic Life
2 Foster, R.F. and Davis, J.J. Aquatic
Life Water Quality Criteria. Second
Progress Report, Aquatic Life
Advisory Committee, Sewage and
Ind. Wastes, 28:678-690. 1956.
3 Fox, H. Munro. Daphnia Hemoglobin.
Nature. London. p. 431.
September 27, 1947.
4 Ingram, W.M. and Wastler, III, T.A.
Estuarine and Marine Pollution.
Selected Studies, U. S. DREW, PHS,
Robt. A. Taft Sanitary Engineering
Center, Cincinnati, Ohio. Technical
Publication No. W6 1-04.
5 Jackson, H. W. and Brungs, Wm. A.
Biomonitoring of Industrial Effluents.
Purdue Industrial Waste Conference,
Layfayette, Indiana. May 3-5, 1966.
6 Rodhe, W. Limnology, Social Welfare,
and Lake Kinneret. Int. Jour.
Limnology, Vol. 17. November 1969.
7 Tennessee Valley Authority, Fish Kill
in Boone Reservoir. TVA Water
Qual. Branch. Chattanooga, Tenn.
1968.
8 Robert A. Taft Sanitary Engineering
Center. Pesticides in Soil and Water.
An annotated Bibliography. PHS
Publication No. 999-WP-17.
September 1964.
9 Stewart, R. Keith, Ingram, William M.
and Mackenthun, Kenneth. Selected
Biological References on Fresh and
Marine Waters. FWPCA Publication
No. WP-23, pp. 126. 1966.
10 Warren, Charles E. Biology and Water
Pollution Control. W. B. Saunders Co.
434 pp. 1971.
This outline was prepared by H. W. Jackson,
Chief Biologist, National Training Center,
EPA, Cincinnati, OH 45226.
5-9
-------
II SURVEY PLANNING
Industrial Waste Surveys
Industrial Liquid Waste Surveys
Statistical Considerations in Survey Planning
Outline Number
6
7
8
-------
INDUSTRIAL WASTE SURVEYS
I
INTRODUCTION
A The industrial waste survey is the project
by which data is collected and the water
pollution control problems generated by a
specific plant. It includes a study of
production processes, the wastes they
generate, the quantities of such wastes
and their effect on the waters which receive
them.
B The survey should be a cooperative venture
of the industrial plant(s) involved and the
public agency having a clean water respon-
sibility. This cooperative approach can
yield a better mutual understanding of the
problems and responsibilities of both
industry and agency.
C Every survey will follow a definite, basic
plan. Modifications to this plan are made
to conform with specific local requirements
and modifying factors of geography,
weather, plant product, receiving water
use and the like.
II
OBJECTIVES
A The industrial waste survey is pesigned to
determine the total pollution load from an
industry and to indicate the source, quantity,
concentration and characteristics of each
major individual waste. Constituent
balances are computed when feasible.
B The industry is afforded an opportunity to
review their waste creating processes.
Process modification or revision to
eliminate or reduce pollution may result.
C Industry can be made more aware of the
problems their wastes create in receiving
waters. Offic1als in the health and
regulatory agencies are exposed to the
problems the industry faces in water
pollution control.
D Defining the problem together, industry and
the control agency can plan for abatement
methods and procedures that are mutually
acceptable.
WP. SUR. 5b. 9. 68
E Industry is given another tool for use in
future planning. This will reduce future
pollution loads.
F The magnitude and complexity of a problem
being defined, the regulatory agency is
furnished data on which to base a reasonable
pollution abatement action, should this
step become necessary.
III
ORGANIZATION OF PROJECT
A Outline program in detail in a letter from
regulatory agency to the company. The
letter should contain the following points:
1 Conduct survey at a time when plant
operations are normal, insofar as this
is possible.
2 Agency to assign professional from its
staff to work with industry technical
staff in organization and conduct of
survey.
3 Analytical work will be performed in
agency laboratory.
4 Industry to install necessary flow
measuring devices.
5 Industry will provide personnel for
collecting samples.
6 Information and data obtained during
the surveys are held confidential.
7 Suggest date for the survey allowing
ample time to organ~ie.the work.
. -.:.~ ..,..',
8 Request confer~nce at plant office for
discussion of the survey.
B Conference with Management
1 Industry and agency should each
designate one man to be their contact
in organizing the program.
6-1
-------
Industrial Waste Surveys
2 Knowledge of the plant and process is a
prime requisite for industry's
representative.
3 Industry's representative should be
acquainted in the company and be
delegated sufficient authority to
expedite the survey.
4 Examination of an up-to-date Plant
Sewer Plan is invaluable and should
be included at this conference.
5 Plant inspection and location of sampling
stations should be made after this
conference.
6 Decide on types of flow measuring
equipment to be installed and preferred
locations.
7 Prepare an over-all estimate of cost of
project to the company, itemized
statement, and report back to manage-
ment for approval and authority to
proceed.
C Henceforth, survey activities proceed under
the supervision of the agency engineer
acting through the company representative.
IV
TECHNICAL STAFF
This is a multiprofessional group requiring
the services of an engineer, a chemist, and
a biologist. Each professional interest is an
important and integral part of the unit.
Competence is essential in the fields of
sanitary, chemical, and hydraulic engineering.
The chemist must be versed in sanitary
chemistry with an aptitude for research.
The role of the biologist required specialized
training in the fields of biology relating to
stream sanitation. The possible role of
each team member may be outlined as follows:
A Engineer
The engineer is responsible for the overall
organization of the work and the specific
duties he may be assigned are:
1 Study of the industrial processes that have
the wastes produced as their byproducts.
6-2
2 Establishment of the hydraulics of the
production system and most particularly
the waste conveying system.
3 Working in conjunction with the chemist
and the biologist establish the sampling
program.
4 Take overall responsibility working in
conjunction with other team members
to analyze data and prepare reports.
B Chemist
The chemist is responsible for the
chemical analytical work and gives
counsel on all matters pertaining to
this phase of the program. Specific
duties include:
1 Collaboration in developing sampling
schedule.
2 Instructions for preservation of samples.
3 Selection of appropriate analytical
procedures.
4 Determination of significance of
interfering substances.
5 Development of new or modified
analytical procedures when necessary.
6 Check all data and confirm or reject
questiOnable results.
7 Aid in analysis of data.
C Biologist
The aquatic biologist evaluates pollutional
materials by determining their effect on
aquatic life. His duties include:
1 Bioassays to:
a Evaluate toxicity of wastes
b Determine required dilution for toxic
substances to render them innocuous
c Test efficacy of treatment processes
-------
2 Determines present and potential future
"health" of receiving water and aid in
establishing degree of necessary pollution
reduction to achieve or maintain proper
water quality.
3 Determines whether or not such pollutants
as excess nutrients, heat, silt and other
industrial wastes of a non-toxic nature
may be detrimental to the receiving
water and its aquatic life.
v
PROCESS STUDY
A Sufficient information must be made available
on process and plant operation, to make
possible correct interpretation of the
analytical data obtained from the survey.
Recognition must be given of the fact that
each manufacturing plant may employ
special operation procedures, developed
by that organization, which may be termed
secret processes. Some of these develop-
ments may be patented whereas others may
be of value without resorting to protection
through patent procedures.
B The agency personnel should be familiar
with various manufacturing processes in
order that the major waste sources will be
recognized. The Stream Control Agency
representative should hold in strict con-
fidence any process or operating information
obtained during the survey when so requested
by the industry.
VI
HYDRA ULIC STUDIES
It is necessary that the volume corresponding
to each sample be determined. Various
methods can be used for measuring flow, the
more common ones being:
A Weirs may be installed in sewer manholes,
at sewer outlets, in channels, and in special
weir boxes. (Estimate flow for design
basis and investigate possible damage
resulting from computed water level rise).
Industrial Waste Surveys
1 Sharp crested, rectangular weirs
2
Q to 3.34 LH 1. 47 (1 + 0.56 H2 )
d
where: Q '" discharge c. f. s.
H '" measured head in feet
d ::: depth of water upstream
from weir in feet
a Correction for end contractions:
1
L '" L - O. 1 NH
where L '" effective length of weir
L 1::: measured length of weir
N '" number of end contractions
2 Right-angled, V -notch
Q = 2.52 H2.47
B Discharge Computed from Size of Sewer,
Slope, and Depth of Flow
1 Measure sewer size
2 Determine slope by use of level
3 Investigate material and condition
C Compute Discharge from Cross Section
Area and Velocity Measurements Made by:
1 Pitot tube
2 Timing of floats
D Critical Depth - Rectangular Section
Q2
g
b2
X d3
c
'"
where
Q ::: c.f. s.
g ::: 32.16 ft. / sec. / sec.
b
II width of channel
d '" critical depth
c
6-3
-------
Industrial Waste Surveys
1 Reference Engineering News-Record
Volume 85, page 1034 (November 25,
1920) "The Hydraulic Jump and Critical
Depth in the Design of Hydraulic
Structures" by Julian Hinds.
E Check total measured discharge against
metered water consumption.
F Miscellaneous considerations in making
such measurements
1 Hazards of working in sewers, and
establishment of safety program.
2 Install flow measuring equipment and
accumulate some data during week
preceding survey.
3 Work up all data daily.
4 Sedimentation back of weirs may clog
sewers and fill weir box with solids.
vn
SAMPUNG PROGRAM
A Collect representative composite samples
over each 24 hour period.
B Sample major individual wastes and check
against outfall.
C Period of sampling may vary between 5
and 14 days. (Obtain sufficient data for
purposes of averaging).
D Interval between sample portions should be
governed by variations in quantity and
quality of discharge but will normally be
not greater than one hour.
E When to weigh samples (proportional to flow).
F Prepare table for weighing samples rather
than curve.
G Employ one sampler per shift.
1 Instruct all samplers at one time;
demonstrate, then observe
H Carry laboratory technique into the
sampling work.
6-4
1 Use of graduates is good psychology.
I
Ice samples during compositing.
J Deliver adequate quantities of daily
samples to laboratory promptly.
K Record unusual occurrences.
VIII
PARAMETERS OF POLLUTION
A The general sanitary criteria frequently
are not well adapted to characterizing
an industrial waste. Pollution parameters
must be worked out for the waste(s) and
the stream involved.
B Decision as to those determinations to be
made should be based on knowledge of the
wastes and uses of the stream below the
point of discharge.
C The determinations should be jointly
agreed on by the industrial representative,
the agency engineer, the chemist who will
perform the analytical work, and the
aquatic biologist doing the receiving water
studies.
D The industry will frequently suggest
special tests and may have proven
analytical procedures.
IX
ANA LYTlCA L WORK
A In the interest of comparing techniques,
"it may prove advantageous to split samples
with the industrial laboratory.
B Samples should be saved until results have
been checked. In case of doubt regarding
a value, the determination should be rerun.
x
REVIEW OF DA TA
A All data, particularly hydraulics data,
should be worked up and reviewed daily.
Computation should be made as rapidly
as laboratory results are available.
-------
Industrial Waste Surveys
B Following completion of the field work and
data analysis, results should be reviewed
with representatives of the industry. This
joint review of the results of the investigation
is advisable even though agency personnel
and plant representatives work closely
throughout the investigation.
XI
PERIOD OF STUDY
A The length of time required to conduct an
industrial waste survey depends on the
magnitude and complexity of the problem,
the wastes produced, the size of the plant,
the present treatment if any, and the
receiving water used for final disposal.
B In the larger plants, it is desirable to make
a separate study of each major department.
The survey in each department should
extend through a minimum of ten operating
days. The time period required must XIV
yield sufficient, accurate data for averaging.
C Irregularities, such as clean-up periods,
should be the object of special study.
Investigational research must pin-point
all significant waste sources.
XII
REPORT
A The final report should include the following
information: describe the plant, process,
and survey project in sufficient detail to
make the work a useful permanent record.
B Tie-in waste data with production.
C Discuss and record the data fully. A full
record of the project must be created for
future use and reference.
D Record and explain unusual occurrences.
E The report should not be considered an
official record until it has been reviewed
and approved by the industry. This is a
courtesy to industry and an invaluable
check on the finished work.
XIII
MISCELLANEOUS CONSIDERATIONS
A Such investigational research may be
expected to serve as basis for develop-
ment of an industrial waste control program.
B Knowledge of the complex nature of the
problem will aid the control agency in
justifying the time required for necessary
research.
C Agency representatives should be briefed
on hazards by the Safety Department the
same as new employees.
D Restricted areas should be clearly defined
prior to initiating the projects.
E Concerted effort should be made to produce
results which will be of maximum value
to both the industry and the agency.
SOURCES OF INFORMA TION
A Technical Journals covering the field of
Sanitary Engineering
B Trade Journals
C Publications of Industrial Associations
D University Engineering Experiment
Sta tion Bulletins
E U. S. Public Health Service, Industrial
Waste Guides
F FWPCA Publications
A CKNOW LEDGMENT
This outline contains certain portions of a
previous outline by Hayse H. Black.
REFERENCES
1
Eldridge, E. F., Industrial Waste Treat-
ment Practice, McGraw-Hill Book Co.
2 Shreve, R. Norris, The Chemical Process
Industires, McGraw-Hill Book Co.
6-5
-------
Industrial Waste Surveys
3 Southgate, B. A., Treatment and Disposal
of Industrial Waste Waters, published
by His Majesty's Stationery Office,
London, England.
4 Besselievre, Edmund B., Industrial Waste
Treatment, McGraw-Hill Book Co.
5 Lipsett, Charles H., Industrial Wastes:
Their Concentration and Utilization,
A tlas Publishing Company.
6-6
6 Nemerow, Nelson L., Theories and
Practices of Industrial Waste
Treatment, Addison-Wesley Publishing
Company, Inc.
This outline was prepared by Robert Roth,
Chief, Manpower Development Branch,
Div. of Air and Water Programs, 1421
Peachtree St., NE, Atlanta, GA 30309
-------
INDUSTRIAL LIQUID WASTE SURVEYS
I
INTRODUCTION
The purpose of industrial liquid waste
surveys is to define the problem and propose
definite alternative solutions to the problem.
A Inspect or consider carefully liquid
processes.
B Determine the liquid waste sources,
quantities and characteristics by
measurement.
C Review liquid waste data and interpret
requirements.
II
ORGANIZA TION
A Industry
B Consultants or consulting engineers
C Municipalities
D State agencies
E Federal Water pollution Control
Administration
III
DEFINITION OF THE PROBLEM
Thc in-plant liquid waste discharges and
their relation to the total combined effluent,
municipal sewer and! or stream
A Process Study
1 Literature review of process
informa tion
2 Information on industry in general and
the plant operations specifically;
i. e., number of production units,
operating day, seasonal variations,
employees
IN. SUR. 3. 11. 66
3 Physical layout of the plant
4 Raw materials, intermediates and
final product list
5 Schematic flow sheet of actual plant
operation
6 Alternative processes used by the
industry
7 By-product or salvage operations
and in-plant housekeeping procedures
8 Liquid flow diagram (from source of
supply to final effluent discharge)
B Parameters of Pollution - Effluent
Criteria
1 Literature review of water quality
criteria
2 Regulatory agencies - Federal and
State
3 Municipal sewer ordinances
4 Independent studies
C Plant and Stream Hydraulic Studies
1 Literature review of applicable
hydraulics
2 Definition by means of a hydraulic
flow diagram
3 Actual measurement of flows
D Analytical Work - Chemist and Biologist
1 Literature review of pertinent methods
2 Determining analytical requirements
3 Planning the analytical schedule
7-1
-------
Industrial Liquid Waste Surveys
E Sampling Program
2) Protection in the field
1
Literature review of sampling methods,
handling procedures, and preservation
3) Multiple bottles dictated by
analytical requirements
2 Collection considerations
4) Shipment and containers
a Manual sampling
5) Storage limitations
1) Volume required for analysis
6) Bottle recommendations
2) Grabs
d Sample preservation
3) Composites, interval
1) Refrigeration
4) Sampling proportional to flow
(weighted)
2) Chemical treatment
e
Miscellaneous sampling problems
and pitfalls
5) Sample at point of homogeneity
6) Precautions with wastes con-
taining settleable solids, oil,
or volatile materials
1) Industrial plants
a) Submerged outfalls
7) Equipment and its care
b) Deep manholes
8) Recording observations
c) Steam-filled sewers
b Automatic sampling
d) Coated sewers and
sedimentation
1) Commercial units
a) Types and description
e) Toxic or explosive liquids
or vapors
b) Installation and calibration
f) Solvents
c) Maintenance
2) Stream or estuary
d) Limitations
a) Floating material
e) Advantages and disadvantages
b) Access to ideal cross section
f) Cost
F Review of Data - Waste Water
Characteristics
2) Improvised units
The in-plant, effluent and stream balance
3) Instrumentation
1 Statistical design of the program
c Handling of samples
a Anticipated uses of data
1) Identification tags
b Minimum period for survey
7-2
-------
Industrial Liquid Waste Survey
c Minimum number of samples
d Minimum number of determinations
2 Correlation of effluent data with plant
operations
a Raw materials
b Finished products
c Intermediate products
d By-products or salvaged materials
e Production, yield
f
Processes employed
g Water use, reuse and recycle
3 Evaluation of Data
a Flow balance - usually pounds
b Material balance - also in pounds
c Statistical analysis
1) Distribution
2) Levels of significance
3) Errors
4) Frequency
5) Confidence limits
6) Means
7) Deviation
8) Probability
N EXPLORING THE SOLUTIONS TO THE
PROBLEM
A Research
1 Literature review of treatment methods
2 In-plant or effluent treatability studies
a Effect of variations in flow rates on
treatment plant hydraulics and pro-
cess performance
b Effect of variation in liquid waste
quality on process performance
c Need for equalization capacity for
either flow or quality reasons
d Possibility for waste water segre-
gation and separate treatment
systems
e In-plant controls, treatment or
process change versus terminal
treatment
B Process Engineering
1 Sizing facilities
2 Cost estimating
v
REPORT
A Preliminary Engineers Report
B Summary Report
7-3
-------
Industrial Liquid ~?ste Survey
FIGURE 1,
SIMPLIFIED FLOW DIAGRAM-CUCUMBER PICKLING
Rough
Sorting
Packing Solution
Water
Initial Salt
Addi tional Salt
Possible
.-.-..
Brine Loss
I
Brine
Recycle
Water
Initial Salt
Additional Salt
Brine Disposal ~.I
at Field Station
Rinse
Washing
Water
Sorting
o
Brine Spillage
.-.-.-.-.-.-.-.-..
Brine From Storage Yards
Recycle
Salt Water
Spices
Sugar
Vinegar
Sweetening, Souring,
or Dilling
o
.-.-._._..Wash Water
~ Spent Freshening Water
--.-.-.-.-.-.-.-.
. - . .. Rinse Water
. -.. Clean-up Water
Liquid to Product
Container
Rinse
Alum
Tumeric
Rinse Water
. -. -. _.~ Cutting Rinse Water
. .Overflow & Drag Out
Rinse Water
Detergent
._.-0wash Water
Feed Waters .
Liquid Effluents -....
7-4
-------
Industrial Liquid Waste Survey
FIGURE 2.
SCHEMATIC DISCHARGE DIAGRAM
Drainage
Ditch
Relish
Plant
Cucumber
Storage
Yards
C li Water f8\
00 ng \V
0@
Vinegar
Plant
Ib/day
Processing
Plant
Effluent
Yard Drainage---+
3-5 gpm (Continuous) =
7,200 gpd = 0.06 x 106 Ib/day
"
~
./
./
Future Municipal J!'./
Sewage Discharge ./
I /
I Proposed By-Pass
-.......... Sewer
30,000 gpd
= .25 x 106
= 21 gpm
37.5 gpm =
18,000 gpd =
0.15 x 106 Ib/day
Rinse @
Salt Stock
Washing
(2)
15 gpm
8 hr/day =
7,200 gpd =
0.06 x 106
Ib/day
Rinse Water
I
Water
Freshening
Spent 0
Freshening
Water
18,000 gpd =
0.15 x 106 Ib/day
27.5 gpm
Pickle
Cutting
Proposed Treatment
FaciH ty
Creek
Estimated 20 cfs Average Flow = 12.93 mgd =
107.87 x 106 Ib/day
o
30 gpm
8 hr/day =
14,400 gpd =
0.12 x 106
Ib/day
Rinse Water
Glass Jar
Washing
New Dam,
10.6 Miles2
Drainage
Area
7-5
-------
Industrial Liquid Waste Survey
Procedures for Determining pollutional Characteristics of Foundry Wastes
Precision of Recorded Results
Result Reported Significant Figures Example of
Characteristic to Nearest - (Not more Than) Reported Result
Flow
Temperature 0c one two 22
Dissolved oxygen tenth two 6.9
pH tenth two 9.1
A lkalini ty one three 117
Acidity one three 76
Turbidity one two 270
Total solid one three 173
Total volatile solids one three 122
Color five two 45
Total suspended solids one three 110
Volatile suspended solids one three 101
Sulfate one three 21
Total oil and grease one two 72
Soluble oil one two 22
5-day biochemical oxygen demand one two 280
Chemical oxygen demand one three 324
Chemical oxygen demand one three 324
Ammonia nitrogen tenth two O. 6
Nitrate nitrogen tenth two O. 7
Organic nitrogen tenth two 1.3
Total phosphate hundredth two 0.84
Phenol hundredth two 0.16
Cyanide
Copper hundredth two 0.21
Lead hundredth two 0.58
Cadmium hundredth two 0.74
Zinc hundredth two 0.62
Nickel hundredth two O. 79
Chromium hundredth two 0.52
Manganese hundredth two O. 71
Soluble iron hundredth two 0.41
Aluminum tenth two 1.1
Boron hundredth two . 18
Magnesium one two 2
Lithium tenth two 1.2
7-6
-------
Table 6
Procedures for Determining pollutional Characteristics of Foundry \Vastes
Sample
Container Sample Volume Sa mple Storage
Characteristic Number Type of Sampling Container Rec'd I\1in. Sample Preservation Limitation Reference* Notes
Flow Four steps for the
Temperature °c 1 pg 311 preservation of all
Dissolved oxygen IV pg 504 sampling containers:
pH Plastic 1 gallon None Within 8 hrs. I pg 225 1. Dichromate acid
rinse.
Alkalinity 1 IV pg 438 2. Tap water rinse.
Acidity IV pg 438 3. Distilled water
Turbidity I pg 312 rinse.
Total solids III pg 423 4. Allowed to dry.
Total volatile solids III pg 423
Color Within 48 hrs. IV pg 443 Sample containers
Total suspended solids 1 III pg 424 for metals should
Volatile suspended solids m pg 425 be finally rinsed in
Sulfa te I pg 287 1: 1 HN03'
Total oil and grease 2 Widemouthed glass-stoppered 1 guart Acidified and stored in Within 24 hrs. III pg 383 Flow. temperature,
and dissolved
bottle refrigerator oxygen measured
Soluble oil 3 Widemouthed glass-stoppered 1 guart Acidified and stored in Within 24 hrs. API"'''' 733- 58 during time of
bottle refrigera tor collection.
5-day biochemical oxygen 4 Plastic 1 gallon Immediate storage 00 ice Within 4 hrs. III pg 415 Explanation of arrows:
demand 1 1 A1d preserved; 3. 5 ml 1 The quantity of
Chemical oxygen demand 4 IV pg 510 sample desig-
Chemical oxygen demand 4A Within 5 days IV pg 510 nated is suffi-
conc. H2S04 per gallon cient to do all
of sample tests as grouped
Ammonia nitrogen 5 Plastic 1 gallon Acid preserved; 3. 5 ml Within 14 days III pg 389 and covered by
j 1 conc. H2S04 per gallon 1 pointing arrow.
of sample
Nitrate nitrogen 5 1 III pg 393
Organic nitrogen 5 ill pg 402 The an,alytical para-
Total phosphate 5 I pg 230 meters suggested
are for guidance
Phenol 6 Plastic 1 gallon Acid preserved; adjust Within 24 hrs. IV pg 514 purposes only and
pH to 4 with H3P04; add the intent is oot to
3. 8 gms. CuS04 per gal. say that all of these
measurements must
Cyanide Plastic 1 gallon NaOH to pH 11 store in Within 14 days IV pg 448 be made. In many S'
cool place instances certain of 0..
these parameters will ~
rn
not apply and thus the <+
Copper '1
8 Plastic 1 gallon Acid preserved with 19 Within 30 days IV pg 479 determina tion may ....
j j ml conc. HN03 per gal- j be eliminated. The $!:I
......
Ion of sample waste engineer must r<
Lead 8 1 IV pg 485 use his own judg- ....
Cadmium 8 IV pg 470 ment in this respect ,D
~
Zinc 8 IV pg 494 and plan his survey ....
Nickel 8 IV pg 492 accordingly. 0..
Chromium 8 IV pg 474 ~
Manganese 8 IV pg 489 $!:I
rn
Soluble iron 8A Glass - screw cap <+
50 to 100 ml Fixed with I, 10 Within 5 days IV pg 482 ro
phenanthroline en
-J ~
Aluminum 9 Plastic 1 ]llon '1
I None Within 7 days I pg 57 <;
-J Boron 9 1 1 1 I pg 60 ro
Magnesium 9 I pg 168 '<
Lithium 9 I pg 166
*Standard Methods for the Examination of Water and Waste Water, 12th edition, 1965. Courtesy of James L. Holdaway
"''''American Petroleum Institute, 1957. Chemist, TA & I Activities, FWPCA
-------
Industrial Liquid Waste Survey
Pollutional
Load
Pounds
Per
Day
CONCENTRATION OF POLLUTIONAL LOAD FOR VARIOUS FLOWS
2, 000
600
10.000
9,000
8.000
7.000
6,000
5.000
4. 000
3.000
100
1
2
3
4
5 6 7 8 9 10
20
Flow - cfs
7~8
-------
:>-. (j)
r-
~ 100
::s 90
en
<
<
o
p::
f;I:1
p.. 10
Cl.I 9
o 8
~ 7
o
p.. 6
~
o 5
Cl.I
~
~
~
~
~
::s
4
3
FLOW CONVERSION CHART
2
I
40 50 60 70 8090100
1
.1
I I I
.4 .5.6.7 .8.9 1 2 3 4 5 6 7 8 9 10
STREAM OR EFFLUENT DISCHARGE-UNITS OF FLOW
30
I
20
. 2
.3
-------
Industrial Liquid Waste Surveys
REFERENCES
Weston, Roy F., Merman, Robert G.,
and DeMann, Joseph G. The Indus-
trial Plant Waste Disposal Survey.
Sewage Works Journal, vol. XXI, No.
2, March 1949.
2 Planning and Making Industrial Waste
Surveys, Metal-Finishing Industry
A ction Committee of the Ohio River
Valley Water Sanitation Commission,
April 1952.
7-10
3 Kittrell, F. W. A Water Pollution
Survey. Eighth Industrial Waste
Conference, Oklahoma State Uni-
versity, Stillwater, Oklahoma,
September 25, 1957.
4 Rudolfs, Willem, Industrial Wastes -
Their Disposal and Treatment,
Reinhold Publishing Corporation, 497 pp.
1953.
5 Nemerow, N. L. Theories and Practices
of Industrial Waste Trf'atment, Addi-
son-Wesley Publishing Company, Inc.
557 pp. 1963.
This outline was prepared by Thomas J.
Powers, Director, Water Quality Standard
Branch, Federal Building, Cincinnati, OR 45202.
-------
STATISTICAL CONSIDERATIONS IN SURVEY PLANNING
I
NEED FOR ADVANCE PLANNING
A Sample must be representative of the
population from which it was drawn.
B The size of the sample should not be
larger than is necessary to give statis-
tically valid results. It is uneconomical
otherwise.
C The user of the sample must specify in
advance the confidence level and the
confidence interval that will be acceptable
to him.
D Types of Samples
1
Census (100o/c sample). Obviously not
applicable here. One cannot analyze
all the water in a stream, lake, or bay.
2 Random Sample. All the drops of water
in the population have the same chance
of being drawn in the sample. You can
divide the surface area of the body of
water into equal sub-areas, number
each one, and then draw numbers
randomly (out of a hat, or by reference
to a table of random numbers). This is
a good method if the water is homogen-
eous in regard to the characteristic in
which we are interested.
3 ,Stratified Sample. If our body of water
is known to be heterogeneous (coliform
count varies with depth, for instance),
the population can be divided into strata,
or layers, and random samples drawn
from each stratum. This method cannot
be used unless some information about
the body of water and its strata is
available. Clearly, the strata must be
related to the characteristic being
studied, and there should be homogeneity
within each stratum. For a non-
homogeneous population, a properly
stratified sample may be expected to
yield more reliable results than a
random sample of the same size. Of
course, a stratified. sample taken from
a homogeneous body of water is no more
reliable than a random sample of equal
size.
4 There are other types of samples, but
random and stratified samples are the
ones most commonly used in water
studies.
ST. 27. 2. 71
II
METHOD OF DETERMINING SAMPLE
SIZE
A Assume that the confidence coefficient
is set at 95 percent and the confidence
interval:i: 1 unit.
B A sample taken from a body of water is
usually so small compared to the total
amount of water present that we may
regard the reciprocal of the population
size as practically zero.
C Some indication of the standard deviation
of the population must be obtained, either
from past experience or from a pilot study.
III
COMPUT A TIONS
A Sample size for finite populations can
be calculated by the formula:
2
(J"x
h2 ~2
-+ vx
Z2 rr
n =
where n2 =
~
Z
sample size
the population variance
standard normal deviate
h
half-width of the confidence
interval
size of population
N
B Assume we have estimated (J to be
about 3.2. We have set h at x:i: 1, N is
so large that CT is practically zero, and
Z (from a tabllof areas under a normal
curve) is found to be 1. 96 for a 95o/c
confidence coefficient.
C Substituting these values in our formula,
we find
(3.2)2
n =
(:i:l)2 + (3.2)2
(1. 96)2 N
(3'. 2)2
(where N is taken as zero)
Sample size is 40.
8-1
-------
Statistical Considerations in Survey Planning
IV
EVALUATION OF PRECISION OBTAINED
A Suppose that a simple random sample of
40 was selected and the following results
obtained:
Mean of the sample X = 17.10
Standard deviation Sx = 3.60
B The standard deviation of the sample mean,
Sx - 3. 6 - 0 57
Sse = Jtt - ::pro - .
C Then, the confidence interval will be
X:l:Z s- or 17.10:1: 1.96 (.57) which is
x
17.10:1: 1. 12 or between 15.98 and 18.22
at the 950/c confidence level.
v
COMMENTS
A Our confidence interval is a bit larger
than was specified in advance. This is due
to the fact that we underestimated the
variance of the population.
B If we made a larger estimate of the variance,
our confidence interval would have been
narrower but the sample would have been
larger.
8~2
C Specifying a higher coefficient of confidence
will also increase the required sample size,
other things being equal.
D The result of underestimating the popu-
lation variance will be that the confidence
interval will be wider than the desired one.
It will not, however, affect the validity
of the confidence interval for evaluating
the precision of the estimate actually
obtained. .
This outline was prepared by Henry P.
Shotwell, North Atlantic Water Quality
Management Center, EPA, OWP, Edison, NJ.
-------
III ANALYTICAL PROCEDURES
Acidity, Alkalinity, pH and Buffers
Laboratory Procedure for Total Alkalinity
Laboratory Procedure for Total Acidity
The Specific Conductance Measurement
Specific Conductivity Laboratory
Chemical Oxygen Demand and COD/BOD
Relationships
Solids Relations in Polluted Water
Determination of Suspended Solids
Laboratory Procedure for Total Solids
Laboratory Procedure for Non Filterable
(Suspended) Solids
Laboratory Procedure for Filterable
(Dissolved) Solids
Laboratory Procedure for Volatile Solids
Bioassay and Biomonitoring
Special Applications and Procedures for
Bioassay
The Use of Bio-Assays: Case Histories
Outline Number
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
-------
ACIDITY, ALKALINITY, pH AND BUFFERS
I
DEFINITIONS OF ACIDS AND BASES
A
Arrhenius Theory of Acids and Bases
(Developed about 1887)
1
Acid: A substance which produces,
in aqueous solution, a hydrogen ion
(proton), W.
2
Base: A substance which produces,
in aqueous solution, a hydroxide
ion, OH-.
3
The Arrhenius theory was confined
to the use of water as a solvent.
