STP 442a-1978
STP 442a-1978
(Fourth Edition)
Sponsored by
Committee D-19
on Water
AMERICAN SOCIETY FOR
TESTING AND MATERIALS
NOTE
The Society is not responsible, as a body,
for the statements and opinions
advanced in this publication.
ASTM Committee D-19 on Water had long believed that something more
than standard methods of testing are needed by those who look to the Society
for aid and technical guidance. It was felt that general discussions of the
nature and uses of water should illuminate these prescribed procedures and
specifications. Hence, the ASTM Manual on Water.
Preparation of the first edition of the manual was begun in 1946. The first
manual task group consisted of R. C. Adams, chairman and editor, A. A.
Berk, T. H. Daugherty, O. M. Elliot, J. A. Holmes,' C. E. Imhoff,1 A. K.
Light, F. U. Neat,1 F. R. Owens, and A. H. Reynolds.1 Each member drafted
an assigned portion of the manual with the assistance from his associates and
other members of Committee D-19. These drafts were modified, critiqued,
correlated, and assembled by the entire task group so that the resulting
manual was a group product rather than a compilation of individual
authorships. Many persons not in the task group also contributed to the first
edition. Particular acknowledgment should be made for the individual
contributions of Max Hecht,1 L. K. Herndon, E. O. Patridge,1 and C. K.
Rice.
The second edition task group consisted of R. D. Hoak, 1 chairman and
editor, F. N. Alquist,1 R. A. Baker, G. D. Beal, F. E. Clarke, E. F. Davidson,
B. W. Dickerson, D. K. French,1 A. S. Goldin, J. E. Kinney, W. W. Leathen,
S. K. Love, W. A. Moore, F. R. Owens, J. K. Rice, C. C. Ruchhoft, 1 R. K.
Scott,1 J. M. Seamon, J. B. Smith, F. N. Speller,1 and R. F. Weston.
Substantial contributions were also made by C. K. Rice, D-19 Standards
Advisor.
The third edition task group consisted of J. F. Wilkes, chairman and
editor, R. A. Baker, F. E. Clarke, E. F. Davidson, R. D. Hoak,1 C. E.
Imhoff, 1 R. S. Ingols, J. K. Jacobsen, Pratt Johnson, Bernd Kahn, F. N.
Kemmer, R. A. Larrick, S. K. Love, J. A. Martucci, W. L. Neiland, E. P.
Partridge,1 J. H. Phillips, E. A. Savelli, J. S. Speer, and S. L. Williams.
Again, many of those named had worked on the previous edition. Prepara-
tion of the manual was a collaborative effort, involving the entire group plus
many other D-19 members not assigned to the group. The major decision to
remove the standard methods of analysis of water from the manual was
made. These methods and specifications are published annually as the
Annual Book of ASTM Standards, Part 31. Each year all newly accepted
methods and revised methods are incorporated into the reissued book.
'Deceased.
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Contents
Introduction 1
Chapter 1—Water Sources and Supply 3
Chapter 2—Uses of Industrial Water 18
Chapter 3—Production and Preservation of Ultrapure Water 28
Chapter 4—Effects of Composition on Industrial Use 38
Chapter 5—Treatment of Process Water and Waste Water 46
Chapter 6—Technology of Industrial Water Reuse 84
Chapter 7—Self-Purification and Other Natural Quality Recovery
Mechanisms 97
Chapter 8—Thermal Loading of Water Supplies 107
Chapter 9—Sampling and Flow Measurement of Water 118
Chapter 10—Water Quality Monitoring 145
Chapter 11— Analysis of Water and Waste Water 177
Chapter 12—Sensory Examination of Water 254
Chapter 13—Sampling and Identification of Deposits in Steam and
Water Systems 276
Chapter 14—Chemical Analysis of Deposits 307
Chapter 15—Sediment in Streams and Other Water Bodies 319
Chapter 16—Radioactive Nuclides in Water 327
Chapter 17—Nuclear Water Technology 352
Chapter 18—Practices for Measurement of Radioactivity 387
Appendix—Reference Tables and Curves 443
Index 459
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STP442A-EB/Jul. 1978
Introduction
previous editions. It has been developed to satisfy the growing need for
dependable information about the characteristics of water and the problems
its use and reuse entail. New chapters have been added to highlight problem
areas and to suggest new approaches for their identification and solution.