B
Bronsted and Lowry Theory of Acids
and Bases (Developed about 1923)
1
Acid: A substance which donates,
in chemical reaction, a hydrogen
ion (proton).
2
Base: A substance which accepts,
in chemical reaction, a hydrogen
ion (proton).
3
Bronsted and Lowry had expanded
the acid-base concept into non-
aqueous media; i. e., the solvent
could, but did not have to be ,water.
C
Further development of acid-base theory
dealing with electron p air donation or
acceptance is unimportant.
II
DEFINITIONS OF ACIDITY,
ALKALINITY AND NEUTRALITY
A
Acidity
A condition in which there is a prepon-
derance of acid materials present in
the water.
B
Alkalinity.
A condition in which there is a prepon-
derance of alkaline (or basic) materials
present in the water.
CH, ALK. 3.12. 71
C
Neutrality
1
It is possible to have present in
the water chemically equivalent
amounts of acids and bases. The
water would then be described as
being neutral; i. e., there is a
preponderance of neither acid nor
basic materials. The occurrence
of such a condition would be rare.
2
The term "neutralization" refers to
the combining of chemically equiv-
alent amounts of acids and bases.
The two products of neutralization
are a salt and water.
HCI + NaOH = NaCl + H20
Hydro- Sodium Sodium
chloric Hydroxide Chloride
acid (a salt)
D
The key word in the above definitions
is "preponderance. II It is possible to
have a condition of acidity while there
are basic materials present in the
water, as well as conversely.
III
HOW A RE DEGREES OF ACIDITY AND
ALKALINITY EXPRESSED?
The pH scale is used to express various
degrees of acidity and alkalinity. Values
can range from Oto 14. These two ex-
tremes are of theoretical interest and would
never be encountered in a natural water or
in a waste water. pH readings from 0 to
just under 7 indicate an acidic condition;
from just over 7 to 14, an alkaline condition.
Neutrality exists if the pH value is exactly
7. pH paper, or a pH meter, provides the
most convenient method of obtaining pH
readings. Some common liquids and their
pH values are listed in Table 1.
9-1
-------
Acidity, Alkalinity, pH and Buffers
~-_..-
TABLE 1. pH Values of Common Liquids
Household lye 13.7
Bleach 12.7
Ammonia 11. 3
Milk of magnesia 10.2
Borax 9.2
Baking soda 8.3
Sea 'water 8. 0
Blood 7.3
Distilled water 7.0
Milk 6. 8
Corn 6.2
Boric acid 5.0
Orange juice 4.2
Vinegar 2.8
Lemon juice 2. 2
Battery acid 0.2
5.9 - 8.4 is the common pH range for most
natural waters.
IV
HARD AND SOFT WATERS
In addition to being acidic or basic, water
can also be described as being hard or soft.
A
Hard water contains large amounts of
calcium, magnesium, strontium, man-
ganese and iron ions, relative to the
amount of sodium and potassium ions
present. Hard water is objectionable
because it forms insoluble compounds
with ordinary soap.
B
Soft water contains small amounts of
calcium, magnesium, strontium, man-
ganese and iron ions, relative to the
amount of sodium and potassium ions
present. Soft water does not form in-
soluble compounds with ordinary soap.
V
TITRA TIONS
A
The conversion of pH readings into such
quantities as milligrams (mg) of acidity,
alkalinity, or hardness, is not easily
carried out. These values are more
easily obtained by means of a titration.
B
In a titration, an accurately measured
volume of sample (of unknown strength)
is combined with an accurately measured
9-2
volume of standard solution (of known
strength) in the presence of a suitable
indicator.
C
The strength (called normality) of the
sample is then found using the following
expression:
milliliters (ml) of sample X normality
(N) of sample = ml of standard solu-:
tion X N of standard solution.
Three of the four quantities are known,
and
N of sample = ml of standard solution
X N of standard solution/ml of sample.
D
In modified form, and a more specific
application of the above equation, alka-
linity is calculated in the following
manner (12th ed. Standard Methods).
mg of alkalinity as mg CaC03 / liter (1)
= ml of standard H2S04 X N of standard
H2S04 X 50 X 1000/ml sample.
VI
INDICATORS
The term "suitable indicator" was use d
above. At the end of a titration, the pH of
the solution will not necessarily be 7. It
may be above or below 7. A suitable indi-
cator, therefore, is one which undergoes
its characteristic color change at the appro-
priate pH. Below are a few examples of
indicators and the pH range in which they
undergo their characteristic color changes.
In some case,>. mixed indicators may be
used in order to obtain a sharper and more
definite color change.
Indicator
Operational
pH Range
2.8 - 4.0
3.1- 4.4
4.4 - 6.2
7.4 - 9.0
8.0- 9.6
10.0-12.0
Methyl Yellow
Methyl Orange
Methyl Red
Cresol Purple
Phenolphthalein
Alizarine Yellow
TABLE 2.
pH Range of Indicators
-------
VII
BUFFERS
A
A buffer is a combination of substances
which, when dissolved in water, resists
a pH change in the water, as might be
caused by the addition of acid or alkali.
Listed below are a few chemicals
which, when combined in the proper
proportions, will tend to maintain the
pH in the indicated range.
Chemicals
AceticAcid + SodiumAcetate
pH Range
3.7 -
5.6
Sodium Dihydrogen Phosphate +
Disodium Hydrogen Phosphate
Boric Acid + Borax
5.8 -
6.8 -
8.0
9.2
Borax + Sodium Hydroxide
9.2-11.0
TABLE 3. oH Ran!1"e of Buffers
B
A buffer functions by supplying ions
which will react with hydrogen ions
(acid "spill"), or with hydroxide ions
(alkali "spill").
C
In many instances, the buffer is composed
of a weak acid and a salt of the weak acid;
e.g., acetic acid and sodium acetate.
In water, acetic acid ionizes or
"breaks down" into hydrogen ions
and acetate ions.
HC2H302 = H+ + C2H302-
(acetic acid) (hydroR:en ion) (acetate ion)
(prOton)
1
2
This ionization occurs to only a
slight extent, however, mostof the
acetic acid remains in the form of
HC2H302; only a small amount of
hydrogen and aceta te ions is formed.
Thus, acetic acid is said to be a
weak acid.
In the case of other acids, ionization
into the component ions occurs to a
large degree, and the term strong acid
is applied; e.g., hydrochloric acid.
= H+ + Cl-
(hydrogen ion) (chloride
(proton) ion)
3
HCl
(hydrochloric
acid)
Acidity, Alkalinity, pH and Buffers
The terms "strong" and "weak" are
also applied to bases. In water
solutions, those which break down
into their component ions to alar ge
extent are termed "strong", and
those which do not are "weak".
Sodium hydroxide is a relatively
strong base, while ammonium
hydroxide is realtively weak.
Sodium acetate (a salt of acetic acid)
dissociates or "breaks down" into
sodium ions and acetate ions when
placed in water.
NaC2H302 = Na + + C2H302-
(sodium acetate) (sodium ion) (acetate ion)
4
5
This dissociation occurs to a large
extent, and practically all of the
sodium acetate is in the form of
sodium ions and acetate ions.
D
It would be difficult and expensive to
prepare large quantities of buffers for
use in a treatment plant. However,
certain naturally occurring buffers may
be available (carbon dioxide is an ex-
ample). It dissolves in water to form
the species indicated below.
C02 + H20 = H2C03
(carbon dioxide) (Water) (carbonic acid)
H2 C03 H+ + HC03 -
(hydrogen ion) (hydrogen car-
(proton) bonate ion)
(bicarbonate)
The hydrogen ions react with hydroxide
ions which might appear in the water
as the result of an alkali "spill".
H+
(in the
buffer)
OH-
(hydroxide ion
"spilled")
+
H20
The hydrogen carbonate ions react with
hydrogen ions which might appear in
the water as the result of an acid "spill".
W + HC03-
(hydrogen ion) (in the
(proton) buffer)
"spilled"
H2C03
This buffering action will be in effect as
long as there is carbonic acid present.
9-3
-------
Acidity, Alkalinity, pH and Buffers
E
Buffering action is not identical with
a process in which acid wastes are
"neutralized" with alkali wastes, or
conversely. The desired effect is
achieved in both cases, however (i. e. ,
the pH is maintained within a desired
range. )
9-4
This outline was prepared by C... R.' Feldmann,
Chemist, National Training Center, MDS,
WPO, EPA, Cincinnati,OH 45268
-------
LABORATORY PROCEDURE FOR TOTAL ALKAUNITY
I
METHOD SUMMARY
(1)
A In the current methods manual of the
Environmental Protection Agency, the
following method is specified for use in
Office of Water Programs laboratories.
The sample is titrated with O. 02N
hydrochloric or sulfuric acid to a final
pH of 4. 5, the end point being determined
electrometrically.
1 The sample must not be filtered,
diluted, concentrated or altered in
any way.
2 Results are reported as mgCaCOg/liter.
g The procedure can be found in Standard
Methods(2) and ASTM Book of Standards.(g)
B The procedure as given in the above
references has been adapted for this
laboratory session to accommodate group
participation and to accomplish in-
structional objectiv:e~.
II
DISCUSSION
In this manual, outline 8 considers the
relationships among the g forms of alkalinity
commonly found in water. Refer to the
graphs in outline 8 for the following:
For Case 1, (OH)- alkalinity only, pH
values change very gradually until the
approach of pH 9. Then an aprupt change
occurs and the addition of a few ml of
titrant causes the value to change rapidly
to about pH 4.
For Case 2, (COg)- alkalinity only, there
is a gradual change of pH values as the
acid titrant is added. Around pH 9 there
is an abrupt change of the scale reading.
Around pH 6, the change is again gradual.
Around pH 5, another rapid change occurs
until pH g is reached.
A pH- of 8. g represents the average pH when
(OH) has been totally neutralized and
CH. ALK.lab. 4.12.71
(CO) - has been half neutralized to
(HCOgf. A pH of 4.5 represents t,!1e
average pH occurring when (HCOg) has
been neutralized to C02 and H20.
(See Case g).
In order to obtain standardized data, the
EP A method specifies stopping alkalinity
tit rations at n.H 4.5. At this pH, any
(OH)-, (COg)- and (HCOg)- in the sample
will be neutralized. Since all three of
these alkalinity forms may be present,
the results are expressed as total
alkalinity. -
It is useful to express total alkalinity as
mg CaCOg/liter.
In INSTRUCTIONAL OBJECTIVES
A You will use the adapted EPA method to
determine total alkalinity by titrating g
solutions of known alkalinities and one
unknown to an end point of pH 4.5. You
will then use the data to calculate the
total alkalinity for each as mg CaCOg/liter.
1 By slowly adding the HCl titrant to
soluti0I!s of (OH) -, of (COg) - and of
(HCOg) and observing the pH scale,
the cfiaracterizing response of each.
alkalinity at different pH values can
be observed.
2 Recording the volume of HCl used to
reach pH 8. g and then pH 4.5 will
also illustrate the pH characteristics
of the three forms of alkalinity.
g Calculating the total alkalinity of these
three solutions will familiarize you
with the calculations for the determination.
B You will also do titrations on the same
solutions using color indicators - --
phenolphthalein (colorless at pH 8) and
methyl orange (amber-orange at pH 4.6)
- - - in order to contrast values obtained
by the pH determination.
10-1
-------
C
Using experience gained in the lab
session, you will estimate the types of
alkalinity present in the unknown sample.
IV REAGENTS
A Carbon Dioxide- Free Distilled Water
B Anhydrous Sodium Carbonate (primary
standard)
C Hy,drochloric Acid Titrant (0. 02~)
D Phenolphthalein
E Methyl Orange
V STANDARDIZATION of the HYDROCHLORIC
ACID TITRANT . I
A Set the temperature reading on the pH
meter dial to match the temperature of
the buffer and sample solutions.
B Standardize the pH meter against a
reference buffer solution.
C Weigh accurately 0.088 + 0.001 g of the
dried sodium carbonate and transfer it
to a 500 ml conical flask.
D Add 50 ml of water and swirl to dissolve
the carbonate.
E While stirring the solution, add the
hydrochloric acid titrant from a 100 ml
buret until a pH of 4. 5 is attained.
F Calculate the normality of the hydrochloric
acid solution as follows:
A= B
0.053XC
A = normality of the hydrochloric acid
B = g of sodium carbonate used
C = ml of hydrochloric acid consumed
0.053 = millequivalent weight of Na2 C03
10-2
Laboratory Procedure for Total Alkalinity
VI TITRATIONS to pH END POINTS
For each of the solutions marked Case 1-
(OH)-, Case 2 (C03)- and Case 3 (HC03)
and for the assignea unknown, A or B,
the following procedure is to be followed.
All data and the calculation results should
be recorded on the Data Table provided.
A Calibrating the pH meter
1 Pour about 50 ml of the buffer solution
into a small beaker.
2 Set the temperature reading on the pH
meter dial to match the temperature
of the reference buffer.
3 Immerse the electrode(s) into the
buffer solution.
4 Turn the meter to ION"(or "Read"
or IpH"). .
5 Using the "Balance" (or "Asymm")
knob, set the scale reading to 6. 84.
6 Turn the meter to "Off" (or II Hold II
or II Standby").
7 Re~ove electrode(s) from buffer and
save this solution for possible later
use.
8 Rinse electrode(s) with distilled
water, then immerse them in a small
beaker of distilled water until time
to use.
B Prepare the buret by rinsing 3 times using
about 15 ml HCI each time. Then fill the
buret with HCI and adjust the volume so
that the top of the liquid column is positiofte'd.
. for a reading.
C Titration Procedure:
1 Each titration will require up to 25 rrll
O. 02N HCl titrant. Refill the buret as
needed before beginning each titration.
2 Pipet 50.0 ml of the solution to be used
into a beaker. .
-------
Laboratory Procedure for Total Alkalinity
3
Remove the pH electrode(s) from the
beaker of distilled water and immerse
electrode(s) in the solution to be
titrated. The sample solution should
cover the glass bulb(s).
4
" N" ( "R d"
Turn pH meter to 0 or ea
or "pH").
5
On the Data Table, record the ml of
HCl in the buret at the start of the
titration.
6
Record the initial pH of the sample
on the Data Table.
7
While gently swirling either the
electrode or the sample in the beaker,
slowly add the HCl titrant, observing
the scale on the pH meter. Stop
adding titrant when pH is about 8.3
and record the buret reading. (This
step is not part of the EP A procedure.
It is included here for instructional
purposes).
Again gently swirling either the
electrode or the beaker, continue
slow addition of the HCl titrant, ob-
~ing the meter scale. Be very
cautious when the scale approaches
ph 5. O. Stop titrating at pH 4.5. If
a lower pH is inadvertently reached,
note this on the Data Table.
8
9
On the Data Table, record the ml HCl
remaining in the buret.
10
" " ( "H Id"
Set pH meter to OFF or 0
or "Standby">.
11
Rinse the pH electrode(s) with dis-
tilled water and immerse in the beaker
of distilled water.
12
Empty the sample solution and rinse
the beaker with distilled water.
13
U sing the next solution, repeat this
procedure (C, steps 1 through 12)
until data has been recorded for the
3 knowns and the 1 unknown sample.
Then proceed to part VII.
DATA TABLE
. TITRATIONS TO pH END POINTS.
, . .. . 0... ...
CASE 1 CASE..? CASE 3 SAMP LE
(OH) (C03)- (HC03f-
Initial pH
m1@pH 4.5
ml@pH 8.3
m1@Start
TOTAL
m1. HCl
TOTAL
ALKALINITY
(mg CaC03
I liter)
VII
TITRA TIONS to. COLOR END POINTS
If time permits, the following procedure
should be used to titrate the 3 solutions
of known constituents and the assigned
unknown, A or B. At least, do one of
the known solutions and the unknown
used for the pH titration. All data and
the calculation results should be recorded
on the Data Table provided.
A
Indicators Used
1 Phenolphthalein indicator is a deep
pink around pH 10 and becomes
colorless at pH 8. In the Data Table,
this colorless end point is designated
as P. End Pt.
B
2 Methyl orange indicator gives a yellow
color to a colorless solution. At
pH 4.6 (referred to as M. O. End Pt.
on Data Table) it becomes amber-
orange. This end point color requires
practice to detect. If the solution
acquires a pinkish cast, you are past
the desired end point.
Tit~ation Procedure
1 Each titration will require up to 25 m1
0.02N HC1 titrant. (If pH determinations
have-been done, refer to these results
for approximations of HCL titrant to
be used). Refill the buret as needed
before beginning each titratio:!1.
10-3
-------
Laboratory Procedure for Total Alkalinity
2 Pipet 50. 0 ml of the solution to be used
into a beaker.
3 Place a piece of white paper under
the beaker.
4 Add 3 drops phenolphthalein indicator
to the sample and swirl to mix.
5 On the Data Table record the ml of
HCI in the buret at the start of the
titration.
6 Using the known re1ationship of the
color of phenolphthalein to different
pH values, record your estimate of
the initial pH of the sample on the Data
Table.
7 If the solution remains colorless,
record 0.0 for P. End Pt. and continue
with step 9.
If there is pink color in the solution,
slowly add HCI titrant while stirring
the sample.
A5 the end point is approached, a
lingering colorless region where the
titrant first contacts the sample will
be observed. Add the titrant very
cautiously at this time, stirring the
sample solution and allowing time for
total mixing and contact before adding
more HCI titrant.
The end point occurs when the entire
solution is colorless. Stop adding
the HCI titrant.
8 Record the ml of HCI in the buret for
the P. End Pt. on the Data Table.
9 Add 3 drops of methyl orange indicator
to the same sample solution.
10 .If the sample solution becomes amber-
orange, record 0.0 for M. O. End Pt.
and continue at step 12.
If the solution becomes yellow, slowly
add HCI titrant while stirring the
sample.
10-4
As the 'end point is approached, a
a lingering amber- orange region where
the titrant first contacts the sample
will be observed. Add the titrant very
cautiously at this time, stirring the
sample solution and allowing time for
total mixing and contact before adding
more HCI titrant.
The end point occurs when the entire
solution is amber orange. Stop adding
the HCI titrant. (If the solution develops
a pinkish cast, you are past the desired
end point and should note this on the
Data Table).
11
Record the ml of HCI in the buret for
the M. O. End Pt. on the Data Table.
12
Empty the sample solution and rinse
the 'beaker with distilled water.
13
Choose the next solution according to
time available and repeat this procedure
(B, steps 1 thru 12).
DATA TABLE
TlTRA TIONS TO COLOR END POINTS
.
:::AS~ 1 CASE 2 CASE 3 AMPLE
(OH) (C03)= (HC03) -
-
initial pH
(Estimate)
ml. @ M.O.
End Pt.
ml. @ P.
End Pt.
ml. @ Start
TOTAL
ml. HCI
TOTAL
ALKALINITY I
,
(mg CaC03
/ liter)
-------
VIII CALCULATIONS:
A
Calculate Total Alkalinity for each
solution titrated, using the following:
mg CaC03/1 = A x N X 50,000
ml. of sample
A = total m1 of standard acid required
for titration to pH 4. 5 end point
N = normality of standard acid
50 = equivalent weight of CaC03
1000 eonverts m1 to liters
B
Record calculation results on the
Data Tables.
Laboratory Procedure for Total Alkalinity
REFERENCES
1
Methods for Chemical Analysis of
Water and Wastes, EPA-AQCL,
Cincinnati, OH 45268, (1971)
2
Standard Methods for the Examination
of Water and Wastewater, 13th edition,
APHA-AWWA-WPCF, Method 102 (1971)
3
ASTM Book of Standards. Part 23,
p. 154 (1970)
This outline was prepared by A. Donahue,
Chemist, National Training Center, DTTB,
MDS, WPO, EPA, Cincinnati, OH 45268.
10-5
-------
LABORATORY PROCEDURE FOR TOTAL ACIDITY
I
REAGENTS
For detailed discussion of reagent preparation,
consult reference 2.
I
A Carbon Dioxide - Free Distilled Water
B Potassium Hydrogen Phthalate
(pri.inary. standard). .
C Sodium Hydroxide Titrant (0. 02 N)
II
STANDARDIZATION OF THE SODIUM
HYDROXIDE TITRANT
A Set the temperature reading on the pH
meter dial to match the temperature of
the buffer and sample solutions.
B Standardize the pH meter against a
reference buffer solution.
C Weigh accurately 0.19 ! 0.005 g of the
dried potassium hydrogen phthalate and
transfer it to a 500 ml conical flask.
D Add 100 ml of reagent water and swirl
gently to dissolve the phthalate.
E While stirring the solution(magnetic bar
and stirrer), add the sodium hydroxide
from a 100 ml buret until a pH of 8.3 is
attained.
F Calculate the normality of the sodium
hydroxide solution as follows:
B
A = 0.20423XC
A = normality of the sodium hydroxide
B = g of potassium hydrogen phthalate
C = ml of sodium hydroxide solution
0.20423 =
milliequivalent weight of
potassium hydrogen phthalate
(KHC8H40 4)
CH.ALK.lab. 3b. 12.71
III
PROCEDURE
A Pipet 100 ml of the sample into a 400 ml
beaker.
B Titrate with the sodium hydroxide to
pH 8.3
C Calculation
Total acidity as mg of CaC03/l =
A X N X 50000
.ml of sample
A = ml of standard NaOH titrant
N = N of standard NaOH titrant
50 = equivalentweight of CaC03
1000 - converts ml to liters
REFERENCES
1 Methods for Chemical Analysis of
Water & Wastes, EPA-AQCL, 1971,
Cincinnati, OH 45268.
2 A. S. T. M. Book of Standards, Part 23,
D 1067-70, pp. 155-158.
This outline was prepared by Charles R.
~eldmann, Chemist,. Na tional Training
, Center, WPO, MDS, Dl'TB, EP A,
. Cincinnati, OH 45268.
11-1
-------
THE SPECIFIC CONDUCTANCE MEASUREMENT
I
INTRODUCTION
An electrical conductivity measurement of a
solution determines the ability of the solution
to conduct an electrical current. Very
concentrated solutions have a large population
of ions and transmit current easily or with
small resistance. Since resistance is 1
inversely related to conductivity K = R'
a very concentrated solution has a very
high electrical conductivity.
Electrical conductivity is determined by
transmitting an electrical current through
a given solution, using two electrodes. The
resistance measured is dependent principally
upon the ionic concentration, ionic charge,
and temperature of the solution although
electrode characteristics (surface area and
spacing of electrodes) is also critical. Early
experiments in standardizing the measurement
led to construction of a "standard cell" in
which the electrodes were spaced exactly 1 cm
and each had a surface area of 1 cm2. Using
this cell, electrical conductivity is expressed
as "Specific Conductance". Modern specific
conductance cells do not have the same
electrode dimensions as the early standard
cell but ha ve a characteristic electrode spacing/
area ratio known as the "cell constant".
1 distance (cm)
Ksp = R X area (cm2) ,
K
sp
1
'" - X k
R
k = cell constant
Specific conductance units are Mhos/ cm or
reciprocal ohms/ cm. Most natural, fresh
waters in the United States have specific
conductances ranging from 10 to 1, 0.9J>
micromhos/ cm. (1 micromho = 10 mho).
II
CONDUCTIVITY INSTRUMENTS
Nearly all of the commercial specific con-
ductance instruments are of a bridge circuit
design, similar to a Wheatstone Bridge.
Null or balance is detected either by meter
movement, electron "ray eye" tubes, or
headphones. Since resistance is directly
related to temperature, some instruments
have automatic temperature compensators,
although inexpensive models generally have
manual temperature compensation.
Conductivity instruments offer direct specific
conductance readout when used with a cell
"matched" to that particular instrument.
Electrodes within the cell may become
damaged or dirty and accuracy may be
affected; therefore, it is advisable to
frequently check the instrument readings
with a standard KCl solution having a known
specific conductance.
III
CONDUCTIVITY CELLS
Several types of conductivity cells are
available, each having general applications.
Dip cells are generally used for field
measurement, flow cells for measurement
within a closed system, and pipet cells for
laboratory use. Many modifications of the
above types are available for specialized
laboratory applications; the Jones cells and
inductive capacitance cells are perhaps the
most common.
Examples of various cell ranges for the RB3
- Industrial Instruments model (0-50
micromhos/cm scale range) are in Table 1.
Cell
Number
Cell VS02
Ce 11 VS2
Cell VS20
Relative
Conductivity
Value
1
10
100
Maximum range
micromhos / cm
- 0 - 50
o - 500
o - 5000
Table 1
Most accurate range
micromhos/ cm
--~- 30
20 - 300
200 - 3000
CI-I. CONDo 2c. 12.71
12-1
-------
The Specific Conductance Measurement
IV Computation of Calibration Constant
A calibration constant is a factor to which
scale readings must be multiplied to com-
pute specific conductance.
K = cM
sp
where K = actual specific conductance
sp
c
= calibration constant
M
= meter reading
For example, a 0.001 N KCl solution
(147 micromhos/ cm standard) may show
a scale reading of 147.
147
147 = c 147, c = ill = 1. 00
In this case the cell is perfectly "matched"
to the instrument, the calibration constant
is 1.00, and the scale reading represents
actual specific conductance. A variety of
cells, each covering a specific range,
may be used with anyone instrument.
However, a calibration constant for each
cell must be computed before solutions of
unknown specific conductance can be
determined.
V
RELATIONSHIP OF SPECIFIC CON-
DUCTANCE TO IONIC CON CENTRA TION
Natural water consists of many chemical
constituents, each of which may differ
widely in ionic size, mobility, and solubility.
Also, total constituent concentration and
proportions of certain ions in various natural
waters range considerably. However, it
is surprising that for most natural waters
having less than 2,000 mg/I. dissolved'
solids, specific conductance values are
closely related to dissolved solids values,
ranging in a ratio of .62 to .70. Of course
this does not hold true for certain waters
having considerable amounts of nonionized
soluble materials, such as organic com-
pounds and nonionized, colloidal inorganics.
12-2
Properties of some inorganic ions in regard
to electrical conductivity are shown below:
Micromhos/ cm
per meq/l conc.
Ion
Calcium
Magnesium
Sodium
Potassium
Bicarbonate
Carbonate
Chloride
52.0
46.6
48.9
72.0
43.6
84.6
75.9
VI ESTIMATION OF CONSTITUENT
CON CENTRA TIONS
Generally speaking, for waters having a
dissolved solids concentration of less than
1,000 mg/l, calcium and magnesium (total
hardness), sodium, bicarbonate and
carbonate (total alkalinity), and sulfate are
the principal or most abundant ions,
representing perhaps 90-990/0 of the total
ionic concentration of the water. Specific
conductance, total hardness and total
alkalinity are all simple and expedient
measurements which can be performed in
the field. Therefore, the remaining principal
ions are sodium and sulfate, and concentrations
of these can be estimated by empirical
methods. For example, we find that a certain
water has:
Ksp :: 500micromhos/ cm
Total Hardness" 160 mg/l or 3.20 meq/l
Total Alkalinity = 200 mg/l or 3.28 meq/l,
as bicarbonate.
Next we multiply the specific conductance by
*0.011 (500 X 0.011 :: 5.50) to estimate the
total ionic concentration in meq/I.
':' This factor may vary slightly for
different waters
Cations (meq/l)
Anions (meq/l)
Calcium
Magnesium
Sodium 5.50-3.20 " 2.30
Total Cations 5.50 .
Carbonate 0.00
Bicarbonate 3.28
Sulfate 5.50-3.28 :: 2.22
Total Anions 5.50
3.20
-------
Hecdizing that several variables are involved
in empirical analysis, application rests
entirely upon testing the formula with previous
com!Jlde laboratory analyses for that
particular water. If correlation is within
acceptable limits, analytical costs may be
suhstantially reduced. Empirical analysis
can also be used in determination of proper
a:iquots (dilution factor) necessary for
labora tory analysis.
Records of laboratory chemical analysis may
indicate that a particular stream or lake
shows a characteristic response to various
streamflow rates or lake water levels. If
the water's environment has not been altered
and water composition responds solely to
natural causes, a specific conductivity
measurement may be occasionally used in
substitution for laboratory analyses to
determine water quality. Concentration of
individual constituents can thus be estimated
from a specific conductance value.
VII APPliCATIONS FOR SPECIFIC
CONDUCT ANCE MEASUREMENTS
Laboratory Operations (2)
A
1
Checking purity of distilled and de-
ionized water
2
Estimation of dilution factors for
samples
3 Quality control check on analytical
accuracy
4 An electrical indicator
B
Agriculture
1
Evaluating salinity
C
2 Estimating Sodium Adsorption Ratio
Industry (3)
1 Estimating corrosiveness of water in
steam boilers
2 Efficiency check of boiler operation
The Specific Conductance Measurement
D Geology
1 Stratigraphic identification and
characterization
a
b
geological mapping
oil explorations
E Oceanography
1 Mapping ocean currents
2 Estuary studies
F Hydrology
1
Locating new water supplies
a
b
buried stream channels (See Fig. 1)
springs in lakes and
streams (See Fig. 2)
2 Detection and regulation of sea water
encroachment on shore wells
G Water Quality Studies
1 Estimation of dissolved solids
(See Section V, also reference 2)
2
Empirical analysis of constituent
concentrations (See Section VI, also
reference 2)
3
Quality control check for salt water
conversion studies
4 Determination of mixing efficiency
of streams (See Fig. 3)
5 Determination of flow pattern of
polluted currents (See Fig. 3)
6 Identification of significant fluctuations
in industrial wastewater effluents
7
Signal of significant changes in the
composition of influents to waste
treatment plants
12-3
-------
The Specific Conductance Measurement
FIGURE 1
DETECTION OF BURIED SlffiIEAM CHANNIELS
TEST WELLS
X-SECT
FIGURE 2
DETECTION OF SPRINGS IN LAKES AND STREAMS
MAN LOWERING
CONDUCTIVITY CELL ~
lAND SURFACE
LAKE OR RIVER
12-4
-------
The Specific Conductance Measurement
FIGURE 3
POllUTION STUDIfS
FAaORY
S,.E"'~
INDUSTRIAL
WASTE EFFLUENT
VIII
EPA METHODOLOGY
The standard deviation of the reported
values was 7.55, 8.14, 66.1, 79.6, 106
and 119J..1 mhos/cm respectively.
A
(1)
The current EP A Methods Manual
specifies that specific conductance be
measured with a self-contained con-
ductivity meter, Wheatstone bridge-
type or equivalent.
The accuracy of the reported values was
-2.0, -0.8, -29.3, -38.5, -87.9 and
-86.9 J..I mhos/ cm bias respectively.
Samples should preferably be analyzed
at 25°C. If not, temperature corrections
should be made and results reported
at 250C.
REFERENCES
1 Methods for Chemical Analysis of Water
and Wastes, EPA-AQCL, Cincinnati,
OH 45268. 1971.
1 The instrument shQuld be standard-
ized using KC1 solutions
2 Standard Methods for the Examination
of Water and Wastewater, APHA-AWWA-
WPCF, 13th edition, 1971.
2 It is essential to keep the conductivity
cell clean
3 ASTM Standards, Part 23, 1970.
B
The EP A manual specifies using the
procedure as described in Standard
Methods(2) or in ASTM Standards(3).
P .. d A (1)
reC1Slon an ccuracy
C
Forty-one analysts in 17 laboratories
analyzed 6 synthetic water samples
containing the following K"sp increments
of inorganic salts: 100, 106, 808, 848,
1640 and 1710 micromhos/ cm.
This outline was prepared by John R.
Tilstra, Chemist, National Eutrophication
Research Program, Corvallis. Oregon
with additions by Audrey E. Donahue, Chemist,
DTTB, MDS, OWP, EP A, Cincinnati,
OH 45268.
12-5
-------
SPECIFIC CONDUCTIVITY LABORATORY
I
EQUIPMENT AND REAGENTS
A Equipment
1 Solu Bridge conductivity meters
2 Probes
a Cell VS02
b Cell VS2
c Cell VS20
3
Thermometers
4 400 ml beakers
B Reagents
1 Standard KC1 solutions
Normality of
KC 1 Solution
Specific Conductance
micromhos / cm.
0.0001
0.001
0.01
0.1
14.9
147.0
1413.0
12900.0
2
Distilled water
II
CHECKING THE INSTRUMENT
A The measurement of specific conductivity
as presented in sections II and III is written
for one type of conductivity meter and probe.
B A battery check is made by depressing the
Battery Check switch, and at the same
time pressing the on-off button. The
meter needle should deflect to the right
(positive) and come to rest in the green
zone.
C Place a 10, 000 ohm resistor in the hc;>les
of the electrical contacts on the meter.
Turn the temperature knob to read room
temperature. Depress the on-off button
and bring the meter needle to a reading
CH. COND.lab. 3b. 12.71
of 0 by turning the specific conductance
switch. The specific conductance reading
should be approximately 200 micromhos/ cm.
III
DETERMINATION OF THE
CALIBRATION CONSTANT
A
Move the temperature switch so that
its reading is the same as the
temperature of the standard KCl and
sample solutions.
B
Connect probe 'Cp.ll VS02 to the con-
ductivity meter.
C
Rinse the probe in the beaker of
distilled water, wipe the excess water
with a kimwipe and place probe in the
first beaker of KCl solution (0.0001 N).
D
Make certain the cell is submerged to
a point at least 1/2 inch above the air
hole and that no entrapped air remains.
The cell should also be at least 1/2
inch from the inside walls of the flask.
E
Press and hold down the ON-OFF
button, simultaneously rotating the main
scale knob until the meter reads zero.
Release the button. (If the meter needle
remains off scale or cannot be nulled,
discontinue testing in that solution.)
F
Record the scale reading in Table 1 and
proceed to KC1 solutions O. 001N,
0.01N, 0.1 N.
G
Repeat steps C through F using the VS2
and VS20 probes.
H
Compute the cell calibration constant-a
factor by which scale readings must be
multiplied to compute specific conductance:
K =cM
sp
where K = actual specific conductance,
c = calib~tion constant
M= meter reading
(continued next page)
13-1
-------
Specific Conductivity Laboratory
TABLE 1
DATA FOR CALIBRATION CONSTANTS
I -------
Probe Cell VS02 Cell VS2 Cell VS20
KCI I
Solution O.OOOIN O.OOIN O.OlN O. IN O.OOOIN O.OOlN O.OIN O.IN O.OOOIN O.OOlN O.OlN O.lN
Test #
1
2
3
Cell
Cons tan
See I B Reagents for the actual specific
conductance values of the KC1 solutions used
for the probes.
Record the computed cell constants on Table 1.
IV DETERMINATION OF THE SPECIFIC
CONDU~TANCES OF THE SAMPLES
Determine the K values of samples
A, B and C usinl¥he procedure as
described in Section III, steps C through
F. Record data in Table 2.
V EP A METHODOLOGY
The current EPA Manual(1)specifies using
the procedures found in References 2 and
3. These procedures have been adapted
for this laboratory session.
TABLE 2.
ACKNOWLEDGMENT
This outline contains certain portions of
previous outlines by Messrs. J. W. Mandia,
and J. R. Tilstra. .
REFERENCES
1
Methods for Chemical Analysis of
Water and Wastes, EPA-AQCL,
Cincinnati, OH 45268, 1971.
2
Standard Methods for the Examination
of Water and Wastewater, 13th
Edition. 1971.
3
Book of ASTM Standards, Part 23, 1970.
This outline was prepared by C. R. Feldmann,
Chemist, National Training Center, and re-
vised by Audrey E. Donahue, Chemist,
National Training Center, DTTB, MDS,
OWP, EPA, Cincinnati, OH 45268.
SPECIFIC CONDUCTIVITY TESTS
Sample A B C
Probe Cell Cell Cell Cell Ce1l' Celli Cell Cell Cell
VS02 VS2 VS:!O VS02 VS2 VS20 \Tc;:n? VS2 VS20
1
2
3 J
rm
onstant
Sp. Condo
>!mhosl em
13-2
-------
CHEMICAL OXYGEN DEMAND AND COD/BOD RELATIONSHIPS
I
DEFINITION
A The Chemical Oxygen Demand (COD) is
an estimate of the proportion of the sample
matter susceptible to oxidation by a .
strong chemical oxidant. The current I
edition of Standard Methods, (2) specifies.
organic material which is generally the
situation but not necessarily applicable.
B A variety of terms have been and are used
for the test described here as COD:
1 Oxygen absorbed (OA) primarily in
British practice.
2 Oxygen consumed (OC) preferred by
some, but unpopular.
3 Chemical oxygen demand (COD) current
preference.
4 Complete oxygen demand (COD)
misnomer.
5 Dichromate oxygen demand (DOC)
earlier distinction of the current pre-
ference for COD by dichromate or a
specified analysis such as Standard
Methods.
6 Others have been and are being used.
Since 1960, terms have been generally
agreed upon within most professional
groups as indicated in I-A and B-3 and
the explanation in B- 5.
C The concept of the COD is almost as old
as the BOD. Many oxidants and varia-
tions in procedure have been proposed,
but none have been completely
satisfactory.
1
Ceric sulfate has been investigated,
but in general it is not a strong
oxidant.
CH.O. oc. 10e.12. 71
2 Potassium permanganate was one of
the earliest oxidants proposed and
until recently appeared in Standard
Methods (9th ed. ) as a standard pro-
cedure. It is currently used in
British practice as a 4-hr. test at
room temperature.
a The results obtained with perman-
ganate were dependent upon concen-
tration of reagent, time of oxidation,
temperature, etc., so that results
were not reproducible.
3 Potassium iodate or iodic acid is an
excellent oxidant but methods employing
this reaction are time-consuming and
require a very close control.
4 A number of investigators have used
potassium dichromate under a variety
of conditions. The method proposed
by Moore at SEC is the basis of the
standard procedure. (I, 2) Statistical
comparison~)with other methods are
described. \;:1
5 Effective determination of elemental
carbon in wastewater was sought by
Busw!,!ll as a water quality criteria.
Van Slyke(4) described a carbon
determination based on anhydrous
samples and mixed oxidizing agents
including sulfuric, chromic, iodic
and phosphoric acids to obtain a
yield comparable to the theoretical
on a wide spectrum of components.
a
b Van Hall, et al., (5) used a heated
combustion tube with infrared
detection to determine carbon quickly
and effectively by wet sample
injection.
6 Current development shows a trend to
instrumental methods autom""Ung
14-1
-------
Chemical Oxygen Demand and COD/BOD Relationships
'-
conventional procedures or to seek
elemental or more specific group
determination.
II
RELATIONSHIP OF THE COD TEST WITH
OTHER OXIDATION CRITERIA IS
INDICA TED IN TABLE 1.
A Table 1
Test Test Reaction Oxida tion Variables
Temp. °c time system
BOD 20 days BioI. prod. Compound, environ-
Enz. Oxidn. ment, biota, time,
numbers. Metabolic
acceptability, etc.
COD 145 2 hrs. 500/0 H2S04 Susceptibility of
K2Cr207 the test sample to
May be cata- the specified
lyzed oxidation
mOD 20 15' Diss. oxyg. Includes materials
rapidly oxidized by
dir-fzt action,
Fe , SH.
Van Slyke 400+ 1 hr. H 3PO 4 Excellent approach
Carbon detn. Hl03 to theoretical oxi-
H2S04 dation for most
K2Cr207 compolinds (N -nil)
Anhydrous
. Carbon by 950 minutes Oxygen atm.. Comparable to
combustion catalyzed theoretical for
+IR carbon only.
Chlorine 20 20 mL'1. HOCI soln. Good NH; 3 oxidn.
Demand Variable for other
compounds..
~
B From Table 1 it is apparent that oxidation
is the only common item of this series of
separate tests.
a given sample to oxidation under.
specified conditions that are different
for each test.
1 Any relationships among COD & BOD
or any other tests are fortuitous be-
cause the conditions of test tend to give
results indicating the susceptibility of
2 If the sample is primarily composed
of compounds that are oxidized by
both procedures (BOD and COD) a
relationship may be established.
14~2
-------
Chemical Oxygen Demand and COD /BOD Relationships
a The COD procedure may be sub-
stituted (with proper qualifications)
for BOD or the COD may be used
as an indication of the dilution
required for setting up BOD
analysis.
b If the sample is characterized by a
predominance of material that can
be chemically. but not biochemi-
cally oxidized. the COD will be
greater than the BOD. Textile
wastes. paper mill wastes. and
other wastes containing high con-
centrations of cellulose have a
high COD. low BOD.
c If the situation in item b is reversed
the BOD will be higher than the
COD. Distillery wastes or refinery
wastes may have a high BOD. low
COD. unless catalyzed by silver
sulfate.
d Any relationship established as in
2a will change in response to
sample history and environment.
The BOD tends to decrease more
rapidly than the COD. Biological
cell mass or detritus produced by
biological action has a low BOD
but a relatively high COD. The
COD/BOD ratio tends to increase
with time. treatment. or conditions
favoring stabilization.
n
ADV ANT AGES AND LIMITATIONS OF
THE COD TEST(2) AS RELATED TO BOD
A Advantages
1 Time. manipulation. and equipment
costs are lower for the COD test.
2 COD oxidation conditions are effective
for a wider spectrum of chemical
compounds.
3 COD test conditions can be standardized
more readily to give more precise
results.
4 COD results are available while the
waste is in the plant. not several
days later. hence. plant control is
facilitated.
5 COD results are useful to indicate
downstream damage potential in the
form of sludge deposition.
6 The COD result plus the oxygen equiva-
lent for ammonia and organic nitrogen
is a good estimate of the ultimate BOD
for many municipal wastewaters.
B Limitations
1
Results are not applicable for estimating
BOD except as a result of experimental
evidence by both methods on a given
sample type.
2 Certain compounds are not susceptible
to oxidation under COD conditions or
are too volatile to remain in the oxida-
tion flask long enough to be oxidized.
Ammonia. aromatic hydrocarbons,
saturated hydrocarbons. pyridine. and
toluene are examples of materials with
a low analytical response in the COD
test.
3 Dichromate in hot 50% sulfuric acid
requires close control to maintain
safety during manipulation.
4 Oxidation of chloride to chlorine is not
closely related to BOD but may affect
COD results.
5 It is not advisable to expect precise
COD results on saline water.
IV
BACKGROUND OF THE STANDARD
METHODS COD PROCEDURE
A The COD procedure (1) considered dichro-
mate oxidation in 33 and 50 percent sul-
furic acid. Results indicated preference
of the 50 percent acid concentration for
oxidation of sample components. This is
the basis for the present standard
procedure.
14-3
-------
Chemical Oxygen Demand and COD/BOD Relationships
B Muers(6) suggested addition of silver
sulfate to catalyze oxidation of certain
low molecular weight aliphatic acids and
alcohols. The catalyst also improves
oxidation of most other organic components
to some extent but does not make the COD
test universally applicable for all chemical
pollutants.
C The unmodified COD test result (A) includes
oxidation of chloride to chlorine. Each mg
of chloride will have a COD equivalent of
0.23 mg. Chlorides must be determined
in the sample and the COD result corrected
accordingly.
1 For example, if a sample shows 300
mg of COD per liter and 200 mg Cl-
per liter the .corrected COD result will
be 300 -(200'x 0.23)01' 300 - 46 = 254
mg COD/l'oo'-a chloride corrected basis.
2 Silver sulfate addition as a catalyst
tends to cause partial precipitation of
silver chloride even in the hot acid. solu-
tion. Chloride corrections are ques-
tionable unless the chloride is oxidized
before addition of silver sulfate, 1. e.,
reflux for 15 minutes for chloride ox-
. idation, add Ag SO , and continue the
reflux or use of2Hg~04(D).
D Dobbs and Williams (7) proposed prior
complexation of chlorides with HgS04 to
prevent chloride oxidati~ during the test.
A ratio of about 10 of Hg + to 1 of Cl- (wt.
basis) appears essential. The Cl- must
be complexed in acid solution before addi-
tion of dichromate and silver sulfate.
1 F or unexplained reasons the HgSO 4
complexation does not completely
prevent chloride oxidation in the
presence of high chloride concentrations.
2 Factors have been developed to provide
some estimate of error in the result
due to incomplete control of chloride
behavior. These tend to vary with the
sample and technique employed.
E It is not likely that COD results will be
precise for samples containing high
chlorides. Sea water contains 18000 to
21000 mgCl- /1 normally. Equivalent
chloride correction for COD exceeds
14-4
4000 mg/l. The error in chloride
determination may give negative COD
results upon application of the correction.
Incomplete control of chloride oxidation
with HgS04 may give equally confusing
results.
HgS04 appears to give precise results
for COD when chlorides do not exceed
about 2000 mg/l. Interference in-
creases with increasing chlorides at
higher levels.
F 'l'he 12th edition of Standard Methods re-
duced the amount of sample and reagents
to 400/c of amounts utilized in previous
editions. There has been no change in
the relative proportions in the test. This
step was taken to reduce the cost of pro-
viding expensive mercury and silver sul-
fates required. Results are comparable
as long as the proportions are identical.
Smaller aliquots of sample and r.eagents
req Ilire more care during manipulation
to promote precision.
G The EP A Methods for COD
1 For routine level COD (samples having
an organic carbon concentration
greater than 15 mg/liter and a chloride
concentration less than 2000 mg/liter),
the EP A specifies the .J?rocedures found
in Standard Methods (~}and in ASTM(B).
2 For low level COD (samples with less
than 15 mg/liter organic carbon and
chloride concentration less than 2000
mg/ liter), EP A provides an analytical
procedure (9). The difference from
the routine procedure primarily in-
volves a greater sample volume and
more dilute solutions of dichromate
and ferrous ammonium sulfate.
3 For saline samples (chloride level
exceeds 1000 mg/liter and COD is
greater than 250 mg/liter), EPA
provides an analytical procedure(9)
involving preparation of a standard
curve of COD versus mg/ liter
chloride to correct the calculations.
Volumes and concentrations for the
sample and reagents are adjusted for
this type of determination.
-------
Chemical Oxygen Demand and CODI BOD Relationships
V The precision of the unmodified COD
result shows a standard deviation of + 4% of the
mean (3) on low chloride samples. Silver
sulfate modified COD results are likely to
show a standard deviation about twice that
without catalysis, due to questionable
chloride behavior. The determination of
chloride fre~uently shows a coefficient of
variation (s/ x) of 10 to 150/c, hence high
chloride samples resu~t in COD precision
controlled more by chloride behavior than
organic oxidation.
VI
REMARKS PERTINENT TO EFFECTIVE
COD DETERMINATIONS INCLUDE:
A Sample size and COD limits for 0.25 N
reagents are approximately as given.
For 0.025 N reagents multiply COD by
0.1. Use the weak reagents for COD's
in the range of 5-50 mgll, (low level).
Sample Size
mg COD II
2000
4000
8000
20 ml
10 ml
5 ml
B Most organic materials oxidize relatively
rapidly under COD test conditions. A
significant fraction of oxidation occurs
during the heating upon addition of acid.
The color change of dichromate after
acid addition indicates the approximate
fraction of dichromate remaining. If
the mixed sample color changes from
yellow to green after acid addition the
sample was too large. Discard without
reflux and repeat with a smaller
aliquot until the color after mixing does
not go beyond a brownish hue. The
dichromate color change is less rapid
with sample components that are slowly
oxidized under COD reaction conditions.
C Chloride concentrations should be known
for all test samples and results inter-
preted accordingly.
D Special precautions advisable for the
regular COD procedure and essential
when using O. 025 N reagents include:
1 Keep the apparatus assembled when
not in use.
2 Plug the condenser breather tube with
glass wool to minimize dust entrance.
3 Wipe the upper part of the flask and
lower part of the condenser with a
wet towel before disassembly to
minimize sample contamination.
4
Steam O'.lt the condenser after use for
high concentration samples and periodi-
cally for regular samples. Use the
regular blank reagent mix and heat,
without use of condenser water, to
clean the apparatus of residual oxidiz-
able components.
5
Distilled water and sulfuric acid must
be of very high quality to maintain low
blanks on the refluxed samples for the
0.025 N oxidant.
ACKNOWLEDGEMENT:
Certain portions of this outline contain
training material from prior outlines by
R. C. Kroner, R. J. Lishka, and J. W. Mandia.
REFERENCES:
1 Moore, W. A., Kroner, R. C. and Ruchhoft,
C. C. Anal. Chern. 21:953 1949.
2 Standard Methods, 13th Edition, APHA-
AWWA-WPCF, 1971.
3 Moore, W.A., Ludzack, F.J. and
Ruchhoft, C. C. Anal. Chern. 23:1297,
1951.
4 Van Slyke, D. D. and Folch, J. J. BioI.
Chern. 136:509 1940.
5 Van Hall, C. E., Safranko, J. and Stenger,
V. A., Anal. Chern. 35:315 1963.
6 Muers, M. M. J. Soc. Chern. Ind. (London)
55:711 1936.
7 Dobbs, R. A. and Williams, R. T., Anal.
Chern. 35:1064 1963
8 ASTM Standards, Part 23, Water:
Atmospheric Analysis, 1970.
9 Methods for Chemical Analysis of
Water and Wastes, EPA-AQCL,
Cincinnati, OH, July 1971.
See Next Page.
14-5
-------
Chemical Oxygen Demand and COD/BOD Relationships
This outline was prepared by F. J.Ludzack,
Chemist, National Training Center, MDS,
, EP A, Cincinnati, OR 45268.
14-6
-------
SOLIDS RELATIONS IN POLLUTED WATER
I MPN, oxygen demand, and solids have
been major water pollution control crHeria
for many years. This discussion is con-
cerned primarily with solids and their inter-
relations with oxygen demand.
A Engineered treatment or surface water
self-purification depends upon:
1
The conversion of soluble or colloidal
contaminants into agglomerated masses
that may be separated from the water.
2 Oxidation of putrescible components
into stable degradation products.
3 Item 1 is the major concern in most
treatment systems because item 2
requires a greater investment in time,
manpower and capital costs.
B Stress on oxygen demand removal frequently
results in an unduely small amount of
attention to the contribution of solids in
the oxygen demand picture.
1
Oxygen demand formulations generally
are specified to be applicable in the
absence of significant deposition.
2 . Increasing impoundment, tidal estu-
aries, and incomplete solids removal,
generally ensure that solids deposition
will be significant.
3 The BOD test stresses the fraction of
oxygen demand that is exerted relatively
rapidly. It includes only the fraction
of unstable material that is exerted
under test conditions - usually short
term.
4 Contributions of a bed load of solids to
oxygen demand frequently are incom-
pletely recognized because they have a
more local effect, are difficult to meas-
ure, tend to move, and are incompletely
understood.
PC. 6a. 9. 72
II A given wastewater may have several
forms of solids in changeable proportions
with time and conditions.
A Solids may be classified among the charted
forms according to biological, chemical
or physical properties. It is not possible
to precisely classify a given material into
anyone form because they usually are
mixtures that may include or be converted
into other forms.
B Interrelationships are indicated by diagram
in Figure 1. Some changes occur more
readily than others.
1
Settleable solids generally consist of
a mixture of organic, inorganic, en-
trained dissolved or colloidal solids
with living and dead organisms.
a They may be hydrolyzed into smaller
molecules to acquire colloidal or
dissolved characteristics.
b They may be converted into a larger
fraction of living material or vice
versa.
2 Colloidal solids also are likely to be a
mixture of organic and inorganic
materials, living or dead containing
associated dissolved materials.
a They are likely to agglomerate to
form settleable masses with time
or changing conditions.
b Chemical reactions may solubilize
the colloidal masses for recombina-
tion into other forms.
3 Dissolved solids are most readily avail-
able of all forms for biological, chemi-
cal or physical conversion.
15-~l
-------
Solids Relations in Polluted Water
=
o
..-4 =
~o
cu ..-4
1-1 U)
Q) 1-1
'" Q)
00-
r-iu)
..-4
"0
cu
Dissolved
Settleable
Cell Mass
.c:
~
CU iJ
Q) 0
"01-1
be
Colloidal
Dead Organic
Inorganic
Figure 1.
SOLIDS INTERRELA TIONSHIPI3 IN WATER
a They may be assimilated into cell
maSs to become colloidal during a
state of rapid growth or form settle-
able masses during slow growth.
Surface phenomena are likely to en-
courage inclusion of other forms of
solids with cell mass.
a Products consist of cell mass and
degradation products.
C Stabilization occurs with each conversion
because energy is expended with each
change.
b Oxidation tends toward production
of C02' H20, N03' S04-2etc. C02
has limited water solubility and
partially leaves the aqueous environ-
ment. More soluble constituents
tend to remain with it for recycle.
1
Biological changes involve oxidation to
obtain enough energy to synthesize cells.
c Biological residues tend to recycle.
Eventually the mass consists of
relatively inert and largely insolu-
ble residues. These make up the
15-2
-------
Solids Relations in Polluted Water
bed load that may decompose at a
rate of less than 1 % per day, but
accumulates in mass until it be-
comes dominant in water pollution
control activities.
III Treatment is an engineered operation
designed to utilize events in surface water
self-purification in a smaller package in
terms of space and time. Effective treat-
ment presupposes oxidation either in the
plant or in facilities to minimize feedback
of solids components to the aqueous
environment.
A Primary treatment consists of a separation
of floatable or settleable solids and re-
moval from the used water.
1
Prompt removal is essential to minimize
return of solubilized or leached materi-
als from the sludge mass.
2
Sludge and scum are highly putrescible
and difficult to drain.
3
Subsequent treatment prior to disposal
serves to enhance drainability, reduce
solids or volume for burial or burning.
B Secondary treatment generally involves
some form of aerobic biological activity
to oxidize part of the colloidal and dis-
solved contaminants and convert most of
the remainder into a settleable sludge.
1
Aerobic systems favor assimilation of
nutrients into cell mass at the expense
of part of the available energy repre-
sented by oxidation to products such as
C02 and water.
2
Cell mass and intermediate degradation
products are only partially stabilized
and tend to recycle with death and decay.
3
Rapid growth of cells tends to produce
sludges that are highly hydrated and
thin.
4 A compromise must be reached to pro-
duce a favorable balance among separa-
tion of solids and feedback of lysed
materials.
a Cell growth continues as long as
essential nutrients are available.
b Under limiting nutrient conditions
the population may show a relatively
low rate overall dieoff but variety
is changing.
c
Species most favored by the new con-
ditions tend to grow while others
die, lyse and release part of their
stored nutrients for subsequent use.
C Anaerobic digestion of solids separated
during treatment is one process used to
increase solids stability and drainability
while reducing total volume or mass for
disposal.
1
Growth of cell mass is relatively slow
under anaerobic conditions while hy-
drolytic cleavage is relatively large
in comparison to that during aerobic
metabolism.
a Feedback to the aqueous envirol}II1ent
represents a significant fraction of
the input in the form of ammonia,
colloidal solids, low molecular
weight acids, and other products.
b
Mass of the sludge is reduced by the
fraction of methane, carbon dioxide,
and other gases produced in process.
Q
c Remaining solids tend to be more
concentrated, are lower in putresci-
bility and give up their water more
readily.
1
2
The liquid fraction of the products re-
maining after anaerobic digestion con-
tain nutrients, oxygen demand, solids,
and malodorous constituents that are
objectionable in surface waters if re-
leased without further aerobic
stabilization.
3
Digester liquids are much more con-
centrated than raw sewage and nutrition-
ally unfavorable, hence they are difficult
to treat and tend to shock aerobic
treatment processes.
15-3
-------
Solids Relations in Polluted Water
D Suitable disposal of solids resulting from
treatment operations takes various forms
of which the most desirable is to oxidize
it completely to gaseous products of oxida-
tion or inert ash. The objective is to limit
feedback into the aqueous environment and
delay the charted interchanges.
1
Deposition of sludge as a cover on crop
land is effective providing surface
drainage is properly designed to limit
washoff.
2 Burial in areas above the flood plain
provides a suitable disposal.
3 Incineration under controlled conditions
to produce complete burning of organics
is preferable.
a Incineration of digested sludge im-
plies substantial feedback in process.
b Incineration of freshly formed sludge
is difficult because of drainability
and concentration problems. It is
preferable from the standpoint of
maximum destruction of organic
pollutants and minimum feedback in
process. Current investigations are
directed toward improving feasibility
of this means of disposal of solids.
1504
IV ANALYTICAL PROCEDURES
A The Analytical Quality Control
Laboratory, Office of Water Programs,
Environmental Protection Agency has
published a manual titled, Methods for
Chemical Analysis of Water and Wastes,
1971.
B In this manual solids are classified into
four groups:
1 Total solids
2 Non-filterable (suspended) solids
3 Filterable (dissolved) solids
4 Volatile solids
C The procedure for the determination of
1, 2, and 3 above is given in the
Analytical Quality Control Laboratory
Manual.
Standard Methods for the Examination
of Water and Wastewater, 13th Ed. ,
page 538, Method 224D (1971) is the
reference cited by the Analytical Quality
Control Laboratory Manual.
This outline was prepared by F. J. Ludzack,
Chemist, National Training Center, Water
Programs Operations, EP A, Cincinnati, OR
45268.
-------
DETERMINA TION OF SUSPENDED SOLIDS
I Wastewater stabilization includes the
conversion of polid, liquid, or gaseous
pollutants to (a) materials at a higher oxida-
tion state or (b) to a more removable form.
Both are interrelated, but (b) is favored
during conventional treatment.
A Economics of treatment are more favorable
when pollutants can be removed and treated
in more concentrated form.
B Pollutant characteristics guide selection
of operations appli~able for contaminant
conversion to suspended solids.
C Control of suspended solids removal is a
major factor in treatment efficiency.
Incomplete removal leads to feedback of
nutrients from the unstable solids during
later stages of stabilization.
II Characterization of the various forms of
solids that may exist or be formed during
stabilization of polluting materials necessarily
depends upon operational factors. These are
usually conditional, but their appreciation is
essential.
A Dissolved solids include solid, liquid, or
gaseous materials that are dispersed in
the aqueous system in molecular or ionic
form. The "solution" may be colored but
it is likely to be clear unless the con-
centration of some items in the mixture
approaches their solubility limits.
B Colloidal solids include a stage or condition
of suspension where the solubility limit
has been reached and the ionic or molecular
dispersion tends to agglomerate to form
"clumps" of insoluble materials or partic-
ulates. These particulates are large
enough to scatter light and form cloudy or
turbid suspensions but are not large
enough to subside without further agglom-
eration. .
C Suspended solids include the colloidally
dispersed solids and the suspended so~ids
that have agglomerated to form particulates
PC. 15c. 3. 71
that will subside or settle under quiescent
conditions to form a solids concentrate
or sludge. Size is a major criterion but
density, shape, and interface character-
istics among the liquid and solid are
important factors.
D Total solids include A, Band C tp.at may
be present in the whole sample.
E Solids interrelationships are discussed in
a prior outline. Determination of sus-
pended solids is the object of this one.
III Sources of suspended solids include both
Natural and man-made operations.
A Rainfall washes particulate material from
the air and from the surfaces of forest,
farmland, undeveloped land and urban or
industrial centers.
B Municipal water supplies are controlled
to maintain negligible suspended solids.
Some may be formed in distribution
systems.
C Groundwaters may contain dissolved solids
that form suspended solids upon exposure
to air or oxidation.
D Wastewaters are likely to contain varied
suspended solids or components that may
be convertec;:l to suspended solids by
biological, chemical or physical trans-
. formations. Their nature varies with
the origin such as household, commercial,
industrial process, mining, washing, or
other operations.
E Breaks below the groundwater level in
partially filled sewers allow infiltration
of suspended materials characteristic of
the surrounding soils and water movement
in them.
F Combined sewer systems, either
intentional or otherwise, permit surface
drainage from roofs, streets, parking lots,
lawns, etc. to enter sanitary sew"!"!';.
16-1
-------
Determination of Suspended Solids
IV The determination of suspended solids
relate to operational factors determining the
particular result obtained.
A A fence of wire or bars of appropriate
sized openings may serve as a barrier
to passage of horses and cattle but fail
to stop cats or dogs.
B Smaller sized particles are commonly
separated by filtratfon, centrifugation,
subsidence, or other hydraulic gradation.
1 Roots, branches, rags, etc., usually
are separated by bar racks or screens
with relatively large openings.
2 Grit, sand and small, but heavy,
particles generally are separated
hydraulically in chambers allowing 1
to 3 minutes detention time.
3 Filtration is the most commonly applied
technique for determination of the
relatively low density particulates that
tend to remain in aqueous suspension
largely as a result of turbulence. Since
pore sizes of filters differ, it is
essential to specify the media used to
interpret results.
1
V Standard Methods refers to residues from
whole sample evaporation as total residue,
suspended solids as the non-filterable residue
retained on or in the filter and dissolved
residue as that appearing in the filtrate.
A Many factors influence the results obtained
during suspended solids determinations
such as
1 Chemical and physical nature of the
solids
2 Sampling techniques
3 Pore size of the filter
A membrane filter of O. 5~ pore size
may retain particulates that are not
retained on paper.
16-2
4 Area, condition, and consistency of
filter media.
5 Technique and manipulative care in
drying, weighing, storage, transfer,
and temperature.
B Standard Methods includes three methods
for non-filterable residue or suspended
solids.
1 Gooch crucible
2 Membrane filter2, 3
3 Buechner funnel-aluminum dish (aerator
or sludge suspended solids).
C A spectrophotometric method was 4
described by Krawczyk and Gonglewski .
The importance of homogenization to
improve sampling uniformity was stressed.
D Chanin, et. al. 5 described the use of
glass fiber media for the determination
of suspended solids.
VI Precision, sensitivity, and applicability
of various methods for determination of
suspended solids are indicated in the cited
references.
A Table I indicates data from several
references on precision of the Gooch
crucible, asbestos fiber mat determination.
B Table 2 presents data published on the
precision of the Gooch crucible, glass
fiber determination.
. 7
C Smith and Greenberg compared results
of 5 replicates each of eight samples
(influents, primary effluents, final
effluents and industrial waste samples)
by five different methods of determination
including:
1 Gooch crucible, asbestos mat
2 Gooch crucible, glass fiber mat
3 Buechner funnel, wire cloth, glass
fiber mat
-------
Determination of Suspended Solids
Range
of Values
mg/l
13-22
20-24
60-72
194-436
60-,196
8-152
56-100
TABLE 1
GOOCH CRUCIBLE
ASBESTOS MA T
Sample
~ange Number Standard Size
of Values of Mean Deviation Filtered
~ ~. Replicates mg/l ~ ml
+ or -
l7U-308 6 10 224 47 25
218-288 6 10 242 24 25
5 360 13 50
5 80 25 100
104 8 100
152 6 100
5 1,023 79 25
5 95 7 100
5 297 27 50
5 96 200
14-26 a 10 17 4 100
190-213 (d)4 10 203 100
100-13~ (d)4 10 122 9 100
52-66 (d) 4 10 59 4 100
a Private communication, Lake Huron Program Office Methods Manual
TABLE 2
GOOCH CRUCIBLE
FIBER FILTER
Sample
Number Standard Size
of Mean Deviation Filtered
Ref. Replicates mg/l mg/l ml
+ or -
a 9 18 3 100
a 9 22 1 100
a 10 67 4 100
6 5 1086 14 25
6 5 361 47 50
6 5 306 15 50
6 5 146 3 100
6 5 104 1 100
6 5 100 1 100
6 5 84 3 100
6 5 79 5 100
5 12 296 119 25
5 14 111 38 25
5 11 100 54 25
5 9 76 17 50
16...3
-------
Determination of Suspended Solids
4 Membrane filter 0.4 to 0.5 IJ pore size
5 Gooch crucible, glass fiber mat, celite
filter aid
a Their conclusions based upon care-
fully controlled technique indicated
that yield and precision were not
statistically different among the five
tested methods.
b Determining factors other than in
(a) included: manipulation time,
required skills, speed of filtration,
consistence of mat quality, equipment
cost and availability.
c Methods 2 and 3 more frequently gave
a lower coefficient of variation
among those tested and were more
favorable with respect to (b).
vn Section VI indicates that good results are
possible among any of the tested methods but
j.t was easier to obtain precise results with
certain methods. The Gooch Crucible-
asbestos mat requires a high degree of skill
and manipulative time to provide consistent
filtration. The membrane filter tends toward
slow filtration, sampling or manipulative
difficulties, and is more expensive.
A Certain precautions essential to consistent
results with Gooch crucible-asbestos mats
include:
1 A thin suspension of asbestos in
distilled water is essential. A walnut-
sized wad of fiber/ 1 is desirable.