The five new chapters are: Production and Preservation of Ultrapure
Water, Chapter 3, which discusses this problem area and the need for the
definition of solutions thereof; Chapter 15, Sediments in Streams and Other
Water Bodies, describes the state of the art in this newly developing field;
Nuclear Water Technology, Chapter 17, pulls together information and
experience in this relatively new water field; and Chapter 18 deals with
practices for the measurement of radioactivity.
Water Quality Monitoring, Chapter 10, while not all new material, has
been expanded extensively with the addition of sections on surveillance and
sample conditioning. The other thirteen chapters have been updated and
revised to a lesser extent over the previous edition. The Appendix has also
been revised but still contains much useful information for the water analyst
or engineer.
A new task group is now being organized to consider further new material,
revisions, and updating of the current edition. If you have comments or
suggestions of material which you think would be helpful to you or to other
users of the manual, please contact the ASTM D-19 Committee on Water.
C. E. Hamilton
Dow Chemical Company,
Midland, Mich. 48640;
editor.
STP442A-EB/Jul. 1978
example, in the North Atlantic Slope area, runoff averages about 5.1 x 102
m 3 /day (136 Bgd); in the Mississippi River basin the average is about
1.5 X 109 m 3 /day (400 Bgd); in the Colorado River basin it is about 5.7 X
107 m3day (15 Bgd); and in the Columbia River basin, about 8.4 X 10*
m 3 /day (223 Bgd).
In 1960 the national average runoff was equivalent to about 25 000
litres per capita per day (led) (6500 gal per capita per day) (gcd). Based on
population growth projections, this figure would be about 18 000 led (4800
gcd) in 1980 and 13 000 led (3500 gcd) in the year 2000. If the total runoff
to the oceans could be apportioned equally to each person, there would be
enough water from this source on a national basis for the foreseeable future.
But based on actual current and anticipated future distribution of popula-
tion and available water resources, the per capita figure may range from as
little as 11 000 litres/day (3000 gal/day) (gpd) to as much as 110 000
litres/day (30 000 gpd).
Groundwater—Invisible Source
In the discussion on runoff, the figures given for runoff to the oceans
include groundwater. The water falling as precipitation to the ground
follows three courses. Some runs off directly to streams and rivers, some
infiltrates to the ground water reservoirs, and the rest evaporates or
transpires through vegetation.
The water in the ground may be thought of as a temporary natural
reservoir. It is invisible and consequently to many people is shrouded in
mystery. Nearly all groundwater is in constant though slow motion toward
streams or other surface water bodies. In fact, in dry periods streams
maintain their flow because of groundwater discharge. Thus the water
discharging through streams to the oceans includes most of the runoff from
the groundwater reservoir. The remainder discharges by underground
routes.
Groundwater reservoirs store far more water than is or conceivably could
be stored in surface reservoirs. The available and accessible supply of ground-
water in the United States is estimated to be in excess of 2.2 X 1014 m3
(59 000 000 billion gallons) [7].' However, when large quantities are being
sought it usually is more difficult and expensive to locate, to study and
evaluate, to develop, and to manage groundwater than surface water.
Furthermore, the management of groundwater is complicated by defi-
ciencies and incorrect concepts of groundwater hydrology and by much of
existing water law. Development of groundwater as a phase of coordinated
multiple-purpose water management can be achieved on a large scale only if
adequate hydrologic information is available [2].
'The italic numbers in. brackets refer to the list of references appended to this chapter.
CHAPTER 1 ON WATER SOURCES AND SUPPLY 5
The cost of converting saline water has been reduced substantially during
the past 20 years. Cost at the conversion plant ranges from about $0.60 to
$1.50 per thousand gallons depending on the process used, the salinity of the
raw water, the capacity of the plant, and other factors. Distribution cost
would have to be added.
In areas where adequate quantities of freshwater are not available, certain
kinds of industries and domestic uses probably can justify the cost of
converted saline water. Reuse of fresh or converted water will keep cost of
industrial water to a minimum.
Water Demands
Demands for water for all purposes are constantly increasing. Estimates of
present and future demands will suggest how the available water resources
should be utilized.
6 MANUAL ON WATER
Water Withdrawals
Many estimates have been made about the quantities of water that are
withdrawn from our surface and underground sources for useful purposes.