2 Shake the suspension vigorously; allow
it to settle 10-20 seconds. Pour the
suspension into another container and
discard asbestos slivers.
3 A more uniform suspension of asbestos
is achieved after 10-30 seconds treat-
ment in a Waring blendor or equivalent.
4 Allow to stand overnight or for a
sufficient time to form an asbestos
fiber concentrate on the bottom.
16..4
Discard any milky fines in suspension
and rewash, if necessary until a
reasonably clear supernatant is
obtained.
5 Insert the clean gooch crucible (30 ml
or other selected size and diameter)
into a Walters crucible adapter fitted
to an 0.5 or 1 1 suction flask.
6 Shake the asbestos suspension
vigorously, add the mixed suspension
to the crucible until it is 1/2 to 2/3
full.
7 Allow the fiber to "mat" for 1/2 to
2 minutes, then apply vacuum slowly.
If a hole forms in the mat the vacuum
was applied too soon and too rapidly.
8 Add additional suspension (vacuum off)
and apply vacuum to withdraw water and
form a mat of 2-3 mm. Waiting period
before vacuum application is not
essential once a mat has formed.
Water penetration rate is an effective
means to judge mat quality. Good
filtering is obtained if the exit stream
from the Walters adapter is continuous
but slow enough to be slightly off axis .
9 Wash the mat with successive portions-
of distilled water (200-250 ml) to clear
the mat of fines.
10 Remowe the crucible, wipe the outside
with clean tissue or cloth and dry and
weigh.
B Precautions and aids for glass fiber mat
usage:
1 Gooch crucibles employing glass fiber
mats of 2. 4 cm diameter may encourage
slow filtration; different shaped units
such as the asphalt filtration crucible
are designed to use larger diameter
mats which may be desirable for
aerator or sludge solids tests.
2 It is advisable to insert glass fiber mats
with the smooth side up. A second mat
may be required if the prewetting rinse
-------
Determination of Suspended Solids
suggests unusually rapid water passage.
Careful placement of the mat is essential.
C Membrane filter precautions include:
1 The filters are fragile and must be
carefully handled to prevent damage
during use.
2 Prewashing in distilled water for 24
hours helps to remove glycerol or
otheI' softening agent that is likely to
be eluted by the sample.
3 Filters tend to curl on drying. An
individual desiccator is described3
that helps to control drying at ambient
temperature and curling in process.
D Beuchner fwmel suspended solids deter-
minations include the (a) aluminum
dish-paper, (b) wire cloth-glass fiber and
(c) paper filtration. The aluminum dish
is designed to support the paper and
prevent losses during drying. The wire
cloth promotes more rapid filtration and
support. When neither supports are used,
the paper or glass fiber may be folded once
with the solids inside during drying.
1 Buechner funnel filtrations always
present the problem of solids adherence
to funnel sidewalls instead of the filter
media. Solids losses due to incomplete
transfer to the filter may be minimized
but not eliminated. A square ended
spatula aids transfer. It is advisable
to adjust sample size to yield> 100 mg
of non-filterable residue to reduce
percentage error for Buechner funnel
tests.
E General precautions applicable for precise
results on suspended solids include:
1 Filters or crucibles must be clearly
identified, dried, genera~ly at 1030 C,
and stored in a desiccator until weighed
and used.
2 The balance should contain a desiccant
to control atmospheric moisture du;ring
weighing. This shou1f;1 be changed
regularly and the doors opened only as
necessary.
3 Filters may be dried in a desiccator
(preferably 24 hours).
4 For rapid, control work with Buechner
funnel-paper filtering, the papers may
be oven dried and equilibrated with
room mois1;ure for 10 minutes to
reduce changes due to rapid moisture
pickup after oven drying.
5 Manufactured filters must be handled
carefully with forceps, polished if
necessary to prevent puncture or
damage to the filter surface.
6 Place the filter media carefully in the
crucible covering all openings in the
support.
a Special care must be used for
membrane filter holders to clamp
the filter in place firmly without
rupture or displacement.
7 Wet the filter media with distilled
water preferably directed at the center
of the mat first. Allow the mat to
become thoroughly wet before applying
vacuum then prewash the filter with
about 100 ml of distilled water.
8 With the vacuum on, add the selected
aliquot of sample.
a The sample volume should be large
eno\,1gh to minimize percentage
errors during weighing. Less
precise technique requires more
weight difference between the pre
and post filtration weights. Three
to five mg weight difference is
adequate for Gooch crucible technique,
> 100 mg required for Buechner
funnel tests. Homogenize the sample
if sampling uniformity is questionable.
9 Rinse the non-filterable residue with
distilled water to wash sidewall solids
down onto the filter mat and to
minimize occluded solubles in the
solids and filter mat.
10 Dry and weigh under the same conditions
as used for preweighing.
16-5
-------
Determination of Suspended Solids
11 Final weight - Initial weight (mg)
1000
X ml sample aliquot =
suspended solids in mg/l
Results are usually expressed in rog/l
(g X 1000). .
12 It is not feasible to dry suspended
solids to a constant weight because of
the interchange of moisture, volatiles
or changes due to oxidation in process.
Weight must be defined in terms of a
routine that minimizes weight change
errors.
13 It is not advisable to pre-ignite glass
fiber mats for the determination of
sample volatile solids as recommended
for asbestos fiber mats. Glass fiber
generally will soften at about 4000 C
but is likely to tolerate ignition at
550 to 6000 C without fusion. It is
advisable to check a given supply of
fiber glass circles by igniting 5 or 6
under carefully controlled ignition
temperatures and time sequence. If
the glass fiber mats are uniform in
weight and composition their weight
loss on ignition will be comparable.
This amount of ignition loss may be
subtracted from the ignition loss for
samples to obtain a corrected value for
sample volatile suspended solids (VSS)
if the loss is acceptably consistent.
14 The aluminum dish may be fabricated
from an aluminum milk dish (listed in
apparatus supply catalogues) by punching
or drilling 1/16 inch holes in the
bottom comparable to those of the
Buechner funnel into which it is inserted.
The aluminum dish and filter may be
weighed before and after sample
filtration and drying. An 0 ring of
silicone M rubber slightly smaller than
the dish may be used to provide a .
vacuum seal with the Buechner funnel.
Sample contents must not overfill the
dish during manipulation to avoid loss
of solids by adherence to the funnel
surfaces.
16-6
VIII The FWPCA "Methods for Chemical
Analy!!is of Water and Wastes", method
for non -filterable solids (Storet number
00530) prescribes filtration through glass
fiber media with drying at 1050 C.
(1969, in press)
REFERENCES
1 Standard Methods,' Water and Wastewater,
APHA, 12th Ed (1965).
2 Engelbrecht, R. S. and McKinney, Ross E.
Membrane Filter Method A pplied to
Activated Sludge Suspended Solids
Determinations. Sewage and Ind.
Wastes, 28:(11) 1321, November 1956.
3 Winneberger, J.H., Austin, J.H., and
Klett, Carol A., Membrane Filter
Weight Determinations. 35:(6), 807
June 1963.
4 Krawczyk, D. L. and Gonglewski, N.,
Determination of Suspended Solids
Using a Spectrophotometer, JWPCF
31: (10) 1159, October 1959.
5 Chanin, G., Chow, E.H., Alexander,
R. B., and Powers, J. Use of Glass
Fiber Media in the Suspended Solids
Determination. Sew. and Ind. Wastes
30: (8) 1062. August 1958.
6 Laboratory Investigation Report # 1,
Technical Advisory and Investigations,
DHEW, PHS, Div. of WS & PC (1963).
7 Smith, A. L., and Greenberg, A. E. ,
Evaluation of Methods for Determining
Suspended Solids, JWPCF 35: (7) 940,
July 1963.
l'hiS outlIne was prepared by D. F. Krawczyk,
Acting Chief Consultant, Laboratory Services,
Pacific Northwest Water Laboratory, Corvallis,
Oregon and F. J. Ludzack, Chemist, Na,tional
Training Center, Environmental ProtectIon
Agency, WPO, Cincinnati, OH 45268
-------
LABORATORY PROCEDURE FOR TOTAL SOLIDS
I
INTRODUCTION
A
This procedure was excerpted from methods
for Chemical Analysis of Water and Wastes,
1971, Environmental Protection Agency,
Office of Water Programs, Analytical Quality
Control Laboratory.
B
The procedure is applicable to surface and
saline waters, domestic and industrial waste,s.
C
The practical rap.ge of the determination is
10-30000 mg/I.
D
Nonhomogenous materials (large floating
particles or submerged agglomerates) should
be excluded from the sample. Floating grease
and oil should be included in the sample and
dispersed in a blender before measuring the
aliquot.
E
Samples shoald be analyzed as soon as
possible.
II
EQUIPMENT
A
Porcelain, Vycor, or platinum evaporating
dishes, 100 ml capacity; smaller sizes may
be used as required.
B
+ 0
Muffle furnace, 550 - 50 C
Drying oven, 103 - 1050C
C
D
Desiccator
E
Analytical balance
F
Steam bath
III
PROCEDURE
A
Heat the clean !fvaP8rating dish in a muffle
furnace at 550 - 50 C for 1 hour.
B
Cool the dish in a desiccator.
PC.lab.16.9.72
C Weigh the dish on an analytical balance.
D StoTe the dish in the desiccator and weigh
just before use.
E Shake the sample container vigorously.
F Measure 100 ml of the well mixed sample
in a graduated cylinder. (At least 25 mg
of residue should be obtained; less volume
of sample may be used if the sample appears
to be high in solids content. If it is low in
solids content, more sample may be added
to the dish after drying).
G Rapidly, but without spilling, pour the
sample into the evaporating dish.
o
H Dry the sample on a steam bath, or at 98 C
(to prevent boiling and splattering) in the
oven.
I
Dry the evaporated sample in the oven at
103 - 105°C for at least one hour.
J Cool the dish in the desiccator and then
weigh it.
K Repeat the heating at 103 - 1050C, cooling
and weighing until the weight loss is less
than 4% of the previous weight, or 0.5 mg,
whichever is less.
:.!
N
CALCULA TIONS
. .
~.I ..
mg total solids/l = (wt dish + residue)':' -
(wt dish)* x 1000 x 1000
ml of sample
':' in grams
This outline was prepared by C. R. Feldmann,
Chemist, National Training Center, WPO, EPA,
Cincirmati, OH 45268.
17-1
-------
LABORATORY PROCEDURE FOR NONFILTERABLE (SUSPENDED) SOLIDS
I
INTRODUCTION
A
This procedure was excerpted from Methods
for Chemical Analysis of Water and Wastes,
1971, Environmental Protection Agency,
Office of Water Programs, Analytical Quality
Control Laboratory.
B
The procedure is applicable to surface and
saline waters, domestic and industrial wastes.
C
The practical range of the determination is
20 - 20000 mg/l.
D
All nonhomogeneous pp.rticulates (such as
leaves, sticks, fish and lumps of fecal matter)
should be excluded from the sample.
E
Sample preservation is not practical; the
analysis should be done as soon as possible.
n
EQUIPMENT
A
Glass fiber filter discs, 4.7 cm or 2. 2cm,
without organic binder. Reeve Angel type
984H, 934H, Gelman type A, or equivalent.
B
Membrane filter funnel (for use with the 4. 7
cm disc), or
C
2S ml Gooch crucible (for use with th,g 2.2 cm
disc).
D
Gooch crucible adapter.
E
SOO ::nl suction flask
F
Drying oven, 103 - 10SoC
G
Desiccator
H
Analytical balance, 200 g capacity, capability
o~ weighing to 0.1 mg.
In
PROCEDURE
A
Assemble the filtering apparatus and suction
flask (either the 2.2 cm disc, Go::>ch crucible
and adapter, or the 4.7 cm disc and membrane
filter funnel).
PC. lab. 17.9.72"
B Apply suction to the flask and wash the
disc with three successive 20 ml portions
of distilled water.
C Continue the suction until all water has
passed through the disc.
D Remove the Gooch crucible plus 2. 2 cm disc
and dry in the oven at 103 - 1 OS 0 C for one
hour, or,
E Remove the 4. 7 cm disc from the membrane
filter funnel and dry ir. the oven at 103 - 10SoC
for one hour. In D or E, if the disc is not
to be used immediately, store it in the
desiccator.
F Weigh the 4.7 cm disc or 2.2 cm disc plus
Gooch crucible just before use.
G Assemble the filtering apparatus.
H Apply suction to the flask.
I
Shake the sample container vigorously.
J Measure 100 ml of the well mixed sample
in a 100 ml graduated cylinder. (If the
sample appears to be low in solids, a
larger volume may be used).
K Rapidly, but without spilling, pour the
sample into the funnel or crucible.
L Continue the suction until all of the water
has passed through the disc.
M Remove the 4.7 cm disc from the funnel
and dry in the oven at 103 - 10SoC to
constant weight, or
N Remove the Gooch crucible plus 2.2 cm
disc and dry in the oven at 103 - 10SoC
to co~stant weight.
Note: Drying to constant weight refers to the
process of:
1) drying the dinc (or disc plus crucible)
at 103 - 10SoC, 2) cooling in the desiccator,
3) weighing, 4) repeating steps 1), 2), and
3). If there is no difference in the two
18-1
-------
LabOl"atory Procedure for Nonfilterable (Suspended) Solids
final weights, the disc (or disc plus
crucible) has been dried to constant
weight. In practice, the initial drying
period is sometimes extended to several
hours. A second heating step is then
generally not carried out.
IV
CA LCULA TIONS
mg nonfilterable (suspended) solids! 1 =
(wt of 4.7 cm disc + residue)':' - (wt of 4.7 cm disc)':' x 1000 x 1000
- ml of sample filtered
or
(wt of 2.2 cm disc + Gooch crucible + residue)~' - (wt of 2.2 cm disc + Gooch crucible)*x 1000 x 1000
ml of sample filtered
~(in grams
This outline was prepared by C. R. Feldmann,
Chemist, National Training Center, WPO, EP A,
Cincinnati, OH 45268. '
18-2
-------
LABORATORY PROCEDURE FOR FILTERABLE (DISSOLVED) SOLIDS
I
INTRODUCTION
A
This procedure was excerpted from Methods
for Chemical Analysis of Water and Wastes,
1971, Environmental Protection Agency,
Office of Water Programs, Analytical Quality
Control Laboratory.
B
The procedure is applicable to surface and
saline waters domestic and industrial wastes.
C
The practical range of the determination is
10-20000 mg/I.
D
Samples high in calcium, magnesium,
chloride, and/ or sulfate may be hygroscopic
and require prolonged drying and desiccation, III
and quick weighing.
E
To insure complete conversion of bicarbonate
to carbonate, samples pigh in bicarbonate
content will require careful and possibly
prolonged drying at 1800C.
F
Excessive residue in the evaporating dish
will crust over and entrap water that will not
be driven off during drying.
G
Samples should be analyzed as soon as
possible.
II
EQUIPMENT
A
Glass fiber filter discs, 4.7 cm or 2.2 cm,
without organic binder. Reeve Angel type
984H. Gelman type A, or equivalent.
B
Membrane filter funnel (for use with the
4.7 cm disc), or
C
25 ml Gooch crucible (for use with the
2.2 cm disc).
D
Gooch crucible adapter
E
500 ml suction flask
Drying oven, 180 + 20C
F
PC. lab. 18.9.72
G Muffle furnace, 5500C
H .I;>rying oven, 180 + 20C
I
Desiccator
J Porcelain, Vycor, or platinum evaporating
dish, 100 ml capacity~
K Steam bath
L Analytical balance, 200 g capacity,
capability of weighing to 0.1 mg.
PROCEDURE
A Assemple the filtering apparatus and
suc;tion flask (either the 2.2 cm disc, Gooch
crucible and adapter, or the 4.7 cm disc
and membrane filter funnel).
B Apply suction to the flask and wash the
disc with three successive 20 ml portions
of distilled water.
C Continue the suction until all water has
passed through the disc.
D Remove the Gooch crucible plus 2. 2 cm
disc and dry in the oven at 103 - 1050C
for 1 hour, or,
E Remove thfi! 4. 7 cm disc from the membrane
filter funnel and dry in the oven at 103 - 1050C
for 1 hour. In D or E, if the disc is not to
be used immediately, store it in the desiccator
F Weigp the 4.7 cm disc or 2.2 cm disc plus
Gooch crucible just before use.
G Heat the clean evaporating dish in the muffle
furnace at 5000C for 1 hour.
H Store the dish in the desiccator and weigh
just before use.
I Assemble the filtering apparatus.
19-1
-------
Laboratory Procedure for Filterable (Dissolved) Solids
J
Apply suction to the flask.
K
Shake the sample container vigorously.
L
Measure 100 ml of the well mixed sample
in a 100 ml graduated cylinder. (A larger
or smaller volume may be used if the .
dissolved solids content is thought to be low
or high).
M
Rapidly, but without spilling, pour the
sample into the funnel or crucible.
N
Continue the suction for at least three
minutes to assure water removal from
the disc.
o
Using a 100 ml graduated cylinder, transfer
100 ml fo the filtrate to the evaporating dish.
P
Evaporate the filtrate to dryness on the
steam bath.
Q
Dry the evaporated sample for at least 1
hour at 180 + 20C.
R
Cool the dish in the desiccator.
S
Weigh the dish.
T
Rep~at the drying, cooling, and weighing
steps until two successive weighings are the
same. or the weight loss is less than
0.5 mg.
19-2
Note: The filtrate from the Non-Filterable
(Suspended) Solids determination may
be used in this procedure.
IV CALCULATIONS
mg filterable (dissolved) solids/l =
(wt dish + residue)* - (wt dish)~c x 1000 x 1000
ml of sample
~cin grams
Ti1i'S outline was prepared by Charles R.
Feldmann, Chemist, National Training
Center. WPO. EPA. Cincinnati. OH 45268.
-------
LABORATORY PROCEDURE FOR VOLATILE SOLIDS
I
INTRODUCTION
A
In the manual, Methods for Chemical
Analysis of Water and Wastes, 1971,
Environmental Protection Agency, Office
of Water Programs, Analytical Quality
Control Laboratory, the reference given
for the determination of volatile solids is
Standard Methods for the Examination of
Water and Wastewater, 13th ed., p 538,
Method 224D, 1971.
B
The Analytical Quality Control Laboratory
manual states that the test is subject to
many errors due to:
1 Loss of water of crystallization.
2 Loss of volatile organic material prior
to combustion.
3 Incomplete oxidation of certain complex
organics.
4 Decomposition of mj,neral salts during
combustion.
The principal source of error is said to be
failure to obtain a representative sample.
C
The procedure in the 13th ed of Standard
Methods involves ignition of the filter disc
from the determination of non-filterable
(suspended) solids at 5500C for 15 minutes,
cooling the disc in a desiccator and weighing.
D
The equipment and procedure paragraphs
below are therefore those from the Analytical
Quality Control Laboratory manual.
IT
EQUIPMENT
A
Glass fiber filter discs, 4.7 cm or 2.2 cm,
withou': organic binder Reeve Angel type
984H, Gelman type A, or equivalent.
B
Membrane filter funnel (for use with the
4.7 cm disc), or
PC. lab. 19.9.72
C 25 ml Gooch crucible (for use with the
2.2 cm disc).
D Gooch cr\lcible adapter.
E 50:'> ml suction flask.
F Desiccator.
G Analytical balance, 200 g capacity,
capability of weighing to O. 1 mg.
o
H Muffle furnace, 550 C.
III
PROCEDURE
A Assemble the filtering apparatus and
suction flask (either the 2.2 cm disc,
Gooch crucible and adapter, or the
4.7 cm disc and membrane filter
funnel).
B Apply suction to the flask and wash the
disc with three successive 20 ml portions
of distilled water.
C Continue the suction until all water has
passed through the disc.
D Remove the Gooch crucible plus 2. 2 cm
disc and dry in the oven at 103 - 1050C
for 1 hour, or,
E Remove the 4. 7 cm disc from the membrane
filter funnel and dry in the oven at 103 - 1050C
for 1 hour. In D or E, if the disc is not to
be used immediately, store it in the
desiccator.
F Weigh the 4.7 em dise or 2.2 em disc
plus Gooch crucible just before use.
G Assemble the filtering apparatus.
H Apply suction to the flask.
I
Shake the sample container vigorously.
20-1
-------
.!;aboratory Procedure for Volatile Solids
J
Measure 100 ml of the well mixed sample
in a 10::> ml graduated cylinder. (If the
sample appears to be low in solids, a
larger volume may be used)...
K
Rapidly, but without spilling, pour the
sample into the funnel or crucible.
L
Continue the suction until all of the water
has passed through the disc.
M
Hemove the 4.7 cm disc from the funnel
and ignite in the muffle furnace at 5500C
for 1 hour, or,
N
Remove the Gooch crucible and 2.2 cm
disc and ignite in the muffle furnace at
5500C for 1 hour.
°
Cool the 4.7 cm disc or 2.2 cm disc plus
Gooch crucible in the desiccator.
P
Weigh the 4.7 cm disc or 2.2 cm disc
plus Gooch crucible.
IV
CALCULATIONS
mg volatile solids/l =
(wt of 4.7 cm disc + residue)* - (wt of 4.7 Crn disc)* x 1000 x 1000
ml of sample filtered
or
(wt of 2.2 cm disc + Gooch crucible + residue)* - (wt of 2. 2 cm disc + Gooch crucible)* x 1000 x 1000
ml of sample filtered
':'in grams
This outline was prepared by Charles R.
Feldmann, Chemist, National Training Center,
WPO, EPA, Cincinnati, OR 45268.
20-2
-------
BIOASSA Y AND BIOMONITORING
I
INTRODUCTION
A An assay is an evaluat~on.
B A bioassay is an evaluation in which living
organisms provide the scale.
1 The scale or degree of response may
be the rate of growth or decrease of a
population, colony, or individual; a
behaviorial, physiological, or repro-
ductive response, or simply a live or
no-live response.
2 All types of bioassays may have a role
to play in water quality evaluation at
one time or another.
3 Th~ particular group of bioassays
discussed below are those which con-
tribute to the evaluation of the effects
of liquid wastes on aquatic environments
in which experimental organisms such
as fish are subjected to a series of
concentrations of a known or suspected
toxicant under adequately controlled
conditions for a stipulated period of
time.
C Historical Highlights
1 Prior to 1940, there was little or no
uniformity in performing or reporting
bioassays of water pollutants.
2 By mid-forties, the need for fI.
standardized technique was becoming
painfully obvious.
a The Atlantic Refining Company
privately published the first
statement of what is today, basically,
our standard method (Hart, Doudoroff,
and Greenbank, 1945).
b This was refined and accorded wide
(but not universal) industrial,
academic, and governmental
acceptance in 1951 (Doudoroff, et aI,
1951).
BI. BIO. met. 17a. 5. 70
3 This method was first developed for
the use of fishes, but has been found
adaptable to a wide variety of
organisms.
D Other Types or Plans of Bioassay
1 Many other designs for the expression
of toxicity have been devised such as
those based on time-concentration
curves. Each has its advantages and
proponents, but the basic Standard
Method design remains the most
widely used.
a In situ exposure of experimental
organisms in cages or live cars,
at selected sites above and below
a suspected point or pollution is an
obvious and time tested procedure,
but lacks the precision of laboratory
tests. It has the advantages of
popular appeal, and of expressing
actual environmental conditions.
b The familiar BOD test is a bioassay
of the organic content of water
subject to biodegradation.
E Biomonitoring
Water quality surveillance or monitoring
by means of observing biota can be con-
sidered from two aspects: field and
laboratory. It differs from bioassay
primarily in the objective: a bioassay
is an attempt to determine a specific
defined value or threshold, whereas a
biomonitoring operation is an attempt to
use living organisms to ascertain whether
or not aquatic life is endangered.
1 Periodic biological field surveys,
samples, or other observation may'
demonstra.te recent excessive pollution
for example.
2 Organisms in a series of flow~through
tanks in a laboratory may demonstrate
the occurrence of an unacceptable
21-1
-------
Bioassay and Biomonitoring
increase in the toxicity of an effluent,
without measuring "how much" or
"what. "
II
THE STANDARD METHOD BIOASSAY
A Introduction
1 This procedure is intended for use by
industrial and other laboratories.
2 Its objective is to evaluate the toxicity
of wastes and other water pollutants
to fish or other aquatic organisms.
3 Potential applications are numerous.
a Dilution and/ or treatment necessary
to avoid acute toxic effects can be
estimated.
b The efficacy of an existing treatment
can be tested.
c The potential usefulness of a proposed
treatment can be estimated.
4 The design of the test need not involve
a chemical knowledge of the toxicant.
a Synergism, antagonism, and other
interactions of chemical components
cannot always be anticipated, but
are automatically included in the
result.
b All chemical and physical information
available is, however, essential to
the adequate interpretation and
application of test results.
5 The test is best used for local
application. Generalizations should
be made with great caution.
6 Field observations should be made of
results of application over a significant
period of time.
7
Careful distinction should be made
between fish mortality due to a
physiological toxicant, and that due
to lack of DO.
2]....2
8 A uniform testing procedure is
essential to effective action in water
pollution control.
B Routine Procedure for Static Tests
1 ~ organisms should be fish or other
organisms of local significance.
a The most sensitive species
available should be selected, but:
b They should be species which are
amenable to captivity.
c They should be accurately identified.
d They should be relatively uniform
in size. Individuals less than 3
inches in length are usually most
convenient.
e They should be healthy and
thoroughly acclimated to the
laboratory.
f A careful .record should be kept
of their origin, handling, and
condition.
2 Test ~ should preferably be taken
from the receiving stream just above
the discharge being evaluated or in a
lake or estuary, beyond the influence
of the discharge.
a If this is unsuitable, cleaner but
similar waters from a more
remote station may be substituted.
b Artificial "standard" waters are
not recommended for general use,
although many formulae have been
proposed.
c In estuarine situations, a series of
tests (marine grid) should~,
using waters of high and low
salinities as characteristic of the
region.
3 Other experimental conditions
-------
Bioassay and Biomonitoring
a Temperature. The tests should be
performed at a uniform temperature
in the upper part of the expected
summer range, e.g.. 25 t 20C for
warm water fish, and 15 t 20 C for
cold water species.
b Test containers should be of glass,
widemouthed "pickle jugs" or
battery jars are satisfactory. Five
and one gallon sizes are both useful,
but the larger size is required for
conclusive results.
TABLE I
A Guide to the Selection of Experimental
Concentrations, Based on Progressive
Bisection of Intervals on a Logarithmic
Scale.
Col. 1 Col. 2 Col. 3 Col. 4 Col. 5
10.0
8.7
7.5
6.5
5.6
4.9
4.2
3.7
3.2
2.8
2.4
2.1
1.8
1. 55
1. 35
1.15
1.0
c Artificial aeration should not be
used to maintain the dissolved
oxygen concentration. If this falls
below approximately 4 or 5 ppm at
any time during the test, fewer fish
should be used per container or an
auxiliary oxygenation procedure
invoked that is designed to avoid
undue loss of volatile toxicants.
d The number of test animals should
not be less than 10 per concentration
for reliable conclusions; these may
be distributed between two or more
containers.
Effluents of unknown, mixed, or
variable composition are usually
best expressed as percent by volume;
while pure substances, or specific
analyzable components are usually
expressed as milligrams per liter
(ppm). A control or reference tank
containing dilution water only (with
no toxicant) is essential, to dem-
onstrate that all experimental
organisms would have survived had
it not been for the toxicant being
tested.
e Ratio of fish to solution. There
should be not more than one gram
of fish per liter of test solution.
4 .Experimental procedure
a All dilutions for a given run should
be prepared from the same sample.
b Duration. Tests should be run for
at least 48 hours, preferable 96.
f
Expression of results. The measure
of relative toxicity is the tolerance
limit (symbol: TL). The time of
exposure lit" must be shown along
with the percentage of fish surviving
(written as a postscript). For
example, a 96 hour TL50 (optional:
TL50 96 hr) of a toxic substance is
that concentration in which 50% of
the experimental organisms survive
for 96 hours. (Figure 1)
c Dead fish should be removed as soon
as observed. Survivors should be
counted and recorded each 24 hours.
d Feeding during the test should be
a voided.
e Experimental concentrations.
Any appropriate series of concen-
trations may be used. A logarithmic-
series such as is suggested in
Table I is very convenient.
21-3
-------
Bioassay and Biomonitoring
111€ CI~llICaL l~arH_1€
In aCU1€ lOXICIT.y
SUB-LETHAL
CONCEN-
TRA TIC1iS
CRITICAL RANGE
100
,4 .
~
PERCENT
SURVIV AL
"~
\
50
--
o
x
o ~ INCREASING CONG.:NTRATION OF TOXICANT ~ 100
Figure 1
THE CRITICA L HA NGE
X = TL50t Concentration
1) A TL50t is the equivalent of a
median tolerance limit (TL t).
m
a The toxicant may be volatile.
2) This is analogous to the LC50
(concentration survived by
50% of the population) of the
toxicologist, but is more
universally usable with the
parameters encountered in the
water environment, some of
which (such as temperature)
cannot be expressed as
"concentrations. "
b Toxic material!? may be masked by
a high BOD.
c The toxicant may be progressively
adsqrped on container walk, fish
slime, metabolized or otherwise
changed so that actual concentrations
in tanks change with time.
2 Standards or requirements other than
those involving toxicity per se may be
involved.
3) TL50's for 96 hours or less are
arbitrarily referred to as
measures of "acute"toxicity,
while TLSO's for longer periods
of time are variously referred to
as sub-acute, chronic, etc.
3 Preliminary and concurrent investi-
gations
a Obtain all available information
about unknown to be tested.
C Special Problems of Static Tests
b Does the material lend itself to this
type of test?
1 Unaerated aquaria with finite quantities
of toxicant are not always satisfactory
(static tests).
c Run feasible on the spot analyses
including 00.
-4
-------
d Significant quantities of solutions
removed from test containers for
analysis should be replaced with
similar volume of same dilution.
4 Wastes with a high BOD or COD
a Suggested preliminary tests:
1) Set up two identical exploratory
tests.
2) Aerate one but not the other.
3) If great difference develops
between them, special pro-
cedures are indicated.
b Oxygenation or aeration of dilution
water before making dilutions may
help.
c Renewal of solutions at stated inter-
vals (12,24, or 48 hours) is approved.
Fish are not harmed by being care-
fully transferred from one container
to another. It is useful where:
1) Initial DO is adequate but slowly
exhausted.
2) Toxicant is volatile, progressively
adsorbed, precipitated, or other-
wise changed.
D Continuous Flow Procedures
1 Continuous flow procedures imply the
continuous or periodic renewal of the
solutions in the experimental containers,
at the same time maintaining the stated
concentrations (including control). The
variety of devices and flow plans to
accomplish this are almost infinite,
two general principals will be outlined
below: assaying and monitoring.
2 Continuous flow bioassay, general
advantages (Figure 2)
a Materials witn moderate oxygen
demands may be tested.
Bioassay and Biomonitoring
b Materials which degrade or are
volatile may be tested.
c Due to the constant removal of
metabolic and other wastes, and
the constant supply of fresh
oxygenated water, fish may be fed
and so maintained over a longer
period of time. Containers must
of course be maintained in reasonably
clean condition.
E Test Concentrations and End Points for
Continuous Flow Assays
I Test concentrations are in general less
restricted than for static tests. They
need not be so high as to insure
achieving the desired end point in 48
or 96 hours, although they may be so
set if desired.
2 Geometric type series of concentrations
are still desirable (See Table 1).
3
Sub-lethal levels may be tested over
entire life histories of organisms to
determine long range effects.
4 In general, the setup should be pre-
pared, calibrated and operated for
several days, or until the concen-
trations have become chemically and
physically stabilized before introducing
the fish or other experimental
organisms.
F Total Fish Weight and Liquid Volume in
Continuous Flow Assays
In general, the constant renewal of test
solution might appear to make possible
testing more or larger fish in less water. .
Actually, flow-through volume and total
weight of fish must be so related that
adequate oxygen is maintained. Further-
more, over the longer periods of time
involved, "lebensraum" (or territory)
must be taken into account. Organisms
must not be crowded to the extent that
aggressive behavior and other ecological
competitive factors are introduced.
21-5
-------
Bioassay and Biomonitoring
CONSTANT HEAO
OILUENT SUPPLY
HEATING OR
COOLING
EQUIPMENT
EFFLUENT OR
TOXICANT SUPPLY
IPUMP, MARIOTTE
BOm ,ETC.I
o
OILUENT WATER
RESERVO IR
A
I
I
I
I
.-------_!
I
I
I
,
I \
I \
I \
w~
THERMOSTAT
I
ACCLIMATIZING
I
TANK
B
I F
OVERFLOW
OVERFLOW TO FLOOR ORAINS
Ji'1nurc 2
BA SIC SETUP FOR CONTINUOUS FLOW BIOASSA Y
g to n rt'prcsl'nts one of several exposure tanka containing Q
Bradcd LU'riCU of dilutions of the toxicant, including one control
with nom',
G End Points or Reactions to be Evaluated
by Continuous Flow Assays
3 Water and/ or power failure may
jeopardize an assay experiment after
months of time have been expended.
1 The original and traditional end point
of biological evaluations such as those
discussed here was the death of the
organism. This was simple, direct,
and unequivocal. Current practice,
however, often involves much more
sophisticated reactions such as
reduction in the reproductive capacity,
or a change in the breathing rate
(movement of gills).
4 The expense of a long continued test
may not be justified by the result.
5 The above points demonstrate that in
general, flow through bioassays are
not a$pted to day-to-day routine
toxicity determinations.
III
REPORTING INTERPRETATION AND
APPLICATION OF BIOASSAY RESULTS
H Special Problems of Flow Through
Bioassays
A Reporting
1 Due to the physical requirements of
maintaining stated concentrations of
chemicals over long periods of time,
laboratory setups are usually com-
plicated and always Tequire attention
and maintenance.
1 Reports should include an orderly
tabulation of all pertinent data such as:
a The type of setup used and duration
of test
2 The problem of disease control
frequently develops in populations held
over a long period of time.
b Identity of experimental animals
6
-------
c Their source, history, average size
and condition, and number used per
concentration
d Source of, and chemical and physical
analysis of experimental dilution
water
e Experimental temperature
f
Volumes of experimental liquid in
each container
g Records of routine analyses such as
DO and pH
h Records of chemical analyses of
toxicants in experimental tanks
TL50t or other end point, and data
from which it was determined.
i
B Interpretation and Application
1 The TL50t is an estimate of the mid-
point of the critical concentration range
the interval between the highest con-
centration at which all test animals
survive, and the lowest at which they
all die (Figure 1).
2
The final step is to extrapolate from
this well established mid concentration
to a safe concentration well below the
"critical concentration range. "
'Extrapolating or rather: "application
factors" to accomplish this are still
under development and will probably
not be fully developed for many years.
Available data indicate that these
factors must be variable according to
the toxicant in question acting in com-
bination with the receiving water in
question, and considering the entire
aquatic community.
3 For a more complete discussion, see
FWPCA Water Quality Criteria
(Reference No.9) pp. 55-72.
4 Other considerations
a Radioactive wastes must be evaluated
with regard to their chemical to:){icity
as well as their radioactivity.
Bioassay and Biomonitoring
b Sub-acute levels of many toxicants
such as lead, arsenic, cadmium,
etc. may exert a low level chronic
toxicity over a long period of time.
c
"Safe levels" of a waste in regard
to toxicity to aquatic life may still
exceed standards of other types such
as color, organic content, suspended
solids, etc.
IV
BIOMONITORING AS COMPARED TO
BIOASSA Y (Figure 3)
A Bioassay is (as stated above) the evaluation
of the effects of stated concentrations of
the test material for given periods of
time.
B Biomonitoring is the use of organisms to
detect change in an effluent (surveillance).
It operates continuously and indefinitely.
C Bioassays typically involve relatively
small flows and employ often especially
prepared (perhaps repeatedly prepared)
batches of experimental material, while
biomonitoring typically involves larger
flows, from operating industries or other
installations.
D Bioassays basically determine:
1 Is the substance deleterious, and if so:
2 How deleterious is it?
E Biomonitoring is useful to
1 Demonstrate the continuous suitability
of an effluent (or a predetermined
dilution thereof) for the survival of the
test organism.
2 Detect a change (usually deleterious)
in the biological acceptability of the
effluent.
3 To detect a change in the effect of a
mixture of the effluent and the receiving
water on the test organism (1. e. to
detect a change in the receiving water).
21-7
-------
Bioassay and Biomonitoring
CONSTANT
SOURCE OF
EFFLUENT
REGULATING DEVICE
b
CONSTANT
SOURCE OF
DILUTION WATER
d
J
,
EXPOSURE
TANK NO.1
o ..p
PROPORTIONING
II
DEVICE
EXPOSURE
I TANK NO.2
V7
EXPOSURE
9 ..p TANK NO.3
DEVICE
SCREENED
OVERFLOW
OUTlETS
Figure 3
BASIC SETUP FOR BIOMONITORING
F Biomonitoring was originally effective
only with relatively fast acting materials,
or in situations where large changes
might occur rather quickly (as for example,
the accidental (?) dumping of a vat of waste
pickle liquor). Recent developments in
the field of biotelemetry now make it
feasible to "wire" a fish with electrodes
(like the astronauts) and so to immediately
record electronically any sudden or subtle
change in the effluent which affects the
physiological parameters being monitored
on the live fish.
REFERENCES
1 American Public Health Association,
Standard Methods for the Examination
of Water and Wastewater, 12th Ed.
(13th edition when available).
New York. 1965.. (13th edition: 1970).
2 Doudoroff, P., et al. Bio-Assay Methods
for the Evaluation of A cute Toxicity of
Industrial Wastes to Fish. Sew. and
Ind. Wastes, Vol. 23, No.1!.
November 1951.
8
3
Doudoroff, P. and Katz, M. Critical
Review of Literature on the Toxicity
of Industrial Wastes and Their
Components to Fish. I Alkalies,
Acids and Inorganic Gases, Sew. and
Ind. Wastes, Vol. 22, No. 11, p. 1432.
November 195.0.
4 Ellis, M.M., Westfall, B.A. and Ellis,
M. D. Determination of Water Quality.
Research Report 9, U. S. Fish and
Wildlife Service, 122 pp. 1946.
5 Hart, W. B., Doudoroff, P. and Greenbank,
J. The Evaluation of the Toxicity of
Industrial Wastes, Chemicals and
Other Substances to Fresh-Water Fishes.
The Atlantic Refining Company,
Philadelphia, Pa. 317 pp.
6 Hart, W. B., Weston, R. F. and DeMann,
J. F. An Apparatus for Oxygenating
Test Solutions in Which Fish are Used
as Test Animals for Evaluating Toxicity.
Trans. Am. Fisheries Soc. 75:228.
1948. .
-------
7 Jackson, H. W. and Brungs, W.A.
Biomonitoring of Industrial Effluents.
Proc. 21st Ind. Waste Conf. Purdue
Univ. (Eng. Extension Bull. No. 121).
p. 117. 1966.
8 Mount, D.l. and Brungs, W.A. A
Simplified Dosing Apparatus for Fish
Toxicology Studies. Water Research
1:21. 1967.
Bio'assay and Biomonitoring
9 U. S. Department of the Interior, FWPCA,
Report of the Committee on Water
Quality Criteria. USGPO, Washington,
DC. April 1, 1968.
This outline was prepared by H. W. Jackson,
Chief Biologist, National Training Center,
Water Programs Operations, EP A, Cincinnati,
OH 45268.
21-9
-------
SPECIAL APPLICATIONS AND PROCEDURES FOR BIOASSAY
I
INTRODUCTION
A The report of the Council on Environ-
mental Quality (1970) repeatedly stresses
the need for the development of predictive,
simulative, and managerial capabilities
to combat air and water pollution. The
last capability depends on the first two.
B The standard static jar fish bioassay,
which uses death as a response, enables
one to predict the toxicity of a particular
waste to fish. One limitation of this
procedure is that it uses a grab sample
which represents the quality of the waste
at only one point in time. The water
used to make the dilutions is also taken
at one point in time. At the actual
industrial site, the quality of the waste
and the river water vary through time.
A composite waste sample partially
overcomes this limitation, but may mask
variations that are biologically important,
C One could put fish in a continuous flow of
waste diluted with river water, but then
there is one further limitation of the
standard bioassay: death is used as th~
response. In order to prevent damage
to organisms, it is necessary to have an
early warning of dangerous conditions,
so that corrective action can be taken.
In other words, symptoms of ill health,
which occur before death, must be detect-
ed if there is to be time for diagnosis
treatment.
II
METHODS AND MATERIALS
A Fish Movement Patterns
1 Fish movement patterns can be monitored
using the technique of light beam inter-
ruption described in detail by Cairns,
et al. (1970). Dawn and dusk are
sim~ated by a motor- driven dimming
unit which gradually increases the
intensity of the room lights over a
half-hour period starting at 6 :30 a. m.
and gradually decreases the intensity
to 0 over a half-hour period starting
at 6:30 p. m. The cumulative movement
BI. BIO. met. 22.11.71
of each of six bluegill sunfish, a
single fish per tank, is recorded
every hour throughout a test except
during the simulated sunrise and
sunset when an additional record is.
made on the half hour. Each day is
divided into four intervals; first
half day, second half day, first half
night and second half night (Table 1).
Before any statistical analysis can
be performed, recordings for day
1 must be completed. After the
cumulative movement for day 1 is
recorde,:!, statistical analyses are
performed after the completion of
each disignated time interval, For
example, the cumulative movement
recorded hourly for each fish during
day 1, first half day values are compar0d
to the cumulative movement recorded
hourly for each fish during day 2, first
half day values.
2
Based on the results of 20 laboratory
experiments "stress detection" is
defined as the presence of two or
more abnormal movement patterns
recorded during the same time interval.
B Fish Breathing
1 Breathing rates may be determined from
polygraph recordings of breathing signals,
The fish are tested in plexiglas tubes
through which dechlorinated tap water
or s-:>me toxic solution is metered 3.t
a flow rate of approximately 100 ml/min.
Breathing signals are detected by three
platinum wire electrodes placed in the
water; an active electrode, an indifferent
electrode, and a ground. The test
chambers and methods of acclimating
the fish are described in more detail
by Cairns, et aI. (1970) The photoperiod
is the same as that for the fish movement
study.
2 The fish are placed in test chambers by
6:00 p. m. and the recordings began at
6: 00 3.. m. the next day to allow the fish
to recover overnight from handling.
, Toxic solutions are introduced at 10:00 a. m,
after the experimental fish have been
exposed to water containing no added
22-1
-------
~l?ecial Applications and Procedure~.fo£..:J?!oa!!sal
toxicant for periods of one to six days.
Each experimental fish thus serves as
its own control. In addition, one or
two fish are never exposed to the
toxicant and serve as controls through-
out each experiment. In one experiment,
using zinc as the toxicant, reported
in Table VI, six control fish were
exposed to water containing no added
zinc for four days.
a Preliminary exidence suggested that
the data could be analyzed by separa-
ting the experimental day into four
periods; a period from 6:00 to 8:00 a. m.
when the breathing rates changed
markedly, a period from 9:00 a. m.
to 5:00 p. m. when the rates were
comparatively high, another period
of rapid change from 6:00 to 8:00 p. m.,
and a night period from 9:00 p. m. to
5:00 a. m. when the rates were compar-
atively low (Sparks, el al., 1970).
b Bluegills increase their breathing
rates when exposed to zinc (Cairns,
et al., 1970). An individual fish was
thus considered to have shown a
response each time its breathing ratE!
during a time period exceeded the
maximum breathing rate observed
during the corresponding period of the.
first day, before any zinc was added. A
response was scored for each value
on the second day that was higher than
the first day maximu::n for the compar-
able period. The control periods
(before any zinc was aided) and the
experiment where no zinc was added
at all were used to determine how many
false detections this method of analysis
would produce. The experimental
periods (after zinc was added) deter-
mined how quickly the method of
a:1alysis could detect zinc concentrations
in water.
c
Zinc concentrations were determined
daily by atomic absorption spectro-
photometry.
22-2
............
------
III
RESULTS
A Fish Movement Patterns
1
Table 1 shows the results of one.
continuous flow experiment carried
out for 20 days. During this experiment
fish were exposed to zinc on day 7
from 1:00 p.m. until 7:00 p.m. at
which time the flow was returned to
normal dilution water. The zinc
concentrations reached their maximum
at 7:00 p.m. and atomic absorption
analyses on effluent samples collected
at this time showed the following
concentrations: tank one, 13.32;
tank two, less than 0.08; tank three,
11.39; tank four, 12.72; tank five,
13.32; and tank six, 12.59 mg/l Zn++.
The results show that these concentrations
of zinc developing over the six hour
interval of exposure were insufficient
to caus~ a detectable change in the
movement patterns of the fish. By
8:30 a. m. of day 8 the effluent zinc
concentrations were less than 0.30 in
all cases.
2
To determine the p~rcent survival and
recovery patterns of the fish once stress
detection occurred, zinc flow was
reinitiated at 1 :00 p. m. on day 13 of
this experiment. Between 8:00 and
9:00 p. m. on day 13 the zinc concentration
in the effluent reached a maximum of:
7.51 for tank one; less than 0.05 for
tank two; 7.49 for tank three; 7.52 for
tank four; 7.49 for tank five; and 7.54 mg/l
for tank six. The concentrations remained
near the above values until the statistical
analyses showed "stress detection"
during the first half night values on day
14 (Table 1). As soon as stress detection
occurred the flow was returned to normal
dilution water. At 10:00 a. m. on d,3.y 15
zinc analyses showed all effluent concentra-
tions to be less than 0.70 mg/l Zn++.
Stress dl~tection continued to be registered
for two consecutive time intervals following
the initial detection, but after that no stress
detection wa.s registered .3.nd the frequency
of abnormal patterns returned to prestress
levels within 48 hOilrs. In this exp~riment
-------
-----
~~l. Applications and Procedures for Bioassay
as with all others in which dilution
water containing zinc was replaced with
dilution water minus zinc at that time
of stress detection !.l! fish survived!
3 The results from the series of experiments
at progressively lower zinc concentrations
indicate that the lowest detectable con-
centration is between 3.65 (Table IT) and
2.93 mg/l zinc (Table Ill) for a !J6-hour
exposure.
B Fish Breathing
1 Table IV shows the :Jreathing rates of
five fish on days 1, 2, and 7 of experiment
8. The first four fish were e:
-------
~c.:.~i~_~I?lica.!!~~.9cedures for J~io~~s,~ay
sunfish can be used to detect sublethal
concentrations of zinc. The criterion
for detection is a certain number of fish
showing an arbitrarily defined response
in breathing rate or activity d11ring one
time period.
B In choosing a specific criterion for
detection, the risk of not detecting stressful
conditions soon enough must be weighed
against the risk of false detections, and
the choice would probably be determined
by the nature of the pollutant. If a pollutant
is easily detected by the biological monitoring
system, is slow-acting, and if the toxic
effects are reversible, then the criterion
for detection might be responses by 3/4
of the test fish, to avoid the false detectiofiS
that would necessitate expensive remedial
a:::tion or a temporary shut-down. On the
other hand, an industry that produces an
effluent containing a fast-acting toxicant
whose effects are irreversible would
probably use a criterion that leads to rapid
detection (responses by 1/4 to 1/2 of the
test fish), and would have to go to the
expense of installing holding ponds or
recycling facilities to accommodate a
relatively high number of false detections.
Alternatively, a safety factor could be
introdu.::ed by metering proportionally
mor-e waste into the dilution water delivered
to the test fish than is delivered to the
stream. The safety factor could be
determined by growth and reproduction
experiments with fish.
C In a.. actual industrial situation water a.nd
waste qualities are apt to vary unpredictably,
and it would certainly be desirable to ha. ve
a redundant detection system. It is conceiv-
able that some harmful combination of
environment3.l condition.'! and waste quality
would be detected by moni.~bring on::: biological
function, but not by monitoring another.
It is also possible that excessive turbidity
would dLsrupt the light beams of the movement
m:)nitor, and not affect the breathing monitor;
or that an excessive concentration of electro-
lytes would affect the electrod,:'!s of the breath-
ing monitor, bu1; not affect the activity monitor.
Therefore, the activity monitor and the
breathLng,monitor have been combined in our
laboratory f01~ further experiments (Fig. 1).
22-4
----
D The rate of data acquisiti0l1 and analysis
could be greatly speeded up if the
monitoring system were automated as
shown in Figure 2. The sampling rate
would be controlled by a minicomputer,
which could receive data from the
movement mon.itor and the polygraph
via a multiplexer as often as every minute.
The minicomputer would be programmed
1:0 perform statistical analyses every 10
minutes, for example, and output the
results on a teleprinter.
E Figure 3 shows how the fish monitoring
units would be used at an actual industrial
site. A mOnitoring unit would be located
on each waste stream in the plant and on
the combined waste stream. The experimen-
tal fish in each unit would be exposed to
waste diluted with water from the river
above the plant, and control fish would be
exposed to upstream water alone (Fig. 4).
The inforomation from each monitoring
unit could be a.~alyzed by a central data
processor, and when there was a warning
response, the industry could tell which
waste stream was at fault. If the pr.oblem
was outside the plant, the control fish
would show responses.
F Figure 5 shows how the in-pla.nt monitoring
systems would be integrated into a river
management system. The in-plant monitoring
units are shown as squares, and in addition
to supplying information to each industry,
the monitoring units also inform the control
center. In such a system, there are several
alternative damage prevention meaS'.lres
that could be used, in addition to whatever
measures, such as sh'.mting wastes to a
holding pond or recycling wastes for further
treatment, are aV'cl.ilable to each industry.
If the monitoring units at Industry 2 indicate
that toxic waste conditions3.re developing,
then the control center might have Industry 1
hold its waste w1til the danger of combining
wastes from Industry 1 and 2 in the river
were alleviated by control measur(~s at
Industry 2. Alternatively, the control center
might call fo!' a release of water from the
upstream dam to dilute the effluent from
industry.
-------
------~- --- -- - ---- _~e..£~a.L~Rcation~-:.~d Procedures !~~~_s_ay.-
G It is likely that "fish sensors" in
continuous monitoring units at industrial
sites can warn of developing toxic conditions
in time to forestall acute damage to the
fish populations in st.reams. In conjunction
with stream water quality standards for
chronic exposure, such biological moni.toring
systems should make it possible for healthy
fish populations to co-exist with industrial
water use.
ACKNOWLEDGEMENT
This research was supported by grants 18050 EDP
and 18050 EDQ from the Water Quality Office, 10
Environmental Protection Agen,~y.
Literature Cited
1 Brungs, W. A. 1969. Chronic toxicity of
zinc to the fathead minnow, ~~ephale~
~Q!!l_e~ Rafinesque. Trans. Amer.
Fish. Soc. 98(2):272-279.
2 Cairns, J., K. L. Dickson, R. E. Sparks,
and W. T. Waller. 1970. A preliminary
report on rapid biological information
systems fOt' water pollution control. Jour.
Water Poll. Contr. Fed. 42(5):685-703.
3 Eaton, S. G. W70. Chronic malathion
toxicity to the bluegill (!:e.£~l~~ ~.9!9~~~
Rafinesque). Water Research. 4:673-634. .
4 ::vIcKim, J. M., and D. A. Benoit. 1971.
Effects of long-term exposures to cooper
on survival, growth, and "'eprodll::tion
of brook trout (Salvelinus fontinalis)
J. Fish. Res. Bd-:-Canacia 28:655:'662.
5 Moot'.:;:, J. G., Jr., Commissioner. 1968.
Water Quali!;' <3!!~~ RepOl"t of the
National Teclmical Advisory Committee
to the Secretary of the Interio t". U. S.
Govt. Printing Office. 234 pp.
6 Mount, D. I. 1963. Chronic toxicity of
cooper to fatheaj minn.;)ws (Pi~ephales
Er~el~~ Rafin.~sq'.le). Water Research.
2:215-223.
7 Mount, D. I. and C. E. Sl:ephan. 1967.
A method for establishing a<:ceptable
toxicant limits for fish-- Malathion
and the butoxyetha.:101 ester of 2, 4-D.
Trans. Amer. Fish. Soc. 96(2):185-193.
8 Solml, R. R. and F. J. Ro:.lf. 1969.
~~E!:t.!.r. w. H. Freeman and Co.
776 pp.
9 Sparks, R. E., W. T. Waller, J. Cairns, Jr.
and A. G. Heat.."1. 1970. Diurnal variation
in the behavior and physiology of blue gills
(Le~~.!-~ ~~!'~s!.~~ Rafinesque).
The ASB Bull. 17(3):90 (Abstract).
Sprague, J. B. 1969. Measurement of
pollutant toxicity to fish I. Bioassay
methods for acute toxicity. Water
Research. 3:793-821.
This outline was -prepa-re-d by JOlmCai"rns:-Ji--.
and Richard .~. Sparks, Center for Environ~
menhl Studies a":l:l Department. of Biology,
Virgi.nia Polytechnic Institute and State
University, Blacksburg, VA 24061
22-5
-------
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Figure 1.
Test chamber for monitoring system, shoWing the electrodes for
recording fish breathing and the light-beam system for recording
fish movement.
-------
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a->
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MOVEMENT
MONITOR
+- .
MULTIPLEXER
6 CHANNELS
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POL YGRAPH
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Figure 2. An automated fish monitoring unit.
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6 IN - STREAM MONITORING UNIT
Figure 3.
Arrangement of fish monitoring units at an industrial site.
-------
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____EE-eci~ AE.EJic~n~_~.j .E!2S~~~~.l.0~ssa:y
IN - PLANT MONITORING UNIT
+
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WASTE
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MONITOR
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MONITOR
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Figure 4.
Detail of a single fish monitoring unit, showing how the
experimental fish are exposed to waste diluted with upstream
water and the control fish are exposed to upstream water alone.
22-9
-------
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0900
-------
THE USE OF BIO-ASSA YS: CASE HISTORIES
I
USE FOR CONTROL OF INDUSTRIA L
WASTES
Bio-assays can be used effectively for many
purposes in industrial operations.
A The toxicity of final effluents and the
probable effects on receiving waters
can be determined.
Examples:
1 A large rayon plant released effluent
into a highly valued recreational stream
which effectively destroyed aquatic
life. 'While this could be shown by
examining the stream biota, con-
ventional physical and chemical tests
(temp., pH, DO, BOD, coliforms, etc. )
gave no evidence of serious pollution.
Bio -assays showed this effluent could
be highly toxic to fish under minimum
river flow conditions and helped in
locating the major toxic component
zinc. Attention to the elimination of
zinc in the treatment process brought
about recovery of this river in a short
time.
2 A number of effluents from different
industries were entering a receiving
. water which was itself of little or no
consequence from the aquatic life
standpoint. Toxicity, which built up
in this basin, was suspected of causing
difficulty in waters of recreational
importance into which this basin drained.
Bio-assays were made on effluents
to evaluate contributions of toxicity.
The following results illustrate how
contributions of toxicity can be
directly shown.
B Toxicity may be traced to process
effluents, which may considerably
reduce volumes requiring treatment.
Examples:
1 Samples of an effluent from a by-
product coke plant appeared to vary
greatly in toxicity. A study was
made to evaluate the sources of
toxicity in this plant. Figure 1 shows
the toxicity of the various process
effluents and their contribution to the
final effluent. It can be readily seen
that a large percentage of toxicity is
contained in several small volume
effluents. If other means of disposal
were found for these process effluents
the toxicity entering the receiving
water would be greatly reduced.
2
Bio-assays at a zirconum separations
plant determined that some process
effluents were highly toxic and must
be eliminated from the receiving
stream for protection of aquatic life.
Other effluents which made up a
larger volume could be released
safely if first mixed (lagooned) and
released in a regulated volume
according to stream flows.
Effluent Number Flow Median Tolerance Limit (TL ) Dilution
Samples cfs % Concentration m Volume
Range Average cfs
A 3 20.6 37 -42 40 32
B 7 17.4 4.4-16 9.1 174
C 7 10.5 13.5-28 20 42
D 8 2.8 4.0-24 9.6 26
E 14 9.85 2.9-22.5 11.0 80
BI.BIO.16a.10.69
23-1
-------
The Use of Bio-Assays: Case Histories
C The effectiveness of treatment processes
may be established.
Example:
1 Bio-assays were used to evaluate the
effectiveness of two different treat-
ment methods in the removal of
toxicity from aircraft washing wastes.
D When locating new plants, the quantity
of dilution water necessary or the degree
of treatment of the wastes may be
ascertained in advance of construction.
Example:
1 Bio-assays of pilot plant wastes from
a synthetic rubber plant indicated
difficulties in waste disposal at a
proposed location for a new plant.
Failure to work out satisfactory
treatment methods caused the
abandonment of this location.
2 Bio-assays of wastes from a similar
facility indicated the feasibility of a
proposed location for air force photo-
graphic laboratory. Removal of silver
and mixing of the process wastes
greatly decreased toxicity.
E Leakage, spills, or other losses of
chemicals into waste streams may be
d.etected and located.
Example:
1
Samples of effluent from a petrochemical
plant were found to be highly toxic
which led to a careful check of process
and sewer systems. Certain im-
perfections in the system were found
and corrected. Later samples
indicated the toxicity had been greatly
reduced.
F Effluents may be continuously monitored
by means of continuous flow bio-assays.
23-2
G Modified bio-assays may be used to
study the effect of chemicals in producing
tastes in fish flesh.
Example:
1 A large chemical company is studying
the effect of effluents containing
chlorinated benzenes and phenols on
production of tastes in fish flesh.
II
OTHER USES
A Toxic concentrations of insecticides,
algicides and herbicides can be
established.
Examples:
1 Runoff from an area treated with
dieldrin was found toxic to fish.
2
Fish toxicity studies are routinely
made when screening potential
algicide s.
B Highly toxic contaminants in drinking
water supplies can be detected.
Example:
1 Detection of possible CW and BW
contaminants.
C May be 1W,ed as an analytical tool for
measuring concentration of toxic
chemicals.
. Example:
1 A time concentration relationship was
established and used in estimating the
concentration of rotenone remaining
and the effectiveness of various water
treatment processes in the removal
of rotenone from water.
-------
The Use of Bio-Assays: Case Histories
FIG URE 1
PERCENT
COnTRIBUTION
BQOSTER COHDEHSER WATER
NO TOX!CITY 0.167 m9
~UEIICIt tlA TER
PRI~ARY COOLER WATER
NO TOXICITY
M~IOIIIA ST I LL
O.O~S m:)
0.630 m!]
O.S~6 m;]
I~
23~
TAR PIJIIT
0.1"9 m~
10%
Intake
2.133 mg
)I
GAS F It:AL COOLER - - - ~T'-m-O.~O I
IIiTERIHTTE';T OVERFLCIo1
llQIIT Oil OECAHTER
0.029111:l
R.B. COlUMII DRAI"
(I BATCH)
0.0007SS mg
D:'
EAST Slr.IP (IJEIiZOl PLAIIT COOLInG I1ATER)
O.S"O III!)
IUSC BEItZOl PLAIIT WASTE
0.026 III~
CAUSTIC WASIt
(2 DATCIIES)
0.00070S III!)
SCIIEHATIC 0 I AGRAH SI/OlfllIG TOX IC I TV OF '~AJOR COKE
n ANT WASTES OISCIIARGF.D TO sn:r::n OUR I ~IG AN e HOUil PER 100
TL 's in % Dilution volumes (DV) in millions of gallons per a-hour period.
m
Since intake water actually had a TL of 60% and a QV of 1. 42 mg, water
from another source was used in the~ tests.
3
-....J
-------
The Use of Bio-Assays: Case Histories
D Used in the development of selective
fish poisons.
REFERENCE
1 Screening of various chemicals for
lamprey control in the Great Lakes
area.
Henderson, C. and Tarzwell, C. M.
Bioassay for Coritrol of Industrial
Effluents, Sew. & Ind. Waste, 29:9
p 1002. 1957.
Example:
This outline was prepared by C. Henderson,
Biologist, FWQA, Colorado River Project
Laboratory, Salt Lake City, Utah.
23-4
-------
IV CONDUCTING THE SURVEY
Sampling in Water Quality Studies
Sample Handling - Field Through Laboratory
Flow Measurement
Tracing Natural Waters
Outline Number
24
25
26
27
-------
SAMPLING IN WATER QUALITY STUDIES
I
INTRODUCTION
A Objective of Sampling
1 Water quality characteri!>tics are not uni-
form from one body of water to a another,
from place to place in a given body of
water, or even from time to time at a
fixed location in a given body of water.
A sampling program should recognize
such variations and provide a basis for
interpretation of their effects.
2 The purpose of collection of samples is
the accumulation of data which can be
used to interpret the quality or condition
of the water under investigation. Ideally,
the sampling program should be so de-
signed that a statistical confidence limit
may be associated with each element of
data.
3 Water quality surveys are undertaken
for a great variety of reasons. The
overall objectives of each survey greatly
influence the location of sampling
stations, sample. type, scheduling of
sample collections, and other factors.
This influence should always be kept in
mind during planning of the survey.
4 The sampling and testing program should
be established in accordance with princi-
ples which will permit valid interpretation.
a The collection, handling, and testing
of each sample should be scheduled
and conducted in such a manner as
to assure that the results wiU be
truly representative of the sources of
the individual samples at the time and
place of collection;
b The locations of sampling stations
and the schedule of sample collections
for the total sampling program shoulcj
WP. SUR. sg. 1a. 6. 66
be established in such a manner that
the stated investigational objectives
will be met; and
c Sampling should be sufficiently
repetitive over a period of time to
provide valid data about the condition
or quality of the water.
B Sample Variations
Interpretation of survey data is based on
recognition that variations will occur in
results from individual samples. While
it is beyond the scope of this discussion
to consider the implications of each in
detail, the following can be identified as
factors producing variations in data and
should be considered in planning the sam-
pling program.
1 Apparent variations
a Variations of a statistical nature,
due to collection of samples from
the whole body of water, as con-
trasted with examination of all the
water in the system.
b Variations due to inherent precision
of the analytical procedures.
c Apparent variations are usually
amenable to statistical analysis.
2 True differences
a Variations of a cyclic nature
Diurnal variations, related to alter-
nating periods of sunlight and
darkness.
Diurnal variations related to waste
discharges from communities.
24,..1
-------
Sampling in Water Quality Studies
Seasonal variations, related to.
temperature and its subsequent
effects on chemical and biological
processes and interrelationships.
Variations due to tidal influences,
in coastal and estuarine waters.
b Intermittent variations
Dilution by rainfall and runoff.
Effects of irregular or intermittent
discharges of wastewater, such as
"slugs" of industrial wastes.
Irregular release of. water from
impoundments, as from power
plants.
c Continuing changes in water quality
Effects downstream from points of
continuous release of wastewater.
Effects of confluence with other
bodies of water.
Effects of passage of the water
through or over geological forma-
tions of such chemical or physical
nature as to alter the characteristics
of the water.
Continuing interactions of biological,
physical, and chemical factors in
the water, such as in the process of
natural self-purification following
introduction of organic contaminants
in a body of wa ter .
II
LOCATION OF SAMPLING STATIONS
A The Influence of Survey Objectives
Much of the sampling design will he
governed by the stated purpose of the
water investigation. As an example of
how different objectives might influence
sampling design, consider a watercourse
with points A and B located as indicated
in Figure 1.
24-2
-----------
.A
X
X
B
).
flow
Figure 1
Point A can be the point of discharge of
wastes from Community A. Point B can
be any of several things, such as an intake
of water treatment plant supplying Com-
munity B, or it might be the place where
the river crosses a political boundary, or
it may be the place where the water is
subject to some legitimate use, such as
for fisheries or for recreational use.
1 Assume that the objective of a water
quality investigation is to determine
whether designated standards of water
quality are met at a water plant intake
at Point B. In this case, the objective
. only is concerned with the quality of the
water as it is available at Point B.
Sampling will be conducted only at
Point B.
2 Alternately, consider that there is a
recognized unsatisfactory water quality
at Point B, and it is alleged that this
is due to discharges of inadequately
treated wastes, originating at Point A.
Assume that the charge is to investigate
this allegation.