Among those frequently quoted are estimates compiled by the U. S. Senate
Select Committee. The total water withdrawn in 1954 for all uses, excluding
hydropower, was about 3.4 X 108 m3 (300 Bgd), which was equivalent to
about 6800 led (1800 gcd). Of this amount 58 percent was used for irrigation,
36 percent for industry, and 6 percent for public supplies, rural and other
purposes. A projection by the Select Committee [3] to the year 2000
anticipates total water use of about 3.1 X 109 m3 (900 Bgd), of which over 70
percent will be used by industry. However, only about one fifth of the water
withdrawn would be consumed and most of this by agriculture.
In another estimate [4} the total water withdrawn in 1960 was 1.0 X109 m3
(270 Bgd), of which 51 percent was for industry, 40 percent for irrigation, 6
percent for public supplies, and 1 percent for rural use.
From 90 to 95 percent of industrial water is used for cooling. After cooling
is accomplished, the water is returned to the water system for reuse. The heat
removed in cooling processes is transferred from the industrial equipment to
the water as it reenters the hydrologic system. The higher temperature tends
to upset the delicate balance established by living plants and animals
indigenous to the receiving streams. The heated water also reduces oxygen
solubility and increases the biochemical oxygen demand, thus producing an
oxygen sag in the streams. In extreme cases, other pronounced and complex
quality changes will occur as a result of the temperature change. As larger
quantities of water are employed for cooling, some of the other uses of water
will be affected to some degree.
Consumptive Use
Consumptive use of water has been defined as ".. . the quantity of water
discharged to the atmosphere (evaporated) or incorporated in the products
of the process in connection with vegetative growth, food processing, or
incidental to an industrial process" [5].
Industry consumes only about 2 percent of the water it uses. This is
divided principally between water evaporated and water incorporated in
products of manufacturing. The heaviest consumption is in connection with
irrigation, where 60 percent or more of the water withdrawn is lost to the
water system through evaporation and transpiration. About 17 percent of
water used for public supplies is consumed.
Storage
Water is stored in reservoirs to control floods, develop power, provide
water supplies for municipalities, industries, and irrigation, dilute wastes,
stimulate recreation, and for other beneficial uses. In 1954 [6] a total of
CHAPTER 1 ON WATER SOURCES AND SUPPLY 7
3.4 X 10" m^ (278 000 000 acre-ft) (91 000 billion U. S. gal) was stored in
conterminous United States having usable capacities of 6.2 X.106 m3 (5000
acre-ft) (1.6 billion U. S. gal) or more.
The distribution of these storage capacities by states is given in Table 2.
U. S.
Billion
0
State Acre-Feet Gallons'
Alabama 2 522 900 822
Arizona 33 246 800 10 834
Arkansas 9 561 800 3 116
California 17 700 900 5 768
Colorado 3 826 700 1 247
TABLE 2—Continued.
Usable Storage
U. S.
Billion
State Acre-Feet " Gallons b
Reusable Supplies
Most of the water withdrawn is not consumed but is returned to a
downstream or underground source. Thus the total supply is depleted by
only a portion of the entire amount withdrawn. For this reason the water
returned augments the original supply and is available for reuse. Were it not
for reuse, some areas would have run out of water. It must be kept in mind,
however, that each use of water (except for generation of hydropower) will
degrade its quality to some extent. Impoundment of water for hydropower
or other uses can cause significant changes in water quality.
Hardness
Because of the importance of the hardness characteristic of industrial
waters, this topic will be discussed in greater detail. For many industries, the
hardness of the intake water is the principal basis for classifying water.
Hardness is defined in accordance with the ASTM Definitions of Terms
Relating to Industrial Water and Industrial Waste Water (D 1129) [7], as a
characteristic of water generally accepted as representing the total con-
centration of calcium and magnesium. Although other constituents, such as
iron, manganese, and other polyvalent cations cause hardness, they usually
are present in such small concentrations that they do not materially affect
the hardness of industrial water. Only calcium and magnesium are included
in the term hardness as used in this discussion.
Hardness may be divided into two types, carbonate and noncarbonate.
Carbonate hardness includes that portion of the hardness which is equiva-
lent to the carbonate and bicarbonate present in the water. Any hardness in
excess of this amount is called noncarbonate. Carbonate hardness generally
is not objectionable in industrial use of water. Where it is excessive, however,
it can be reduced or removed rather simply and inexpensively. Noncar-
TABLE 3—Analyses of typical surface and groundwaters in the United States. [From U. S.