In this case the selected sampling sites
will include at least three elements:
a At least one sampling site will be
located upstream from Point A, to
establish base levels of water quality,
and to check the possibility that the
observed conditions actually originated
at some point upstream from Point A.
b A site or sites must be located down-
stream from Point A. Such a site
should be downstream a sufficient
distance to permit adequate mixing in
the receiving water.
c Sampling would be necessary at Point
B in order to demonstrate that the
water quality is in fact impaired, and
that the impairment is due to influences
traced from Point A.
-------
Sampling in Water Quality Studies
B Hydraulic Factors
1 Flow rate and direction
a In a survey pf an extended body of
water it is necessary to de~ermine
the rate and d~rection of water move-
ment influences selection of t;lam-
pIing sites. Many workers plan
sampling statipns representing not
less than the di::!tance water flpws
in~ a 24-hour period. Thus. in
Figure 1. intervening sampling
stations would be ~elected ~t points
representing the distance water
would flow in about 24 houl's.
b In a lake or impoundment direction
of flow is the major problem influenc-
ing selection of sampling stations.
Frequently it is nece~sary to estab.,
lish some sort of grid network of
stations in the vicinity of the sus-
pected sources of pollution.
c In a tidal estuary. the oscillating
nature of water movement will re-
quire establishment of sampling
stations in both directions from
suspected sources of pollution.
2 Introduction of other water
a In situations in which a stream being
studied is joined by q.nother stream
of significant size and chay;acter.
sampling stations will be located
immediately above the extraneous
stream. in the extraneous stream
above its point of juncture with the
main stream. and in the main
stream below the point of juncture.
b Similar stations will be needed with
respect to other water discharges.
such as from industrial outfalls.
other communities. or other instal-
lations in which water is introduced
into the main stream.
3 Mixing
a Wherever possible. one sampling
point at a sample collec~ion site is
used in stream surveys. This
usually is near the surface of the
water. in the main channel of flow.
b In some streams mixing does not
OCCUr quickly. and introduced water
moves downstream for considerable
distances below the point of con-
fluence with the main streams.
~~ample; Susquehanna River at
Harrisburg. where 3 such streams
are recognizable in the main river.
Prelimin
-------
Sampling in Water Quality Studies
D Access to Sampling Stations
For practical reasons, the sampling site
should be easily reached by automobile if
a stream survey, or by boat if the survey
is on a large body of water. Highway
bridges are particularly useful, if the
sample collector can operate in safety.
III
FACTORS IN SCHEDULING OF SAMPLING
PROGRAMS
A Survey Objectives
B Time of Year
1 In short-term water quality investiga-
tions, particularly in pollution
investigations, there often is need to
demonstrate the extremes of pollution
effects on the aquatic environment.
For this reason, many short-term
surveys are conducted during the
warmer season of the year, at such
times as the water flow rate and
volume is at a minimum and there is
minimum likelihood of extensive
raiufall.
2 In a long-term investigation, sampling
typically is conducted at all seasons
of the year.
C Daily Schedules
As 'shown in an introductory paragraph,
water quality is subject to numerous
cyclic or intermittent variations. Sched-
uling of sample collections should be de-
signed to reveal such variations.
1 In short-term surveys it is comrpon
practice to collect samples from each
sampling site at stated intervals through
the 24-hour day, continuing the program
for 1 - 3 weeks. Sampling at 3-hour
intervals is preferred by many w9rkers,
though practical considerations may re-
quire extension to 4- or even 6-hour
intervals.
24-4
2 In an extended survey there is a ten-
dency to collect samples from each
site at not more than daily intervals,
or even longer. In such cases the
hour of the day should be varied through
the entire program, in order that the
final survey show cyclic or intermittent
variations if they exist.
3 In addition, sampling in tidal waters
requires consideration of tidal flows.
If samples are collected but once daily,
many workers prefer to make the col-
lections at low slack tide.
4 In long-term or any other survey in
which only once-daily samples are
collected, it is desirable to have an
occasional period of around-the-clock
sampling.
IV
IDENTIFICATION OF SAMPLING SITES
A River Mile System
The FWPCA method of identifying points
on a water course is by counting river
miles from the mouth (or junction with a
larger stream) back to the source. This
should not be confused with other systems,
such as those in which the river mile is
started at the source of the stream and
proceeds to the mouth of the stream or
confluence with another body of water.
B STORET System
The STORET System is a computer-oriented
data processing system used by FWPCA for
storage, retrieval, and analysis of water
quality data collected by federal, state,
local, and private agencies.
The system includes a complex system -
based on the river mile system - for
identifying sampling locations on all rivers
and streams in the United States. A recent
addition to the system introduces a location
procedure based on geographic coordinates;
this procedure is especially adapted to
location of sampling stations in large bodies
of water such as lakes and impoundments.
-------
Sampling in Water Quality Studies
Not all locations have been coded at this
time, although the coding systems have
been established. The interested worker
should consult Public Health Service Publi-
cation No. 1?63, "The Storage and Retrieval
of Data for Water Quality Control," 1963.
v
SAMf'LE COLLECTION
A Types of Samples
1
"Grab" sample - a grab sample is usually
a manually col~ecteQ single portion of the
wastewater or stream water. An analysis
of a grab sample shows the concentration
of the constituents in the water at the time
the sample was taken,
2
"Continuous" sample - when several points
are to be sampled at frequent intervals or
when a continuous record of quality at a
given sampling station is required, an
automat~c or continuous sampler may be
employed.
a Some automatic samplers collect a
given volume of sample at definite time
intervals; this is satisfactory when the
volume of flow is constant.
b Other automatic samplers take samples
at variable rates in proportion to chang-
ing rates of flow. This type of sampler
requires some type of flow measuring
device.
3 '''Composite'' sample - a composite
sample is the collection and mixing
together of various individual samples
based upon the ratio of the volume of
flow at the time the individual samples
were taken to the total cumulative
volume of flow. The desired composite
period will dictate the magnitude of the
cumulative volume of flow. The mOre
frequently the samples ;;tre collected,
the more representative will be the
composite sample to the actual situa-
tion. Composite samples may be
obtained by:
a Manual sampling and volume of flow
determination made when each sam-
ple is taken.
'"
b Constant automatic sampling (equal
volumes of sample taken each time)
with flow determinations made as
each sample is taken.
c Automatic sampling which takes
samples at pre-determined time
intervals and the volume of sample
taken is proportional to the volume
of flow at any given time.
B Type of Sampling Equipment
1
Manual sampling
a Equipment is specially designed
for coll~ction of samples from the
bottom muds, at various depths,
or at water surfaces. Special
designs are related to protection of
sample integrity in terms of the
water characteristic or component
being measured.
b For details of typical sampling equip-
ment used in water quality surveys,
see outlines dealiqg with biological,
bacteriological, and chemical tests
in this manual.
c Manual sampling equipment has
very broad application in field work,
as great mobility of opera tion is
possible, at lower cost than may be
possible with automatic sampling
equipment.
2 Automatic sampling equipment
A utoma tic sampHng equipment has
several important advantages over
manual methods. Probably the most
important considerat~on ~s the reduction
in personnel requirements resulting
from the use of this equipment. It
also allows more frequent sampling
than is practical manually, and elimi-
nates many of the human errors in-
herent m mapual sampling.
Autoqw.tic sampling equipment has
some disadvantages. Probably the
most important of the se is the tendency
Qf many automatic devices to become
24-5
-------
~ampling in Water Quality Studies
u
a Compositing samplers
clogged when liquids 'high in solids are
being sampled. Individual portions of
composite samples are usually quite
small which may in some cases be
disadvantageous. In using automatic
samplers, sampling points are fixed,
which results in a certain loss of
mobility as compared to manual
methods.
Automatic sampling equipment should
not be used indiscriminately; some types
of samples - notably bacteriological,
biological, and DO samples - should
not be composited. In cases of doubt,
the appropriate analyst should be
consulted.
1) Jar and tube sampler - this typl'
samples effectively when flow
is nearly constant. As water
drains from the upper carboy,
the vacuum created syphons
waste into the lower one. The
rate-of-flow is regulated by the
pinch clamp to fill the lower
carboy dur ing the sampling
period. (See Figure 2 )
~@~lrU ~01J@01J~ ~lA\~ (p(lrn~
A
C
SCREW CLAMP
WASTE STREAM
C MUST BE GREATER THAN A+B
Figure 2
24-6
-------
2) Scoop type
a) Rotating scoop
This device consists of a
power driven scoop mounted
upstream from a weir. The
scoop is so desigped and
mounted that the sample vol-
ume grab~ed on each rotation
of the scoop is proportional to
the flow. as governed by the
head on the weir. The scoop
may be rotated at fI. constant
speed or timed to sample
at fixed time intervals.
b) Revolving wheel with cups
(Figure 3)
This device consistt;! of a
power driven wheel or c;iisc
mounted upstream from a
weir. A number of freely
suspended buckets are mount-
ed at vl1-rying distances from
the axis so that increased
flow will cause more buckets
to be filled. thereby giving a
sample proportionate to flow.
Both this device and tl).e
rotating s~oop sampler can.
of course. be used for nop-
proportionate sampling.
c) Bucket elevators
This device may consist of a
single bucket alternately
lowered into and raised out of
the waste stream. or it may
consist of a series of buckets
on an endles!3 chain passing
through the waste stream. In
either case. it will include a
tripping mechanism to cause
the bucket or buckets to spill
into a sampling funnel. Both
types may be operated contin-
uously or timed for intermittent
operation. This method is not
well adapted to proportionate
sampling.
Samplin~ Water Quality_Stu~~
~
0-
~
rr
WEIR CREST
Fig\U"e 3
WHEEL W!:TH BUCKETS
3 Pumps
a) Cheqlical feed pumps have
been found useful for sampling.
because of their ability to
meter out small doses of
liquids. A timing mechanism
may be used to make the pump
run for longer periods during
heavy flow. thereby allowing
collection of the sample in
proportion to flow. These
pumps are usually provided
with adjustable stroke and
variable speed feature s which
allow variation of the volume
of sample being pumped.
Figure 4 illustrates a battery
operated pump.
b) Automatic shift sampler
(Figure 5 )
Figure 5 shows the automatic
shift sampler. It consists
first of a Randolph or other
"squeegee-" type pump unit.
24-7
-------
Sampling in Water Quality Studies
---
The 2-rpm gear motor drives
the pump at between 1 and 2
rpm through the spring-loaded
adjustable-pitch pulley and
adjustable motor-base arrange-
ment.
We use 1/8-in. (. 32-cm) ID
or 1/4-in. (. 64-cm) ID
polyethylene tubing for sam-
ple intake from the waste
stream. The sample flow is
delivered to the distributor
via a 3/16-in. (. 48-cm) ID
Tygon tube which is supported
loosely by a wire attached to
the framework.
Operation of the distributor is
very simple. The 1-rpm clock
motor powers the chain-and- '
sprocket drive which turns a
threaded bolt. Rotation of the
bolt moves the discharge tube
down the plastic trough at a
rate equal to one division
every eight hours. With the
10 sample-jar receivers the
timer can be set on Friday.
and the 9 week-end shift
samples can be picked up on
Monday.
24~8
Figure 4
BATTERY OPERATED PUMP
4) Solenoid-valve arrangements
A solenoid valve employed in
connection with a timing device
may be used for withdrawing
waste from a pipe under pressure.
Used in connection with a pump
such devices may be employed in
sampling free flowing streams.
(See Figures 6 and 7. )
SOLENOID VIII.!r~
(INSTALL so AS NOT
TO ACT AS TRAP)
jTlMlNO "Ee"
nACCIIIIULATINO TA".
PU..P ~ $IIIIII'UHIJ flU>
- eeREItN TO \
PROTECT PUMP. '--- RETURN LIllI
Figure 6
PUMP - SOLENOID VALVE - TIMER
TYPE SAMPLER
5) Vacuum operated
In its simplest form. the vacuum
is created by a suitably mounted
siphon. It collects the sample
at a uniform rate and is not
suitable for use when proportional
sampling is required.
-------
"
Po.ltlon 01 Sample
Tub., DisChG1'IJn9 to
COII.ctl.9 Y""'~.
Guide ,',
--SOLENOIO .-uSHER
-Normal Position of
$cllnplinv rube ~bI,
to $.....
PumJ)..............
;J
Sampl. Collee-tint "'....I
c..
--AetlU''' Pipe
~
Figure 7
PUMP - SOLENOID-DIVERTER - TIMER
TYPE S1\MPLER
6) Air vent control
c
This type of device is illustrated
in Figure 8. The rate of sample
collection is controlled by the
bubbling mechanism. It is not
suitable for use when proportion-
ate sampling is required.
AlA OUT 7
Lq-
PIPE 18' LOIIG
Figure 8
AlR RELEASE TYPE SAMPLER
Sampling in Water Quality Studies
7) Drip samph;~r
Two types of this device are
illustrated in Figures 9 and 10.
Both devices are simple methods
of obtaining a composite sample
at a fairly constant rate.
WASTES \
FROM SEW£R ~
WIRE ROD SOLDE!lED
TO fUNNEL ANO 8[NT
TO PASS TNROUGH
{/ WATER JET
FUNNEL WITH
NARROW SLOT
CUT IN SID£
:'
'.
o
Fig ure 9
FUNNEL AND ROD DIVERTER
Gt.A5S TUlI7 SMALL WOlfS ltUIetlt TU8IMO QDTTtD UO
~:f'-'-] -'-~G=)
000
SAMPU C~U:CTINO IO'TTLU
Figure 10
DRIP TUBE SAMPLERS
24-9
-------
Sampling in Water Quality Studies
b Continuous recording equipment
Instruments have been developed
which provide direct measurement
of temperature, pH, conductivity,
color, and dissolved oxygen. Such
instruments may be equipped for
continuous recording. Instruments
of this type are quite expensive and
their installation is often difficult.
They are best adapted to permanent
installations, although good portable
non-recording instruments are
available for the measurement of
temperature, pH, and conductivity.
VI
SOME CONSIDERATIONS IN SAMPLING
OPERA TrONS
All procedures in care and handling of sam-
ples between collection and the performance
of observations and tests are directed toward
maintaining the reliability of the sample as
an indication of the characteristics of the
sample source.
A Sample Quantity
1 Samples for a series of chemical
analyses requires determina tion of the
total sample volume required for all
the tests, and should include enough
sample in addition to provide a safety
factor for laboratory errors or acci-
dents. Many workers collect about
twice the amount of sample actually
required for the chemical tests. As
a rule of thumb, this is on the order
of 2 liters.
2 Bacteriological samples, in general,
are collected in 250 - 300 ml sterile
bottles; approximately 150 - 200 ml of
samples is adequate in practically all
cases.
B Sample Identification
1 Sample identification must be main-
tained throughout any survey. It is
vital, therefore, that adequate records
be made of all information relative to
24..10
the source of the sample and conditions
under which the collection was made.
All information must be clearly under-
standable and legible.
2 Every sample should be identified byO
means of a tag or bottle marking,
firmly affixed to the sample bottle.
Any written material should be with
indelible marking material.
3 Minimum information on the sample
label should include identification of
the sample site, date and time of col-
lection, and identification of the
individual collecting the sample.
4 Supplemental identification of samples
is strongly recommended, through
maintenance of a sample collection
logbook. If not included on the sample
tag (some prefer to duplicate such infor-
ma tion) the logbook can show not only
the sample site and date and hour of
collection, but also the results of any
tests made on site (such as temperature,
pH, dissolved oxygen). In addition, the
logbook should provide for notation of
any unusual observations made at the
sampling site, such as rainfall, direc-
tion and strength of unusual winds, or
evidence of disturbance of the collection
site by human or other animal activity.
C Care and Handling of Samples
1 As a general policy, all observations
and tests should be made as soon as
possible after sample collection.
a Some measurements require perform-
ance at the sampling site, such as
temperature, light intensity (if
determined), flow-rate, etc.
b Some tests are best made at the
sampling site because the procedures
are simple, rapid, and of acceptable
accuracy. This m:ay include such
determinations as pH and conductivity.
c Some additional determinations, such
as alkalinity, hardness, dissolved
-------
oxygen, and turbidity may b~ maj:ie
in the field, provided that ease, con-
venience, and reliability of results
are acceptable for the purposes of
the study.
2 Samples to be ~l1alyzed iq the laboratory
require special protection to assure that
the quality measured in the sample repr~-
sents the condition of the source. Many
sampl\,!s, espec~l;ll1y those subjected to
biological analysis, require special pre,.
servation, protection, and handling pro-
cedures. In case pf doubt, the appropriate
analyst should be consulted. Most com-
mon procedures for sample protection
include:
a Examination with;i.n brief time after
collection.
b Temperatl,lre control.
c Protection from light.
d Addition of preservative 9hemicals.
Applications of these sample protective
procedures are along the following
lines:
3 Early examination of sample
Applicable to all types of sampleI'.
4 Temperature control
~ All biological materials for examina-
tion in a living state should be iced
between collection and examination.
b Bacteriological samples, according
to "Standard Methods" should be
maintained at the same temperature
as the source of the sample between
collection and starting the laboratqry
tests. Most survey worf~-
ever, continue to ice samples and
start laboratory tests within 6 hours
after collection.
c Chemicl,ll samples often require
icing.
Samples for dissolved oxygen can
be maintained several Qours if kep,t
iced, ancl protectecl from the light.
Sampling in Water Quality Studies
BOD s;,lmples can be held several
ho1,l~s in an iced condition.
Quick freezing will permit retention
of many l3amples for up to several
months prior to laboratory examina-
tion.
5, Protection from light
a Any constituent of water which may
be influenced by physiochemical
reactions involving light should be
protected. DO sam?les brought to
the iodine stage, for example, should
be protected from light prior to
titra tion.
b 11'1 addition, any water constituent
(such as dissolved oxygen) which
may be influenced by algal activity
should be protected from light.
6 Addition of chemical preservatives
a BacteriQlogical sample s never
should be "protected" by addition
of preservative agents. The only
permissible chemical additive is
SOdium thiosulfate, which is used
to neutralize free residual chlorine,
if present.
b Samples for biological examination
should be protected by chemical
additives only under specific
direction of the principal biologist
in a water quality study. Limited
applications of chemical preserva-
tives are discussed in the biology
putline/> in this manual.
c For chemical tests, preservatives
are useful for a number of water
components. The following examples
are cited:
Nitrogen and phosphorus analyses:
The addition of 1 ml concentrated
H2S04/liter of sample will retard
biological p.ctivity, which otherwise
might alter the concentration of
these cOnstituents. However it
should be noted that some pr~cedures
for these determinations will require
24-11
-------
Sampling in Water Quality Studies
subsequent neutralization of the
sample.
Metals: The addition of 1 - 5 ml of
acid (HCI, HNOa, or H2S04) pre-
vents precipitation of the metal in
the container. The choice of acid
depends on what other analyses are
to be made on the sa1p.ple (e. g. HCI
would not be used to preserve a sam-
ple which later will be analyzed for
chlorides).
COD and ABS: Addition of 1 ml
sulfuric acid per liter of sample is
suggested.
In general, samples requiring re-
tardation of biological activity can
be temporarily preserved by addi-
tion of chloroform; tests should be
run as soon as possible, however.
Determination of ratio of volatile
to suspended solids can be delayed
up to 6 months if 2% for maldehyde is
added.
, ,
24-12
Cyanide determinations may be
delayed temporarily through ,addition
of a!kali to the sample. A few
pellets of sodium hydroxide are
sufficient.
Sulfide analysis ~ay be delayed up
to as much as 6 months by addition
of 2 ml/liter of sample of 2N solu-
tion of z,inc acetate.
Phenol analysis can be delayed
temporarily by acidification to below
pH 4. 0 with phosphoric acid and
preservation with 1 gram CUS04
per liter of sample.
REFERENCES
1 Standard Methods for the Examination of
Water, Sewage and Industrial Wastes.
12th Ed. A. P. H. A. 1965.
2 Planning and Making Industrial Waste
Surveys. Ohio River Valley Water
Sanitation Commission.
3 Industry's Idea Clinic. Journal of the
Water Pollution Control Federation.
April, 1965.
This outline was prepared by H. L. Jeter,
Director, National Training Center, WPO ,
EPA, Cincinnati, OH 45226 and P. F.
Atkins, Jr., formerly Sanitary Engineer,
FWPCA Training Activities, SEC.
-------
SAMPLE HANDLING - FIELD THROUGH LABORATORY
I
P LANNING A SAMP LING PROGRAM
A Factors tp Consider:
1
Locating sampling site!;!
2
Sampling equipment
3 Type of sample required
a grab
b composite
4 Amount of sample required
5 Frequency of collection
6 Preservation measures, if any
B Decisive Criteria
1 Nature of the sample SOUI'ce
2
Stability of constituent(s) to be measured
3 Ultimate use of data
II
REPRESENTATIVE SAMPLES
If a sample is to provide meaningful and
valid data about the parent population, it
must be representative of the conditions
existing in that parent source at the
sampling location.
A The container should be rinsed two or
three times with the water to be collected.
B Composiqng Samples
1 For some sources, a composite of
samples is made which will represent
the average situation for stable
constituents.
2
The nature of the constituent to be
determin~d may require a series of
separate samples.
WP. SUR. sg. 6.12.71
C The equipment used to collect the sample
is an important factor to consider.
ASTM( 1} has a detailed section on various
sampling devices and techniques.
D Great care must be exercised when
collecting samples in sludge or mud areas
and near benthic deposits. No definite
procedure can be given, but careful
effort should be made to obtain a rep-
resentative sample.
III SAMPLE IDENTIFICATION
A Each sample must be unmistakably
identified, preferably with a tag or label.
The required information should be planned
in advance.
B An information form preprinted on the
tags or labels provides uniformity of
sample records, assists the sampler, and
helps ensure that vital information will
not be omitted.
C Useful Identification Information includes:
1 sample identity code
2 signature of sampler
3 signature of witness
4 description of sampling location de-
tailed enough to accommodate repro-
ducible sampling. (It may be more
convenient to record the details in the I
field record book).
5 sampling equipment used
6 date of collection
7 time of collection
8 type of sample (grab or composite)
9 water temperature
10 sampling conditions such as weather,
water level, flow rate of source, etc. "."
11 any preservative additions or techniques. .
12 record of any determinations done in
the field . .
13 type of analyses to be done in laboratory. .
"~
25- 1
-------
Sample Handling - Field Through Laboratory
IV SAMPLE CONTAINERS
A Available Materials
1 glass
2 plastic
3 hard rubber
B Considerations
1 Nature of the sample - Organics
attack polyethylene.
2 Nature of constituent('s) to be determined
- Cations can adsorb readily on some
'plastics and on certain glassware.
Metal or aluminum foil cap liners can
interfere with metal analyses.
3 Preservatives to be used - Mineral
acids attack some plastics.
4 Mailing Requirements - Containers
should be large enough to allow extra
volume for effects of temperature
changes during transit. All caps
should be securely in place. Glass
containers must be protected against
breakage. Styrofoam linings are
~seful for protecting glassware.
C Preliminary Check
Any question of possible interferences
related to the sample container should
be resolved before the study begins. A
preliminary check should be made using
corresponding sample materials, con-
tainers, preservatives and analysis.
D Cleaning
If new containers are to be used, prelim-
inary cleaning is usually not necessary.
If the sample containers have been used
previously, they should be carefully
cleaned before use.
There are several cleaning methods
available. Choosing the best method in-
volves careful consideration of the nature
of the sample and of the constituent(s) to
be determined.
25- 2
1 Phosphate detergents should ~ be
used to clean containers for phosphorus
samples.
2
Traces of dichromate cleaning solution
will interfere with metal analyses.
E Storage
Sample containers should be stored and
transported in a manner to assure their
readiness for use.
V SAMP LE PRESER VA TION
Every effort should be made to achieve
the shortest possible interval between
sample collection and analyses. If there
must be a delay and it is long enough to
produce significant changes in the sample,
preservation measures are required.
At best, however, preservation efforts
can only retard changes that inevitably
continue after the sample is removed
from the parent population.
A Functions
Methods of preservation are relatively
limited. The primary functions of those
employed are:
1 to retard biological action
2 to retard precipitation or the hydrolysis
of chemical compounds and complexes
3 to reduce volatility of constituents
B General Methods
1 pH control - This affects precipitation
of metals, salt formation and can
inhibit bacterial action.
2
Chemical Addition - The choice of
chemical depends on the change to be
controlled.
Mercuric chloride is commonly used
as a bacterial inhibitor. Disposal of
the mercury- containing samples is a
problem and efforts to find a substitute
for this toxicant are underway.
-------
Sample Handling - Field Through Laboratory
To dispose of solutions of inorganic
mercury salts, ~ r!'}comme~ded
procedure is to captur!'} I;Uld retain the
mercury salts as the sulfide at a high
pH. Severa~ firms have tentatively
agreed to accept the mercury sulfide for
re-processing after pre~iminary con-
ditions are met. (4)
3 Refrigeration and Freezin~ - This is
the best preservation technique avail-
able, but it is not applicable to all
types of samples, It is not always a
practical technique for field operations.
C Specific Methods
The EP A Methods Manual(2) U1cludes a
table summarizing the holding times and
preservation techniques for several
analytical,procedures. Tl:rls ~nformation
also can be found in the standard refer-
ences (1,2,3) as part of th~ discus~ion
of the determination of interest.
VI METHODS OF ANALYSIS
Standard reference books of analytical
procedures to determine the physical
and chemical characteristics of various
types of water samples are available.
A EP A Methods Manual
The AI1alytical QualitY Control Labor<;i.tory,
Office of Research and Monitoring,
Environmental Protection Agency, has
published a manual of analytiqal procedures
to be used in Office of Water Programs
laboratories for the analysis of water
and wastes. The title of this manual is
"Methods for Chemical Analysis of Water.
and Wastes" (1971).
For some procedures, the analyst is
referred to Standard Methods and/or to
ASTM Standards.
B Standard Methods
The American Public Health Association,
the American Water Works Association
and the Water PollutiQn Control Federation
prepare and publish a volume describing
methods of water analysis. These include
physical and chemical procedures. The
title of this book is "Standard Methods
for the Examination of Water and Waste-
water", 13th edition, 1971.
C
ASTM Standards
The American Society for Testing and
Materials publishes an annual "book"
of specifications and methods for testing
materials. The "book" currently con-
sists of 33 parts. The part applicable
to water is a book titled, "Annual" Book of
ASTM Standards, Part 23, Water;
" AtI~ospheric Analysis".
D
Other References
Current literature and other books of
analytical procedures with related in-
formation are available to the analyst.
VII ORDER OF ANALYSES
The ideal situation is to perform all
analyses shortly after sample collection.
In the practical order, this is rarely
possible. The allowable holding time
for preserved samples is the basis
for scheduling analyses.
A
The allowable holding time for samples
depends on the nature of the sample, the
stability of the constituent(s) to be de-
termined and the conditions of storage.
1 For some constituents and physical
values, immediate determination is
required, e. g. dissolved oxygen, pH.
2 Using preservation techniques, the
holding times for other determinations
range from 6 hours (BOD) to 7 days
(COD). Metals may be held up to 6
months. (2),
3 The EPA Methods Manual(2) includes
a table summarizing holding time s and
preservation techiliques for several
analytical procedures. This information
can also be found in the standard
25-3
-------
Sample Handling - Field Through Laboratory
(1' 2 3)
references" as part of the
discussion of the determination of
interest.
4 If dissolved concentrations are
sought, filtration should be done in
the field if at all possible. Other-
wise, the sample is filtered as soon
as it is received in the laboratory.
A 0.45 micron membrane filter is
recommended for reproducible
filtration.
B
The time interval between collection
and analysis is important and should be
recorded in the laboratory record book.
VIII RECORD KEEPING
The importance of maintaining a bound,
legible record of pertinent information
on samples cannot be over-emphasized.
A
Field Operations
A bound notebook should be used. Sample
information written in it would include:
1 Sample identification records (See
PartllI)
2 Any information requested by the
analyst as significant
3 . Details of sample 'preservation
4 A complete record of data on any
determinations done in the field.
(See B, next)
5
Shipping details and records
B
Laboratory Operations
Samples should be logged in as soon as
received and the analyses performed
as soon as possible.
A bound notebook should be used.
Preprinted data forms provide uniformity
of records and help ensure that required
information will be recorded. Such sheets
should be permanently bound.
25-4
Items in the laboratory notebook would
include:
1 sample identifying code
2 date and time of collection
3 date and time of analysis
4 the analytical method used.
5 any. deviations from the analytical
method used'
6 data obtained during analysis
7 quality control checks used
8. any information useful to those who
interpret and use the data
9 signature of the analyst
IX
SUMMARY
Valid data can be obtained only from a repre-
sentative sample, unmistakably identified,
carefully collected and stored. A skilled
analyst, using reliable methods of analyses
and performing the determinations within
the prescribed time limits, can produce data
for the sample. This data will be of value
only if a written record exists to verify sample
history from the field through the laboratory.
REFERENCES
1
ASTM Standards, Part 23, Water;
Atmospheric Analysis.
2'
Methods for Chemical Analysis of Water
and Wastes, EPA-AQCL, 1971,
Cincinnati, OH 45268.
3
Standard Methods fox: the Examination of
Water and Wastewater, 13th edition,
APHA-AWWA-WP.CF, 197L
4
Dean, R., Williams, R. and Wise, R.,
Disposal of Mercury Wastes from
Water Laboratories, Environmental
Science and Technology, October, 1971.
This outline was prepared by A. Donahue,
Chemist, National Training Center, DTTB,
MDS, OWP, EPA,Cincinnati, OH 45268.
-------
FLOW MEASUREMENT
I
INTRODUCTION
Flow measurements are among the more
important data collected during a water
quality survey. Such measurements are
used to interpret data variations, calculate
loadings, and expedite survey planning. If
the analysis of survey data involves estima-
tion of loads, the accurate measurement of
discharge assumes a level of importance equal
to that of laboratory and analytical results.
In the following discussion, procedures for
measurement of stream flow and waste dis-
charge are described. Some of these pro-
cedures are used in long-term, very detailed
water quality and supply studies; others are
more suited to short-term pollution surveys.
II
PLA NNING
A Station Location
Four factors influence location of gauging
or flow measurement stations:
1
Survey objectives
2 Physical accessibility
3 Characteristics of the stream bed
4 Hydrologic effects
Survey objectives represent the major
influence on station location; depending
upon objectives, gauging stations may be
located above and/or below confluences
and outfalls.
Physical accessibility determines the
ease and cost of installation and main-
tenance of the station. The characteristics
of the stream bed may greatly influence
the obtainable accuracy of measurement.
For instance, rocky bottoms greatly
reduce the accuracy of current meters.
Sedimentation in pools behind control
structures may influence stage-discharge
relationships. Hydrologic variations in
stream flow may cause washout or bypass
of the gauging station. In the Southwest,
flash floods have been known to wash out
or bypass gauging stations by assuming
different channels of flow.
IN. SG. 13a. 8.68
B Methodology
Choice of a specific measurement pro-
cedure is dependent upon at least three
considerations:
1 The relation between obtainable and
desired accuracy
2 Overall cost of measurement
3 The quantity of flow to be measured
Ideally, discharge measurements should
be reported to a specific degree of accuracy;
the gauging procedure greatly influences
this accuracy. The influence of overall
cost on the gauging program is readily
apparent. Extensive, detailed studies are
usually characterized by high costs for
automatic instrumentation and low personnel
cost; the opposite is usually true for less
detailed studies. The range of flows to be
measured (within acceptable accuracy) is,
of course, not known prior to the survey.
However, experienced personnel usually
can make reasonable estimates of expected
flows from visual observations and other
data, and may recommend appropriate
gauging procedures. In this regard,
experienced personnel always should be
consulted.
III
MEASUREMENT
A Streams, Rivers, and Open Channels
1 Current Meter
The current meter is a device for
measuring the velocity of a flowing body
of water. The stream cross section is
divided into a number of smaller sections,
and the average velocity in each section
is determined. The discharge is then
found by summing the products of area
and velocity of each section.
2
Stage-discharge relationships
Large flows usually are measured by
development of and reference to a stage-
discharge curve; this procedure has long
been used by the U. S. Geological Survey.
Such gauging stations are composed of a
control structure located downstream of
the location Of measurement and some
type of water level indicator which iden-
tifies the height of the water surface
above a'previously determined datum.
26-1
-------
Flow Measurement
Location of the control structure so
that reliable measurements of flow
will be obtained at all river stages is
particularly important. The water level
may be continuously recorded by an
automatic rec order located in a wet
well or may be indicated directly on a
staff gauge located at the bank of the
river. Such stations must be calibrated
by measurement of flow by velocity-
area methods (current meter) at all
expected stages of river flow.
commonly used to measure the dis-
charge of small streams.
The standard equation for discharge
of a suppressed rectangular weir
(F rancis equation) is:
Q =
3.33 LH3/2
where
3 Weirs
Q =
L =
H =
discharge, cfs
length of the weir crest, feet
weir head, feet
A weir may be defined as a dam or
impediment to flow, over which the
discharge conforms to an equation.
The edge or top surface over which the
liquid flows is called the weir crest.
The sheet of liquid falling over the weir
is called the nappe. The difference in
elevation between the crest and the
liquid surface at a specified location,
usually a point upstream, is called the
weir head. Head-discharge equations
based on precise installation require-
ments have been developed for each
type of weir. Weirs so installed are
called standard weirs. Equations for
non-standard installations or unusual
types may be derived empirically.
The performance of this type of weir
has been experimentally investigated
more intensively than that of other
weirs. At least six forms of the dis-
charge equation are commonly
employed. The standard suppressed
weir is sometimes used when data
must be unusually reliable.
Weirs are simple, reliable measure-
ment devices and have been investigated
extensively in controlled experiments.
They are usually installed to obtain
continuous or semi-continuous rec ords
of discharge. Limitations of weirs
include difficulty during installation,
potential siltation in the weir pond,
. and a relatively high head requirement,
0.4 - 2. a feet. Frequent errors in
weir installation include insufficient
attention to standard installation re-
quirements and failure to assure com-
pletely free discharge of the nappe.
b Standard contracted rectangular weir
The crest of this type of weir is
shaped like a rectangular notch.
The sides and level edge of the crest
are so removed from the sides and
bottom of the channel that contraction
of the nappe is fully developed in all
directions. This weir is commonly
used in both plant surveys and meas-
urement of stream discharge.
The standard equation for discharge
of a contracted rectangular weir
(corrected Francis equation) is
Q =
1...
3.33 (L - O. 2H)H3/ 2
where
a
Standard suppressed rectangular
weir
Q =
L =
H =
O.2H =
discharge, cfs
length of the level crest
edge, feet
weir head, feet
correction for end contractions
as propos ed by Francis
This type of weir is essentially a dam
placed across a channel. The height
of the crest is so controlled that con-
struction of the nappe in the vertical
direction is fully developed. Since
the ends of the weir are coincident
with the sides of the channel lateral
contraction is impossible. This weir
requires a channel of rectangular
cros s section, other special instal-
lation conditions, and is rarely used
in plant survey work. It is more
c Cipolletti weir
The Cipolletti weir is similar to the
contracted rectangular weir except
that the sides of the weir notch are
inclined outward at a slope of 1
horizontal to 4 vertical. Discharge
through a Cipolletti weir occurs as
though end contractions were absent
and the standard equation does not
include a corresponding factor for
correction.
26-2
-------
Flow Measurement
The standard equation for discharge
of a 900 triangular weir (Cone
formula) is
Q =
2. 49H2. 48
where
Q =
H =
discharge, cfs
weir head, feet
Crest height and head
are measured to and from the point
of the notch, respectively.
e Accuracy and installation
requirements
Figure 1. STANDARD CONTRACTED
RECTANGULAR WEIR
Q = discharge, cfs
L = length of the level crest edge, feet
Quotations of weir accuracy express
the difference in performance between
two purportedly identical weirs and
do not include the effects of random
error in measurement of head. Weirs
installed according to the following
specifications should measure dis-
charge within:!: 5o/c of the values
observed when the previously cited
standard equations were developed.
The standard equation for discharge
through a Cipolletti weir is
. Q = 3.367 LH3/2
where
H = weir head, feet
The discharge of a Cipolletti
weir exceeds that of a suppressed
rectangular weir of equal crest
length by approximately 1 percent.
1) The upstream face of the bulkhead
and/or weir plate shall be smooth
and in a vertical plane perpendicular
to the axis of the channel.
The crest of a triangular weir is
shaped like a V-notch with sides
equally inclined from the vertical.
The central angle of the notch is
normally 60 or 90 degrees. Since
the triangular weir develops more
head at a given discharge than does
a rectangular shape, it is especially
useful for measurement of small
or varying flow. It is preferred for
discharges less than 1 cfs, is as
accurate as other shapes up to 10
cfs, and is commonly used in plant
surveys.
2) The crest edge shall be level, shall
have a square upstream corner,
and shall not exceed O. 08 in (2 mm)
in thickness. If the weir plate is
thicker than the prescribed crest
thickness the downstream corner
of the crest shall be relieved by a
450 champfer.
3) The pressure under the nappe
shall be atmospheric. The maxi-
mum water surface in the down-
stream channel shall be at least
0.2 ft. below the weir crest.
Vents shall be provided at the
ends of standard suppressed weirs
to admit air to the space beneath
the nappe.
d Triangular weirs
3
-------
Flow Measurement
4) The approach channel shall be
straight and of uniform cross
section for a distance above the
weir of 15 to 20 times the maximum
head, or shall be so baffled that a
normal distribution of velocities
exists in the flow approaching the
crest and the water surface at the
point of head measurement is free
of disturbances. The cross-
sectional area of the approach
channel shall be at least 6 times
the maximum area of the nappe at
the crest.
5) The height of the crest above the
bottom of the approach channel
shall be at least twice, and
preferably 3 times, the maximum
head and not less than 1 foot.
For the standard suppressed weir
the crest height shall be 5 times
the maximum head. The height of
triangular weirs shall be measured
from the channel bottom to the
point of the notch.
6) There shall be a clearance of at
least 3 times the maximum head
between the sides of the channel
and the intersection of the maximum
water surface with the sides of the
weir notch.
7) For standard rectangular suppressed,
rectangular contracted, and
Cipolletti weirs the maximum head
shall not exceed 1/3 the length of
the level crest edge.
8) The head on the weir shall be taken
as the difference in elevation
between the crest and the water
surface at a point upstream a
distance of 4 to 10 times the
maximum head or a minimum of
6 feet.
26-4
9) The head used to compute dis-
charge shall be the mean of at
least 10 separate measurements
taken at equal intervals. The
head range of the measuring
device shall be O. 2 - 1. 5 feet.
The capacities of weirs which conform
to these specifications are indicated
in Table 1.
4 Parshall flume
The Parshall flume is an open constricted
channel in which the rate of flow is
related to the upstream head or to the
difference between upstream and down-
stream heads. It consists of an
entrance section with converging
vertical walls and level floor, a throat
section with parallel walls and floor
declining downstream, and an exit
section with diverging walls and floor
inclining downstream. Plan and
sectional views are shown in Figure 2.
Advantages of the Parshall flume include
a low head requirement, dependable
accuracy, large capacity range, and
self cleaning capability. Its primary
disadvantage is the high cost of
fabrication; this cost may be avoided
by use of a prefabricated flume. Use
of prefabricated flumes during plant
surveys is becoming increasingly
popular..
a Standard equations
The dimensions of Parshall flumes
are specified to insure agreement
with standard equations. Table of
dimensions are available from
several sources 3, 4. For flumes of
6 inch to 8 foot throat width the
following standard equations have
been developed.
1) 6 inch throat width
Q = 2. 06 H 1. 58
a
2) 9 inch throat width
Q = 3.07 H 1.53
a
-------
Flow Measurement
TABLE 1 DISCHARGE OF STANDARD WEIRS
Crest Length Contracted Rectangular" Suppressed Rectangular" Cipolletti* 900 Trisngular*
(Feet) Weir Weir Weir Weir
(discharge-cfs) (discharge-cts) (dischq.rge-cts) (discharge-cts)
Max. Min. Max. Min. Max. Min. Max. Min.
1.0 .590 .286 .631 .298 .638 .301
1.5 1.65 .435 1.77 .447 1.79 .452
2.0 3.34 .584 3.65 .596 3.69 .602
2.5 5.87 .732 6.30 .744 6.37 .753
3.0 9.32 .881 10.0 .893 10.1 .903
3.5 13.8 1.03 14.8 1.04 15.0 1.05
4.0 19.1 1.18 20.4 1. 19 20.6 1. 20
4.5 25.6 1.33 27.5 1.34 27.8 1.35
6.55 .046
5.0 28.8 1. 48 30.6 1.49 30.9 1.51
6.0 34.9 1. 78 36.7 1.79 37.1 1.81
7.0 41.0 2.07 42.8 2.08 43.3 2.11
8.0 47.1 2.37 48.9 2.38 49.5 2.41
9.0 53.2 2.67 55.0 2.68 55.7 2.71
10.0 59.3 2.97 61.1 2.98 62.0 3.01
*H~0.2ft.H~I.5ft.H~ 1/3L
Converging
\, secti on
\
\
\
\
\
Diverging
sectiop
,
,
,
/
,
.'
section
PLAN
. .
FLOW
~
Ho
-"""'"=::::::::
-
"Water surface. s
".
df'~ggo(~,oo"b° 0
SECTION
FIGURE 2
PARSHALL FLUME
5
-------
Flow Measurement
Q CI free-flow discharge,
defined as that condition
which exists when the
elevation of the down-
stream water surface
above the crest, l\' does
not exceed a prescribed
percentage of the upstream
depth above the crest, H .
The prescribed percenta~e
of submergence is 60
percent for 6 and 9 inch
flumes and 70 percent for
1 to 8 foot flumes
water surface has already begun
to decline. Table 2 indicates the
total head requirements of standard
Parshall flumes. These losses
should be added to the normal
channel depth to determine the
elevation of the water surface at
the flume entrance. No head
losses are indicated for discharge-
throat width combinations for which
Ha is less than 0.2 ft. or greater
than 2/3 the sidewall depth in the
converging section.
3) 1 to 8 foot throat width
1 522W 0.026
Q CI 4WH .
a
where
c Accuracy and installation require-
ments
A Parshall flume will measure
discharge within t 5% of the
standard value if the following
conditions are observed.
W = throat width, feet
H = upstream head above the
a flume crest
1) The dimensions of the flume
shall conform to standard
specifications.
The head required by a Parshall
flume is greater than (H - Hb)
because Ha is measuredaat a point
in the converging section where the
2) The downstream head, Hb' shall
not exceed the recommended
percentage of the upstream head,
H.
a
b Head loss
TABLE 2 HEAD LOSS IN STANDARD PARSHALL FLUMES
UNDER FREE DISCHAR"C?;E
Discharge Head Loss, Feet, in Flume of Indicated Width
(ds)
1 foot 2 feet 3 feet 4 feet 5 feet 6 feet 7 feet 8 feet
0.5 .08
1.0 .14 .09 .06
2.5 .26 . 16 .12 .10 .08 .07 .06 .05
5.0 .42 .27 .20 .16 .13 .12 .10 .09
10.0 .70 .45 .34 .27 .22 .19 .17 . 15
30.0 .70 .56 .47 .40 .35 .30
50.0 .68 .57 .49 .41
H > 0.2,
a -
H < 2.0
a -
26-6
-------
Flow Measurement
3) The upstream head shall be
measured in a stilling well
connected to the flume by a pipe
approximately 1-1/2 inches in
diameter.
4) The flume shall be installed in a
straight channel with the centerline
of the flume parallel to the direction
of flow.
5) .The flume shall be so chosen,
installed, or baffled that a normal
distribution of velocities exists at
the flume entrance.
5 Tracer materials
Techniques, materials, and instruments
are presently being refined to permit
accurate measurement of instantaneous
or steady flow with several tracer
materials. Measurements are made by
one of two methods:
a Continuous addition of tracer
b Slug injection
With the first method, tracer is injected
into a stream at a continuous and uniform
rate; with the second a single dose of
tracer material is added. Both methods
depend on good transverse mixing and
uniform dispersion throughout a stream.
The concentration of tracer material is
measured downstream from the point
of addition. When continuous addition
is employed, flow rates are calculated
from the equation:
q . C = (Q + q) c
in which q = rate of tracer addition to
the stream at concentration, C, Q = the
stream flow rate, and c = the resulting
concentration of the stream flow com-
bined with the tracer. For the slug
injection method
Q =
s
cAt
in which Q = the stream discharg~,
S = the quantity of tracer added, c =
the weighted average concentration of
tracer material during its passage past
the sampling point, and At = the total
time of the sampling period.
Disadvantages of tracer methods include
mixing, natural adsorption
and interference, and high equipment
costs.
6 Floats
Floats may be used to estimate the time
of travel between two points a known
distance apart. The velocity so obtained
may be multiplied by O. 85 to give the
average velocity in the vertical.
Knowing the mean velocity and the area
of the flowing stream, the discharge
may be estimated. Floats should be
employed only when other methods are
impractical.
B Pipes and Conduits
1 Weirs and Parshall flumes
Weirs and Parshall flumes are commonly
installed in manholes and junction boxes
and at outfalls to measure flow in pipes.
All conditions required for measurement
of open channel flow must be observed.
2 Tracer materials
These methods are popular for
measurement of pipe flow because
they do not require installation of
equipment or modification of the flow.
These are especially convenient for
measurement of ex filtration and
infiltra tion.
3 Depth-slope
If the depth of the flowing stream and
the slope of the sewer invert are known,
the discharge may be computed by
means of anyone of several formulas.
a Manning formula
Q = ~ A R2/3S1/2
n
where
Q = discharge, cfs
26-7
-------
Flow Measurement
n = roughness coefficient
A = area of flow, sq. ft.
R = hydraulic radius, ft.
= area divided by wetted perimeter, ft.
S = slope, ft. per ft.
b Chezy formula
Q= CA~
where
Q = discharge, cfs
C '" friction coefficient
A = area of flow, sq. ft.
R = hydraulic radius, ft.
= area divided by wetted perimeter, ft.
S
= slope, ft. per ft.
4 Open end pipe flow
The following methods can be employed
when other more precise means are not
practical. They can be employed,
however, only when there is free dis-
char ge to the air.
a Coordinate method
(Figures 3,4, and 5)
Discharge may be computed by the
following formula: .
1800 AX
Q (gpm) '" y
where
A = cross sectional area of liquid
in the pipe (sq. ft.)
X = distance between the end of the
pipe and the vertical gauge in
ft., measured parallel to the
pipe.
26-8
Y = vertical distance from water
surface at the end of the pipe
to the intersection of the water
surface with the vertical gauge,
in ft.
AdJuJII,lnble nul so that
I ulll 1s parallel to R""r
and , alia 18 nrUC81
'(deplh In ...er1 ~-=-~_1-=-
~~"
b = (dlltucl t.... bot~ ot plpo to ..rtoci ot tllll.. liquid)
~
II
.
V
Q
~
- IIr
Por eloped; sewera or plpea:
OPEN-PIPE FLOW MEASUREMENT - THIS DEVICE, ADJUSTED TO THE
SLOPE OF A SEWER AND CALIBRATED, CAN THEN BE CLAMPED TO
THE SEWER OUTFALL.
....,.
Figure 3
x
--_..
-!
Q.--
..
~ "'"--
=-- --:::::-~~
--_-..:::--.:-~~
~ -===-:::-.~~~"
~~~~\-
~",~~~"
~~\\~\\\, ~
"\\\~~\~
~~ \\\\\~\\\,~
lIT
For sloped pipes:
OPEN-PIPE FLOVI MEASUREMENT RE(.UIRES !WO DIMENSIONS THAT
LOCATE THE SURFACE OF ST~EAM AFTER IT LEAVES THE PIPE.
-------.
Figure 4
-------
Flow Measurement
IhcnY'lrt
..
VolocH1 (V)
. 4.0 .
DlschorlP! In GPI!
. 450 AV
x (ft) to c:~t."r of stream
HOW TO MEASURE VELOCITY AND DISCHARGE FROM A PIPE.
Figure 5
b California pipe flow method
(Figure 6)
This method may be used only for
horizontal pipes having free dis-
charge. If the pipe is not horizontal.
a connection must be made to one
that is. The horizontal length must
be not less than 6 times the diameter
of the pipe. Discharge may be com-
puted by the following formula:
Q (gpm) = T X W
where T = 3.900 (1 - ~) 1. 88
d
W = d2.48
where a and d are measured in feet
~BiiE-~~
f ,,~~~
~n~d ~~~
,
MEASUREMENTS NEEDED FOR
CALIFORNIA PIPE FLOW METHOD
Inclined plpoe ehould be COIUIoctad to
o horlzonta' lonRth o( pipe b1 bo.a.
Figure 6
C Head Measuring Devices
Several of the above gauging methods re-
quire the measurement of water level in
order that discharge may be determined.
Any device used for this purpose must be
referenced to some zero elevation. For
example. the zero elevation for weir
measurements is the elevation of the weir
crest. The choice of method is dependent
upon the degree of accuracy and the type
of record desired.
1 Hook gauge
The hook gauge measures water eleva-
tion from a fixed point. The hook is
dropped below the water surface and
then raised until the point of the hook
just breaks the surface. This method
probably will give the most precise
results when properly applied.
2 Staff gauge
The staff gauge is me rely a graduated
scale placed in the water so that eleva-
tion may be read directly.
3 Plumb line
This method involves measurement of
the distance from a fixed reference
point to the water surface. by dropping
a plumb line until it just touches the
water surface.
4 Water level recorder
This instrument is used when a continu-
ous record of water level is desired. A
float and counterweight are connected
by a steel tape which passes over a
pulley. The float should be placed in
a stilling well. A change in water level
causes the pulley to rotate which. through
a gearing system, moves a pen. The pen
traces water level on a chart which is
attached to a drum that is rotated by a
clock mechanism. When properly in-
stalled and maintained. the water level
recorder will provide an accurate.
continuous record.
26-9
-------
Flow Measurement
ACKNOWLEDGMENT:
Certain portions of this outline contains
training material from prior outlines by
P.E. Langdon, A.E. Becher, and P.F.
Atkins, Jr.
REFERENCES
1 Planning and Making Industrial Waste
Surveys - Ohio River Valley Water
Sanitation Commission.
2 Stream Gauging Procedure. U. S. Geological
Survey. Water Supply Paper 888. (1943)
26-10
3 King, H. W. Handbook of Hydraulics.
4th Edition; McGraw-Hill. (1954)
4 Water Measurement Manual. United
Sta tes Department of the Interior,
Bureau of Reclamation. (1967)
This outline was prepared by F. P. Nixon,
formerly Acting Regional Training Officer,
Northeast Regional Training Center, OWP,
Edison Water Quality Laboratory, Edison,
NJ 08817.
-------
TRACING NATURAL WATERS
I
INTRODUCTION
The validity of water pollution studies is de-
pendent upon an ability to describe the actual
time and space situation of a pollutant as it
blends with the natural receiving water. This
understanding is important in order to predict
the subsequent effects of the pollutant on the
receiving water and subsequent users or to
detect the sources of pollution.
The nature of this blending is dependent upon
the physical and chemical properties of both
the pollutant and the receiving water as well
as the mixing and flow characteristics of the
receiving channel, basin, or aquifer. Tracing
is an attempt to approximate the actual motion
and mixing of this blend as it moves through
the channel, basin or aquifer.
Although there has been scant reference to
tracers in texts there has been rapidly in-
creasing number of technical articles de-
scribing their use in recent years. A com-
prehensive compilation of early radioactive
tracer studies may be found in the report of
the "Time of Flow Studies, Ottawa River,
Lima, Ohio,,(l) one of the early attempts to
compare various tracer techniques under
similar field conditions. Several reports
(see Bibliography) have discussed the use of
dyes 'during the early 1960's.
More refined and extensive tracer investiga-
tions may be expected as experience is gained
and as more complex studies arise. A water
quality agency should develop competence in
at least one tracer technique and would be
wise to be capable in some others as well.
II
PURPOSES
Tracer applications are still in a highly
developmental stage. One finds many words
or phrases to suggest similar field findings.
WP. SUR. tr.lb.:3, 71
In broad terms these measurements are con-
cerned with indications of mass movement,
blend mixing, and flow direction. Basically,
tracers are used to determine:
A Flow Rates
1
In freshwater channels or lakes such
terms as passage time, time of travel,
time of flow, flow quantity or flow
volume are used.
2 In estuaries such terms as rate of re-
newal, flushing rate, drift velocity,
mass transfer or net (tidal) drift are
used. The tidal fluctuation imposes a
need for consideration of flow reversal
effects.
3 In subsurface waters such terms as
recharge rate, flow rate and residence
time are used. Related factors such
as basin capacity, porosity and per-
meability are determined.
B Flow Direction
1
In estuaries
a Direction of flow relative to tidal
phases which do not necessarily
correspond to slack conditions.
b Obscure current circulation as in-
fluenced by the interlated factors of
tides, winds, Coriolis forces,
topography and density gradients.
2 In ground water
a Aquifer may flow contrary to initial
superficial impression.
b Hydrostatic conditions may change
and reverse normal flow direction.
27.1
-------
Tracing Natural Waters
C Mixing Patterns
1
Short circuit effects
a Eddying - primarily the result of
surface channel and basin
configuration.
b Stratification - primarily due to
temperature and density differences.
c Inter-connections - between aquifers
in ground water as well as solution
channels and open fractures.
2 Distribution phenomena
a Dispersion of colloidal, soluble and
suspended substances
b Diffusion of temperatures or gaseous
substances
III
TYPES OF STUDIES
Tracers are used in many situations,
including:
A Treatment Plant Units
B Closed Conduits
C Open Channels
D Large Water Bodies
E Hydraulic Models
F Subsurface Aquifers
G Subsurface Basins
IV
TYPES OF TRACERS
Materials used for tracers include:
A Floats
1
Surface (wooden and plastic devices as
well as fruit). Influenced by wind
action and debris.
27-2
2 Sub-surface "drogues". Apparent di-
rection must be carefully evaluated.
B Salts
1 Common salt - hard to detect when less
than 1 mg/l.
2 Brackish and freshwater mixing in
estuaries and coastal aquifers.
3 Ammonium chloride.
(See Table 1)
C Dyes, such as:
1
Rhodamine series - See section VI
2 pontacyl Brilliant Pink B - most stable
of fluorescent dyes. Rather expensive
dye.
3 Fluorescein - very inexpensive. Fluo-
resces very near natural stream back-
ground level.
4 Uranine - fluoresces near stream
background level.
D Radioactive substances, such as: (see
Table 2) AEC must approve all experi-
ments. AEC has published tables on
permissible concentrations in unrestricted
areaS. (13)
1
Rubidium -86
2 Iodine-131
3 Tritium (H3) gives b~st overall perfor-
mance in subsurface 6) tracing.
4 Krypton-85 - used recently in gas
transfer measurement in laboratory
and stream studies. (12)
E Waste return characteristics; significant
built-in factors such as:
1
Silt - understandably dependent upon
velocity and obstructions.
2 Foam - ABS will foam at levels as low
as 1 - 5 mg/l depending on hardness.
-------
Tracing Natural Waters
Table 1. SUBSURFACE NONRADIOlSOTOPE FLUID TRACERS
Remarks
Tracer Form
Chloride NaCl
Dextrose Sugar
Fluorescein
Dye
Chloride NaCl
Dextrose Sugar
Fluorescein
Dye
Dextrose Sugar
Ammonia Chloride
Fluorescein
Dye
Boron H3B03
Boron
Test conditions
Lab: Columns of sand and
sandy loam.
Field: 4 feet thick aquifer of
sand and gravel, 90 feet below
surface.
Field: Added in Conc. of 10,000
ppm, 500 ppm, 50 ppm, and 200
ppm respectively into a 4 foot
thick sand horizon at 2,100 feet
below surface in McKean
County, Pennsylvania.
Chloride most rapid. Fluores-
cein far from satisfactory,
Fluorescein considered best of
dyes. Chloride in the large conc.
required caused density currents.
Adsorption observed: dextrose -
little or none, boron - slight
(conc. dropped 300/0) ammonia -
moderate, fluorescein - strong
(moved at rate about 1/ 10 that of
flood water). Greenburg(33)found
that borax in Hanford fine sandy
loam penetrated only 2 feet.
Na2B407' 10H20 Field: Injection into input wells. Limit of3detection is reached
H3B03 Dilution factor "'5. after 10 dilution.
Thiocyanate
NH 4 SCN
Alkali - Metal
SCN
Rhodamine B
Oxygen-18
Deuterium
H20
HDO
Field: Water flooding.
Field: Karst topography.
Dilution possible 105.
6
Dye not detected after 6 X 10
dilution.
Variations resulting from sea-
sonal fluctuations are useful to
study climate. (Also useful in
meteorology and glaciology).
Reproduced with permission of Isotopes, Inc.
27-3
-------
Tracing Natural Waters
Table 2. SUBSURFACE RADIOISOTOPE FLUID TRACERS - FIELD TESTS(6)
Tracer Half-life Form Test conditions Remarks
H3 12.5 y. HTO Karst groundwater Useful results up to 30 km
distance.
Chalk River soil, undistur- Fluorescein dye traveled only
bed, but penetrated with about 3/4 as fast as tritium.
driven piezometers.
Glaciofluvial sand and gravel, Chromium complex traveled
various till soils, and fis- as fast as tritium.
sures and channels.
S35 89.d Na2S0 4 Chalk River soil at waste Lags behind tritium indicating
disposal site. some interaction with the soil.
In soil containing appreciable
amounts of gypsum there would
be exchange and loss of S35.
1131 8 d. Iodine, 4 feet thick aquifer of sand Should be used with several ppm
carrier free and gravel, 90 feet below stable iodine carrier.
surface.
1131 8 d. KI Tracer compounds used with C060 complex ~suitable in this
C060 5.2 y. EDTA - (Co) carriers KI, EDTA~(Na) and aquifer. K3Co (CN) appeared
and K3Co(CN)6' Limestone aqui- to be most suitable of tracers
K3Co(CN) 6 fer consisted of some argil- tested in limestone aquifer.
laceous material and marly
dolomite. Single-well pulse
technique.
Br82 36 h. NH4Br Aquifers in alluvium and per- Br82 satisfactory under these
meable strata in calcareous conditions.
marl series.
Rb86 19 d. RbCI Groundwater direction at re- Tracer detectable 7 miles from
servoir site in Egypt. injection after 5 d.
1131 8 d. NaI Single pulse tracing at dam Detected very high subterranean
p32 14 d. Na2HPO 4 site for Jesenitz Reservoir water velocity necessitating
on Odrava River in sealing of porous layer.
Czechoslovakia.
1131 8 d. NaI Single pulse tracing at dam Determined direction and velo-
82
Br24 36 h. NaBr site on arges River in city of flow of subsurface water.
Na 15 h. NaCI Roumania.
Reproduced with permission of Isotopes, Inc.
27-4
-------
3 Acid - severe effects upon total stream
ecology .
4 Temperature - infra-red filming
techniques reveal loC temperature
differences.
5 Lignins - "Orzan" is a commercial
product based upon these non -degrading
materials.
6 Dyes - prevalent in te~tile wastes.
F Biota, various techniques possible with:
1
Mammals
2 Fish
3 Shellfish
v
DESIRABLE CHARACTER~STICS
Ideally a tracer should be;
A Biologically innocuous to human and
aquatic life, with special reference to
1 Acute toxicity
2 Long-term toxicity
3 Carcinogenic effects
4 Genetic effects
B Stable or persistant despite the effects of
1
Stream chemical constituents
2 Bacteria
3 Sunlight
4 Adsorption
5
Temperature
6
Wind action
7 Inherent decay
Tracing Natural Waters
8 Channel obstructions
9 Stratification
C Readily detectable either
1 Visually and/or
2 Instrumentally despite dilution or
background effects;
D Representative: coincide with the real
waste and stream blend under study: this
involves miscibility and specific gravity
characteristics similar to the blend.
E Economic: this involves careful evaluation
of the costs for
1
Materials
2 Material preparation, and release -
ease of handling
3 Detection equipment
4 Detection technique and recording -
convenience in operation
5 Stream deterioration
F Esthetically agreeable: inoffensive to:
1 Taste
2 Sight - conflict with easy detection
VI
ELEMENTS OF A TRACER STUDY -
USING RHODAMINE DYES (Currently
in widespread use for surface studies. )
A Rhodamine Dyes
1 A vailable from American Cyanamid,
DuPont, Allied Chemical and General
Aniline.
2 Price $4.95 per pound except
Rhodamine WT which is $10.00 per
pound.
27-5
-------
Tracing Natural Waters
3 Specific gravity of 0.99 to 1. 12 depending
on the proportions of Alcohol, Ethylene
Glycol, Acetic Acid, and Water used as
solvents in preparing the solution.
4 Solutions normally 15%, 20%, 30%, or
40% dye by weight.
5 pH 1. 0 to 9. O.
6 Peak wavelength of adsorption at 525-556~
and of fluorescence at 548-585~ are not
normally found in natural waters.
7 Detectable to O. 5 ~g/l with continuously
sampling and recording equipment.
8 Visibly red to approximately 1. 0 mg/l.
9 Rapid dispersion when dropped in water.
10 Subject to some destruction by light, but
much less than experienced with
fluorescein.
11 Destroyed by agents such as hypochlorite.
Rhodamine WT is more resistant.
12 Essentially non-toxic.
B Measuring Equipment
1 Available from Turner Associates,
Beckman Instruments, Inc., American
Instrument Co., Inc.
so two or more runs with temperatures
covering the expected range of the study
water are desirable. Also it is advisable
to make a calibration with the study water.
This will check for background and any
difference in fluorescent characteristics.
A few helpful hints are:
1 Pumping a known concentration sample,
from a plastic bag immersed in a
constant temperature water bath,
through the .meter is a convenient
calibration procedure. Continuous
dousing with a concentrated solution
into the bag will give various instrument
readings through the detectable ranges.
2 Flush the system with methyl or butyl
alcohol solution before each calibration
to remove traces of dye.
3 Bubbles in the flow cuvette will cause
erratic readings.
4 The fluorometer door is not light tight,
so the instrument should be draped and
used out of intense light to prevent
erroneous high readings.
5 The sample lines on a continuous flow
system will transmit light through the
instrument door causing erroneous high
readings. Taping these tubes with
black electrical tape for about one foot
will alleviate problem.
2 Price as low as $1, 000 for photofluorometer D Study Procedures
complete or $500 for unit to modify a
spectrophotometer.
3 A vailable for individual grab sample
analysis or continuous analysis of
sample pumped through instrument.
4 Automatic recorders available.
5 Will measure several dyes (fluorescein,
rhodamine, etc.)
C Fluorometer Calibration
The instrument should be calibrated before
and after a study. The calibration is a
function of temperature (about 2.3%/0 C)
27-6
1 Select objectives which then dictate:
a Length of time to be studied
b Release point
c Monitoring locations and schedules
2 Determine physical properties of
affected area.
a Probable net flows
b Total water volumes
c Probable water temperature
-------
Tracing Natural Waters
d Natural fluorescent background
e Salinity
f Suspended solids
3 Estimate required quantities of dye
4 Calibrate fluorometers
5 Conduct mock run to test equipment
6 Public relations
7 Release and monitor dye
8 Process and interpret data
9 Report
VIII DISPERSION STUDY COMPUTATIONS
A Most Dispersion Equations are Normalized
Solutions of Ficks Second Law
2
2..£-D~
o t - x ih2
c = concentration, x = distance,
t = time, D = diffusion coefficient
x
B Hydraulic Model Studies of the Fate of
Pollution
From instantaneous release compute
steady state nonconservative pollutant
distribution
C(xy) = /f(t) + g (t)
where f(t) represents concentration
function and g (t) = decay function
C Coastal Water Dispersion Study, Hilo
Bay, Hawaii(9)
1
From instantaneous relea$e measu;r-e
concentration profile during slack
water
2 Using these measurements and a two
dimensional dispersion model com-
pute D and D .
x y
3 Two dimensional model
2 2
oc - D ~ + D ~ - U oc
at - x () x 2 y ()/ 0 x
- oc
V-
oy
U = velocity in x direction
V c velocity in y direction
Normalized solution:
C =
2=:~y exp - i [E - :~+~ - :~]
D Channel Studies
1
From instantaneous release compute
longitudinal dispersion coefficient
2 Measure time-concentration profile
at given station
3 This C vs. t curve fits equation
C =
(x - ut) 2
1 exp - 4 Dt
A(41TDt)Z
M
4 Take log of both sides
i - (M \ (x - ut) 2
Ct - log \A41TD) - 4 Dt log e
5
D can be determined from semi-log
1 2
plot of Ctl vs. (x - ut)
27-7
-------
Tracing Natural Waters
REFERENCES
1
Straub, C. P., Ludzack, F. J., Hagee,
G. R., and Goldin, A. S. Time of Flow
Studies. Ottawa River, Lima, Ohio.
Transactions, Amer. Geophysical
Union, Vol. 39, pp 420-426. 1958.
2 Feuerstein, D. L., and Selleck, R. E.
Flourescent Tracers for Dispersion
Measurements. Journal of the Sanitary
Engineering Division, ASCE, Vol. 89,
No. SA4, Proc. Paper 3586, pp 1-21.
August, 1963.
3
Buchanan, Thomas J. Time of Travel of
Soluble Contaminants in Streams.
Journal of the Sanitary Engineering
Division, ASCE, Vol. 90, No. SA3,
Proc. Paper 3932, pp 1-12. June, 1964.
4 Wright, R. R. and Collings, M. R. Appli-
cation of Fluorescent Tracing Tech-
niques to Hydrologic Studies. Hydraulic
Engrs., USGS, Atlanta, Ga., Jour.
A WWA, Vol. 56:748. June, 1964.
5 Pritchard, D. W. and Carpenter, J. H.
Measurements of Turbulent Diffusion
in Estuarine and Inshore Waters. Ches-
. apeake Bay Institute, Johns Hopkins
University. Contribution No. 53. 1960.
6 Ault, W.U., and Hardeway, J.E. Surface
Tracing with Radioisotopes. Isotopics,
Isotodes, Inc. Vol. 2 #1. January, 1965.
7 Diachishin, A. N. Dye Dispersion Studies.
Jour. San. Engr. Div., ASCE, Vol. 89,
No. SAl, Proc. Paper 3386, p. 29.
January, 1963.
27-8
8 O'ConneU, R.l.., and Walfer, C. M.
Hydraulic Model Tests of Estuarial
Waste Dispersion. Jour. San. Engr.
Div., ASCE, Vol. 89, No. SA 1, Proc.
Paper 3394, January, 1963. p. 51.
9 O'Connell, R. L., and Walter, C. M. A
Study of Dispersion in Hilo Bay, Hawaii.
Report prepared for the U. S. Army
Engineer District, Honolulu, Hawaii.
September, 1963.
10 Tsivoglou, E. C., et al. Tracer Measure-
ments of Atmospheric Reaeration. 1.
Laboratory Studies. Presented at the
Water Pollution Control Federation
Conference, Bal Harbour, Florida.
September, 1964.
11 Cawley, W. A. and Rutledge, W. C.
Application of Radioactive Tracer
Techniques to Stream Improvement.
Journal, San. Eng. Div., ASCE, Vol.
92, No. SAl, Proc. Paper 4640, p. 1,
February, 1966.
12 Tsivoglou, E.C., O'Connell, R.L..
Walter, C. M., Godsil, P. J., and
Logsdon, G. S. Tracer Measurements
of Atmospheric Reaeration-1. Labora-
tory Studies. Jour. WPCF, Vol. 37,
p. 1343.
13 U. S. Atomic Energy Commission, Re-
print from Federal Register, 17915,
Part 30.70, Dec. 17, 1964, p. 5.
14 American Cyanamid Company, A
Discussion of Techniques and Tracer
Dyes used in Water Tracing, Dyes
and Textile Chemicals Department -
Bound Brook, N. J. 08805.
This oUtline was prepared by Dale B. Parke,
Former Sanitary Engineer, Hudson- Delaware
Basins Office, ()NP, EPA, Edison, NJ.
-------
V SURVEY EVALUATION AND REPORT
Outline Number
Preparation of Survey Reports
28
Presentation of Data
29
Case Preparation and Courtroom Procedure
30
-------
WATER QUAUTY SURVEYS
PREPARATION OF SURVEY REPORTS
I
TYPE OF REPORT
The type of stream survey report to be pre-
pared depends on two basic factors. These
are the purpose and the audience for whom
intended.
o
A The Purpose of the Report
1 A report of findings or basic data
2 A report of existing causes and effects
together with an explanation of how and
why.
3 An exposition of existing causes and
effects and a projection of conditions
that reasonably may occur due to natural
variations in stream flow and temperature.
4 A purpose similar to 3 above plus a pre-
diction of the effects of population growth
and industrial change.
5 The same purpose as 4 above plus an
estimate of the need to protect water
uses, and cause reduction in waste
loads.
B The Specific Audience for Whom the Report
Is Prepared
1 For the record - no expository purpose
2 Other technical agencies with compe-
tencies in the same field
3 Other technical agencies in other fields
4 Public officials supporting or opposing
the recommendations of the report
5 The general public
C Both in style and content the report should
be adequate to serve as a basis for action
to accomplish the recommended objectives.
WP. SUR. 18b. 10.71
II
ORGANIZATION OF REPORT
A Title, Authors, Contents
B Acknowledgement of Aid and Assistance
1 Can be included in a letter of trans-
mittalor submission
2 Can be incorporate4 in a preface or
foreword
3
Should include names of persons and
of corporations, public and private,
who assisted or aided the survey
C Authority
1
Source of Authority
2 Date of authorization
D Report Summary
1 A brief summary of the report and its
recommendations generally precedes
the report proper and should include
three topics:
a Summary of specific findings
b Conclusions drawn from findings
c Recommendations in general terms.
2 Brevity is essential but not at the
expense of clarity.
3 A very brief but lucid description of the
stream section involved should be
included.
4 This will be the only part of the report
. read by many of its audience. Conse-
quently it should be drafted with the
utmost care.
28-1
" ...
-------
Water Quality Surveys
CLIMAX
MAJOR DETAILS
Iii
...
III::
...
~
u
z
iii
cr:
...
III::
(,,)
...
Q
Figure 1
5
Figure 1 illustrates the principles of
written communication format. It is
important that technical reports be
presented in factual report arrange-
ment and NOT in one similar to that
of fiction.
6
Figure 2 shows how the various
portions of a survey report relate
to the generalized factual report.
7 Recommendations, although briefly
stated in general terms, should be
couched in positive, unexaggerated
language.
8
Cost estimates of compliance with
recommendations is helpful but not
essential.
9 Both tangible and intangible benefits
may be listed briefly under conclusions.
E
INTRODUCTION
The body of the report should begin with a
statement of the problem and a discussion of
the reasons for and the location of the study.
2
o
l-
II)
...
III::
...
~
CHRONOLOGICAL
DEVELOPMENT
CLIMAX
SUMMARY.
CONCLUSIONS
RECOMMENDATIONS
Iii
...
III::
...
I-
!:
u
z
iii
cr:
...
III::
(,,)
...
Q
INTRODUCTION
METHODOLOGY
SUMMUIZED DATA
DATA ANAL YSIS
CONCLUSIONS
BASIS FOR RECOMMENDATI O'N
BIBLIOGRAPHY
SUBSTANCE OF
SURVEY REPORT
IINVE TED PYRAMID TYPE')
of writing structure
Figure 2
I
Sta tement of the problem
a A description of the area, empha-
sizing pertinent features, should
be included.
-------
Water. Quality Surveys
1) The inclusion of pertinent histor-
ical data is of value for audience
orientation.
2) The relationship of this study to
other current water resource
studies.
3) Water use and economic data may
be important.
b An area map is an absolute necessity.
1) Features included should be care-
fully selected and section of the
stream involved shou1,d be
emphasized.
2) Do not include unnecessary detail.
3) A general location map usually
orients the reader to the area
map.
2 Objectives of the Survey
a A statement of the purpose by listing
the specific answers sought by. the
survey to address various aspects of
the problem.
b The geographical and time scope of
the objectives of the survey.
F Survey Methodology
A 'complete description of the methods of
study employed is an important part of
the re cord.
1 The time period of survey should be
notec;l.
2 All sampling and gauging station loca-
tions should be identified by river
mile.
3 Sampling and analytical methods
a Provide adequate description of
all non-standard methods.
b An appendix for these descriptions
may be required if they are lengthy.
4 Frequency of sampling
5 Description of laboratory types and
locations
6 Hydrological methods employed for:
a Times of water travel
b Stream flow data
c Any waste flow measurements
G Survey Results
1 Sources of wastes
a Computed waste loads based on
known contributing populations and
industrial waste strength
b Results of sampling and gauging
program
c Data summaries or displays suffice
for text of report.
. 2 Stream data
a Summarized survey in the text
b Complete tabulations including time
of collection and averages in appendix
3 Hydrological data
a Usually tabulated with analytical
results both in the text and in
appendices
b Time of water travel curve or curves
c Stream flow frequency charts
d Pertinent groundwater data
4 Aesthetic considerations are of real
importance.
28-3
-------
. Water Quality Surveys
H Analysis and Interpretation ~f D~ta
1 Three fundamental procedures are
required:
a Comparison of survey results and
appropriate water quality criteria"
b Projection of survey data to provide
for comparison of stream conditions
with water quality criteria under
more adverse conditions
c Estimates of permissible wastes
loads under present and future
conditions.
2 Since this topic is the subject of other
outlines it will not be further developed
here.
3 A description of the methods of analysis
and interpretation belong in the report.
a Necessary assumptions should be
stated.
b All statistical methods used should
be identified.
4 Results of analysis and interpretation
are best presented in chart form insofar
as possible, to support discussion and
interpretation rationale.
I
Conclusions
1 Focus of attention, much of it critical,
is on this section of the report.
2 Clearness, conciseness, and positive-
ness are essential.
3 This section indicates reasoning that
leads from findings to conclusions.
28-4
J Recommendations
1 This is the crux of the report and
should answer the question, "What
needs to be done to resolve problems
delineated in the report?"
2 Cost estimates are highly desirable, if
possible, and appropriate.
K Bibliography
1 Useful to the student and perhaps to
future workers
2 Enta,ils additional time and effort in
assembling references in proper form
III
TECHNIQUES AND TOOLS
A Prepare a Detailed Outline
1 This is an important step if the cover-
age of the report is to be complete and
its arrangement logical. It is also a
time-saver if properly done.
2 Topics to be included in the outline will
become apparent from the foregoing dis~
cussion of report content.
B Words are Your Tools
1 Keep dictionary, thesaurus, and
glossa~~ available.
2 Define any vague terms or abbreviations.
3 Control superlatives and slang.
4 Avoid emphatics such as "it is to be
noted" or "it is a well-known fact".
5 Limit intensive expressions, such as
"extremely" or "undoubtedly. "
6 Use active verbs when possible.
C Regularly review the report organization
and development with a colleague.
This outline was prepared by Staff Members,
National Tr1iining Center, WPO~'. .~p A.
Cincinnati, OH 45268.
-------
PRESENTATION OF DATA
I INTRODUCTION
The data collected during any water quality
survey must ultimately be reduced to some
simple, expressive form for presentation.
Ideally, the data presentation should be
easily understood by the least trained per-
sonnel as well as by the trained professional.
The data presentation alone may determine
the response to the survey.
II ANALYSIS OF DATA
A Before one analyzes any information, the
data must be set into logical order and
the analyst must preseot the information
to himself.
In developing this order, the analyst should
keep in mind the objectives of the survey,
and the variables encountered during the
study.
The analyst's "private" presentation to
himself enables him to evaluate or inter-
pret the data in a logical and scientific
manner.
B
Orderly
Presentation / J Logic demands
\ order
Simple, .
..
. Logical" ...
/ ",
Interpretation Know Audience
\ ----
Scientifically Accurate
m
PRESENTATION OF DATA
This is one of the most important areas of
report writing and unfortunately is often
neglected or overlooked.
A Common Methods of Presenting Data
1 Single value
2 Single value plus related i~formation
3 Graphic methods
WP. SUR. in. 4a. 3. 71
B Single Value Approach
1 Methods commonly used
a Arithmetic mean
b Geometric mean
c Median value
d Mode value
2 Advantages of using single value approach
a Economical - engineering design
criteria is often based on average
values. In some instances minimum
and maximum values are more
critical.
b Instrumentation - advanced analytical
techniques and instrumentation are
accounting for the collection of tre-
mendous amounts of information.
The tendency is to compile this infor-
mation on computers and use sophis-
ticated statistical methods to arrive
at representative mean values.
c A udieoce - since some readers
(local, state or federal legislators)
do not have the technical background
or (especially), interest to read
through many pages of numbers, it
becomes convenient to summarize ';
the numerous observations by using
single representative values. In
effect, the analyst is a salesman,
his report being his product.
C Single Value Plus Related Information
"I Methods commonly used
a Single value plus maximum or mini-
mum value
b Single value plus pe'rcentage range
(usually BOo/e) of surveyor laboratory
results
c Single value plus standard deviations
from the mean (depending upon de-
gree of confidence req uired)
d Distribution and frequency distribution
tables
29-1 '
-------
Presentation of Data
2 Advantages of using single value plus
related information.
a Eliminates some misinterpretation
caused by extremely high or low
results that occur rarely.
b Gives an idea of what type of distri-
bution is occuring (normal, skewed,
etc. )
c Average values are extremely use-
ful but it is usually the maximum
or minimum values that pose serious
problems.
D Graphic Methods
One of the easiest, most attractive, and
most efficient ways to present numerical
information is by use of graphs.
1 Graphs commonly used
a Normal graph paper (Cartesian
Coordinate paper) - This is the
most generally used graph paper
and is most useful in obtaining an
idea of the trend the numerical
observations are taking. This type
of paper is most helpful in prelimin-
ary plotting of information to decide
if semi-log, log-log or other types
of functional graph paper would be
more desirable to use.
b Functional graph paper (semi-log,
log-log) - Use of this paper allows
for the plotting of results in straight
line fashion that would appear on
normal graph paper (Cartesian
Coordinate paper) as a curved line.
c Arithmetic or geometric (log) proba-
bility paper - this type of graph plots
the normal frequency curve (Bell
shaped curve) as a straight line.
d Nomograph - Used where complex
equations or complicated mathemati-
cal manipulations and calculations
are involved. Nomographs have
been develop"ed for numerous
applications.
e Special graphs
1
3-dimensional diagrams
2 pie-diagrams
29-2
3 histograms, etc.
2 Desirable characteristics of graphs
a Fairly simple
b Be able to stand alone
c Graphs should be designed so they
may be easily reproduced.
IV SUMMARY
The presentation of information is one of the
first steps in report writing. It is one of the
most important parts of any report and if
properly handled can produce a report that
is brief, understandable and useful to the
reader. The manner in which results are
presented (written or oral) may serve as a
basis for judgment of the whole survey.
This outline was prepared by P. F. Atkins,
Jr., Sanitary Engineer, formerly with Training
Activities, Ohio Basin Region, FWQA.
-------
CASE PREP.-\R."HIO:\ A:\D COl.RTROO::\I paOCEDrRE
TYPES OF PROCEEDI:\GS 1:\ WHICH
"".-\ TER QL-\UTY EVIDE:\CE ::\L-\Y
BE rSED
.-\ Administrative Proceedings
1 Rule making
a
Setting up of regulations haYing
general application, e. g., stream
classifications and implementation
plan target dates
b Factors of safety and absolute
prohibitions may be appropriate
2 Adjudications
a Determinations by agency having
expertise with respect to particular
discharge or discharger, e. g.,
approval of plans and specs and
time schedule of a particular
discharger
B Court .-\ctions
1
Civil in behalf of state or federal
government
"a !~ctions to compel action or sus-
pension of action - nuisance, health
hazard, etc., --including court
action following federal conference
- - hearing procedure
b
Violations of Water Quality Standards
c Violations of Effluent Standards or
discharge permits
d Tort or contract actions relating to
design and/ or operation of treatment
facilities
2
Criminal (dependent on content of
applica ble statute s)
a Discharge of specific materials
\'-.Q.l£.la.l.72
b Discharges from specific industries
c
Littering
d Discharges harmful to fish and/or
crl'staceans
e Discharges harmful to specific
types of receiving ""aters
f
Discharges of poisons
:\OTE- - In some of these situations
doing the act may constitute
the viole-tion; in others
proof of intent or knowledge
of effects may ah:o have to
be proved.
3 Prh-ate actions for damages or
to compel action
a .-\lleged harm to plaintiff, e. g. ,
pollution of stream killing animals
C Procedural ::\Iatters
1
See .-\ttached sheet ".-\dministrative
and Court Proceedings" on Burden
of proof, fact finding, and methods of
presentation of evidence.
D Classes of Evidence - General Rules
1
Facts - direct
a The material was floating from
the outfall.
2
Derived values - expert testimony
- test results and/ or opinion as to
effects
a The D. O. was zero; the waten'"ay
""as polluted; the plant can be built
in 6 months.
3
Hearsay
a Joe told me
;)0-1
-------
Case Preparation and Courtroom Procedure
4 Relevancy
5 Admissibility vs. weight
a Even if admissible, the weight to be
given is up to fact finder--credi-
bility.
E Admissibility of Results of Sampling
and Testing (Numbers)
1
Sampling
a Chain of custody
b
Tags, etc.
c Containers
d Place and time
e Retention of samples (Proving that
the sample represents what is at
issue in the action (relevancy), that
there has been no opportunity for
tampering; and availability of
portions for analysis by other side
(non-transitory criteria) ). .
2 Analysis
a Who performed (Can identity of
each participant be shown?)
b Admission through supervisor -
custodian
c Scientific acceptance of method.
Is there a particular method required
to be used by the agency?
d Propriety of conduct
e Retention of bench cards and other
indicia of results. (Your attorney
can make arrangements to substitute
copies for originals).
3
Te sts
a Comparison with actual conditions
b Mathematical models - how can a
computer be cross-examined?
30..2
F
Admissibility of Expert Opinion on
Causes and Effects
1 Who has special knowledge - and of
what particular areas?
2 Indicators
3
Significance of num€rical determin-
ations or observations
4 Consistency with own prior publications
and testimony
5 Have underlying facts been or need to
be proved- -first hand information of
this and/or comparable situations.
6 Use of treatises
G Conduct on the Witness Stand
1 Gerleral
a On direct - know what counsel will
ask and let him know generally
what you will answer, but don't
make it sound rehearsed.
b Use layman's language to extent
possible.
c
Listen to question and answer it
to best of your ability.
d Speak so that court reporter, judge,
jury, and counsel can hear you.
e Speak in language that will be
understood; don't talk down.
f
Answer only what you are asked
- - don 't volunteer; however, answer
with precision.
g There is nothing wrong with asking
to have a question repeated or
rephrased.
h There is nothing wrong with saying
that you consulted with your
attorney before you testified, but
beware of the question "Did Mr. X
tell you what to say? "
-------
i
There is nothing wrong with thinking
out your answer before responding.
You are not expected to know all
the answers--if you do not know,
admit it.
k Don't attempt to answer questions
outside your area of personal
knowledge (hearsay) or beyond your
expertise. (Your may be an expert
on conducting laboratory tests, but
not on epidimeological inferences
from results).
1
Don't try to answer before the judge
rules on objection.
m Show that you are an impartial
dispenser of information and/ or
opinion, not a protagonist.
n Don't be afraid to admit what may
appear to be damaging.
2
If you are testifying as an expert:
a Establish qualifications - - give
information relevant to your area
of expertise - - educational (in-
eluding this course?), work,
publications, number of times you
have testified previously.
b
Differentiate between physical facts
(measurements and observations)
and opinion (derived values).
c Be prepared to discuss theory (in-
cluding assumptions) instruments
used, techniques(including choice
of a particular technique), physical
limitations and errors, inter-
ferences.
d If experiments were conducted,
be able to justify both as to theory
and relevancy to this litigation.
e
If you're being paid to testify,
admit it.
3
Scientific personnel as advisers to
counsel:
Case Preparation and Courtroom Procedure
a
Review and refamiliarize self with
materials before you discuss with
your attorney.
b Be in a position to present all facts
known to you simply and concisely:
Who, What, When, Where, and
Why, How.
c Don It overlook facts and/ or test
results because you don't think
theylre important. Let attorney
decide what he needs.
d Use of standard report forms
e Ability to recommend additional
witnesses with needed specialized
knowledge
f
Ability to aid in cross-examination
of other side's experts and reconcile
opinions and/ or results
g Be candid - sometimes better not
to start a lawsuit or accept a
settlement than lose in the end.
H Non-Verbal Presentation of Evidence
1
Exhibits - including photographs
2
Summaries
3
Business and/ or government records
a Prepared cQntemporaneously and
in usual course of activities
4 Pre-prepared direct examination
a Usually limited to actions before
ICC, FPC, and other federal
agencies.
1
Criminal Procedure
1 Privilege Against Self Incrimination
(available only to persons)
a Warning and suspects
b
Effect of duty to report spills
3'()-3
-------
Case Preparation and Courtroom Procedure
c Effect of duty to obtain license or
permit and/ or furnish operating
reports
d Immunity from prosecution
2
Double Jeopardy
30~4
3 Unreasonable search and seizure
a Available to persons and
corporations
4 Procedures and need for arrest and
search warrants -- possible cause
This outline was prepared by David 1. Shedroff,
Enforcement Analyst, Office of Enforcement
and General Counsel, Cincinnati Field
Investigations Center, 5555 Ridge Avenue,
Cincinnati, OH 45268.
Administrative & Court Proceedings,
and Excerpts from Revised Draft of
Proposed Rules of Evidence for the
United States Courts can be found on the
following pages.
-------
Court or A~ency
State Pollution Control
Agency
Rule making-adjudi-
cation
Federal Water Pollution
Control Act
Conference
Hearing
Court
Court
Civil Case --
- for money only
- injunction
preliminary or
temporary
pe rmanent
- administrative
appeal
w
o
I
CJl
Criminal case
includes penalties
ADMINISTRATIVE & COURT PROCEEDINGS
Fact Finder
Comments
Agency
Head of agency
Hearing Boatd
Judge
Judge or jury
Judge
Judge
Judge - whether
"arbitrary and
capricious" or sub-
stantial evidence.
Jury unless waived.
Burden of Proof
As per statute -
usually weight of
evidence.
W eight of evidence
Must show immediate
harm or danger.
Usually clear and convincing.
Beyond reasonable
doubt.
Hearing may be conducted by hearing
examiner, agency member, or full
agency. Appeal may be on facts and
law or law alone, depending on statute.
C1
PJ
m
(1)
"d
Ii
(1)
"0
PJ
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~
.....
g
~
p.
C1
o
~
:4-
Ii
o
o
S
"d
Ii
o
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(1)
g.
Ii
(1)
Reports acceptable.
Specific testimony.
Uses prior material. and may take
additional testimony.
Must also show likelihood of success at
final hearing - bond required for non-
government plaintiff. .
"Balance Equities"
Sometimes have complete new trial.
Proof of intent may be required.
-------
Case Preparation and Courtroom Procedure
Excerpts from Revised Draft of Proposed
RULES OF EVIDENCE FOR THE UNITED STATES COURTS
GENERAL PROCEDURES
Rule 102.
PURPOSE AND CONSTRUCTION
These rules shall be construed to secure fairness in administration, elimination
of unjustifiable expense and delay, and promotion of growth and development of
the law of evidence to the end that the truth may be ascertained and proceedings
justly determi~ed.
Rule 101.
PREUMINARY QUESTIONS
(a) Questions of Admissibility Generally. Preliminary questions concerning the
qualification of a person to be a witness, the existence of a privilege, or the
admissibility of evidence shall be determined by the judge, subject to the pro-
visions of subdivision (b). In making his determination he is not bound by the
rules of evidence except those with respect to privileges.
(b) Relevancy Conditioned on Fact. When the relevancy of evidence depends upon
the fulfillment of a condition of fact, the judge shall admit it upon, or subject to,
the introduction of evidence sufficient to support a finding of the fulfillment of the
condition. .
Rule 615.
EXCLUSION OF WITNESSES
At the request of a party the judge shall order witnesses excluded so that they
cannot hear the testimony of other witnesses, and he may make the order of his
own motion. This rule does not authorize exclusion of (1) a party who is a natural
person, or (2) an officer or employee of a party which is not a natural person
designated as its representative by its attorney, or (3) a person whose presence
is shown by a party to be essential t? the presentation of his cause.
Rule 611.
MODE AND ORDER OF INTERROGATION AND PRESENTATION
(a) Control by Judge. The judge may exercise reasonable control over the mode
and order of interrogating witnesses and presenting evidence so as to (1) make the
interrogation and presentation effective for the ascertainment of the truth, (2) avoid
needless consumption of time, and (3) protect witnesses from harassment or undue
embarrassment.
(b) Scope of Cross-Examination. A witness may be cross-examined on any matter
relevant to any issue in the case, including credibility. In the interests of justice,
the judge may limit cross-examination with respect to matters not testified to on
direct examination.
30-6
-------
Case Preparation and Courtroom Procedure
Rule 613.
PRIOR STATEMENTS OF WITNESSES
(a) Examining Witness Concerning Prior Statement. In examining a witness
concerning a prior statement made by him, whether written or not, the state-
ment need not be shown or its contents disclosed to him at that time, but on
request the same shall be shown or disclosed to opposing counsel.
JUDICIAL NOTICE
Rule 201.
JUDICIAL NOTICE OF ADJUDICATIVE FACTS
(b) Kinds of Facts. A judicially noticed fact must be one not subject to reasonable
dispute in that it is either (1) generally known within the territorial jurisdiction of
the trial court or (2) capable of accurate and ready determination by resort to
sources whose accuracy cannot reasonably be questioned.
(g) Instructing Jury. The judge shall instruct the jury to accept as established
any facts judicially noticed.
RELEVANCE
Rule 401.
DEFINITION OF "RELEVANT EVIDENCE"
"Relevant evidence" means evidence having any tendency to make the existence
of any fact that is of consequence to the determination of the action more probable
or less probable than it would be without the evidence.
Rule 402.
RELEVANT EVIDENCE GENERALLY ADMISSIBLE;
IRRELEVANT EVIDENCE INADMISSIBLE
All relevant evidence is admissible, except as otherwise provided by these rules,
by other rules adopted by the Supreme Court, by Act of Congress, or by the
Constitution of the United States. Evidence which is not relevant is not admissible.
COMPETENCY OF WITNESSES
Rule 601.
GENERAL RULE OF COMPETENCY
Every person is competent to be a witness except as otherwise provided in these
rule s .
3 ()~7
-------
Case Preparation and Courtroom Procedure
Rule 602.
LACK OF PERSONAL KNOWLEDGE
A witness may not testify to a matter unless evidence is introduced sufficient
to support a finding that he has personal knowledge of the matter. Evidence to
prove personal knowledge may, but need not, consist of the testimony of the
witness himself. This rule is subject to the provisions of Rule 703, relating to
opinion testimony by expert witnesses.
EXPER T TESTIMONY
Rule 702.
TESTIMONY BY EXPER TS
If scientific, technical, or other specialized knowledge will assist the trier of
fact to understand the evidence or to determine a fact in issue, a witness qualified
as an expert by knowledge, skill, experience, training, or education, may testify
thereto in the form of an opinion or otherwise.
Rule 703.
BASES OF OPINION TESTIMONY BY EXPERTS
The facts or data in the parHcular case upon which an expert bases an opinion or
inference may be those perceived by or made known to him at or before the hearing.
If of a type reasonably relied upon by experts in the particular field in forming
opinions or inferences upon the subject, the facts or data need not be admissible
in evidence.
Rule 705.
DISCLOSURE OF FACTS OR DATA UNDERLYING EXPERT OPINION
The expert may testify in terms of opinion or inference and give his reasons
therefore without prior disclosure of the underlying facts or data, unless the
judge requires otherwise. The expert may in any event be required to disclose
the underlying facts or data on cross-examination.
Rule 706.
COURT APPOINTED EXPERTS
(a) Appointment. The judge may on his own motion or on the motion of any
party enter an order to show cause why expert witnesses should not be appointed,
and may request the parties to submit nominations. The judge may appoint any
expert witnesses agreed upon by the parties, and may appoint witnesses of his
own selection. An expert witness shall not be appointed by the judge unless he
consents to act. A witness so appointed shall be informed of his duties by the
judge in writing, a copy of which nhall be filed with the clerk, or at a conference
in which the parties shall have opportunity to participate. A witness so appointed
shall advise the parties of his findings, if any; his deposition may be taken by any
party; and he may be called to testify by the judge or any party. He shall be subject
to cross-examination by each party, including a party calling him as a witness.
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Case Preparation and Courtroom Procedure
HEARSAY
Rule 801.
DEFINITIONS
The following definitions apply under this Article:
(a) Statement. A "statement" is (1) an oral or written assertion or
(2) nonverbal conduct of a person, if it is intended by him as an assertion.
(b) Declarant. A "declarant" is a person who makes a statement.
(c) Hearsay. "Hearsay" is a statement, other than one made by the declarant
while testifying at the trial or hearing, offered in evidence to prove the truth
of the matter asserted.
Rule 802.
HEARSAY RULE
Hearsay is not admissible except as provided by these rules or by other rules
adopted by the Supreme Court or by Act of Congress.
Rule 803.
HEARSAY EXCEPTIONS: AVAILABILITY OF DECLARANT IMMATERIAL
The following are not excluded by the hearsay rule, even though the declarant is
available as a witness:
(5) Recorded Recollection. A memorandum or record cuncerning a matter about
which a witness once had knowledge but now has insufficient recollection to enable
him to testify fully and accurately, shown to have been made when the matter was
fresh in his memory and to reflect that knowledge correctly. If admitted, the
memorandum or record may be read into evidence but may not itself be received
as an exhibit unless offered by an adverse party.
(6) Records of Regularly Conducted Activity. A memorandum, report, record,
or data compilation, in any form, of acts, events, conditions, opinions, or
diagnoses, made at or near the time by, or from information transmitted by,
a person with knowledge, all in the course of a regularly conducted activity, as
shown by the testimony of the custodian or other qualified witness, unless the
sources of informatio:l or other circumstances indicate lack of trustworthiness.
(18) Learned Treatises. To the extent called to the attention of an expert witness
upon cross-examination or relied upon by him in direct examination, statements
contained in published treatises, periodicals, or pamphlets on a subject of
history, medicine, or other science or art, established as a reliable authority
by the testimony or admission of the witness or by other expert testimony or by
judicial notice. If admitted, the statements may be read into evidence but may
not be received as exhibits.
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Case Preparation and Courtroom Procedure
IDENTIFICATION OF PERSONS AND SAMPLES
Rule 90l.
REQUIREMENT OF AUTHENTICATION OR IDENTIFICATION
(a) Gen8ral Provision. The requirement of authentication or identification as a
condition precedent to admissibility is satisfied by evidence sufficient to support
a finding that the matter in question is what its proponent claims.
(b) Illustrations. By way of illustration only, and not by way of limitation, the
following are examples of authentication or identification conforming with the
requirements of this rule:
(1) Testimony of Witness with Knowledge. Testimony that a matter is what it is
claimed to be.
(3) Comparison by Trier or Expert Witness. Comparison by the trier of fact or
by expert witnesses with specimens which have been authenticated.
(9) Process or System. Evidence describing a process or system used to produce
a result and showing that the process or system produces accurate result.
ADMISSIBIUTY AND PROOF OF SPECIAL MATTERS
Rule 406.
HABIT; ROUTINE PRACTICE
(a) Admissibility. Evidence of the habit of a person or of the routine practice of an
organization, whether corroborated or not and regardless of the presence of eye-
witnesses, is relevant to prove that the conduct of the person or organization on a
particular occasion was in conformity with the habit or routine practice.
(b) Method of Proof. Habit or routine practice may be proved by testimony in the
form of an opinion or by specific instances of conduct sufficient in number to warrant
a finding that the habit existed or that the practice was routine.
Rule 612
WRITING USED TO REFRESH MEMORY
If a witness uses a writing to refresh his memory, either before or while testifying,
an adverse party is entitled to have it produced at the hearing, to inspect it, to
cross-examine the witness thereon, and to introduce in evidence those portions which
relate to the testimol1Y of the witness.
Rule 1006.
SUMMARIES
The contents of voluminous writings, recordings, or photographs which cannot
conveniently be examined in court may be presented in the form of a chart, summary,
or calculation. The originals, or duplicates, shall be made available for examination
or copying, or both, by other parties at a l'easonable time and place. The judge may
order that they be produced in court.
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