Geological Survey Water Supply Paper 1812 (milligrams per litre).]
Analysis number? 1 2 3 4 5 6 7 8
Date of collection 8/22/61 9/1/61 10/19/61 1961 8/9/61 9/15/61 8/23/617/25/61
Silica (SiCh) 5.9 2.1 5.5 8.7 25 8.3 9.1 21
Iron (Fe) 0.00 0.17 0.40 0.03 0.72 0.10 0.01
Manganese (Mn) 0.00 0.14 0.00 0.01 0.06 0.00
Calcium (Ca) 8.5 28 37 84 65 12 57 26
Magnesium (Mg) 2.6 7.0 8.9 28 23 6.1 32 6.2
Sodium (Na) 3.6 4.1 17 92 14 7.5 3.4 86
Potassium (K) 1.5 0.9 5.1 4.0 1.8 0.7 1.7 1.9
bonate hardness, on the other hand, especially where sulfate is the pre-
dominant anion, may result in formation of hard, adherent scale in boilers
and other heat-exchange equipment. This type of hardness is more difficult
and more costly to remove.
Any descriptive or numerical classification of hardness of water is
arbitrary. A water that is termed hard in some areas may be considered soft
in other areas. The U. S. Geological Survey uses the following classification:
Range of Hardness
mg/ litre (ppm) Descriptive Classification
I to 60 soft
61 to 120 moderately hard
121 to 180 hard
Above 180 very hard
Figure 1 shows the hardness in the foregoing ranges for the finished public
supplies of the 100 largest cities in the United States in 1962. The numbers in
the map identify the cities listed in Table 4. The tables also gives, in figures,
the approximate average hardness in these cities.
FIG. 1—Hardness of treated public water supplies of the 100 largest cities in the United
States, 1962 (average weighted by population served).
1-2 MANUAL ON WATER
TABLE 4—Hardness of finished water supplies of 100 largest cities in the United States, 1962.
[From\J. S. Geological Survey Water-Supply Paper 1812 (hardness in milligrams
per litre of calcium carbonate).]
Number on map Average
State (Fig. 1) City Hardness
Alabama 1 Birmingham 88
2 Mobile 35
3 Montgomery 42
California 6 Fresno 82
7 Long Beach 110
8 Los Angeles 110
9 Oakland 58
10 Sacramento 65
11 San Diego 235
12 San Francisco 35
13 San Jose 205
Colorado 14 Denver 78
Connecticut 15 Bridgeport 31
16 Hartford 28
17 New Haven 42
Georgia 23 Atlanta 23
24 Savannah 105
Hawaii 25 Honolulu 60
(Continued)
CHAPTER 1 ON WATER SOURCES AND SUPPLY 13
TABLE 4—Continued.
Number on map Average
State (Fig. 1) City Hardness
Louisiana 38 Baton Rouge 5
39 New Orleans 91
40 Shreveport 60
Maryland 41 Baltimore 55
Massachusetts 42 Boston 13
43 Springfield 12
44 Worcester 15
Minnesota 48 "Minneapolis 65
49 St. Paul 90
Mississippi 50 Jackson 50
Oregon 76 Portland 7
(Continued)
14 MANUAL ON WATER
TABLE I—Continued.
Number on Average
State map (Fig. 1) City Hardness
Pennsylvania 77 Erie 120
78 Philadelphia 105
79 Pittsburgh 110
Tennessee 81 Chattanooga 87
82 Memphis 40
83 Nashville 92
Texas 84 Amarillo 215
85 Austin 88
86 Corpus Christi 135
87 Dallas 90
88 El Paso 97
89 Fort Worth 145
90 Houston 60
91 Lubbock 310
92 San Antonio 230
Virginia 94 Norfolk 77
95 Richmond 60
Washington 96 Seattle 20
97 Spokane 150
98 Tacoma 15
Wisconsin 99 Madison 290
100 Milwaukee 130
Summary
The country is not likely to run out of water in the foreseeable future. The
total water supply is essentially the same now as in the past and will be in the
future. The distribution of water, however is highly variable as to time and
place. In addition, the needs for water on a countrywide basis cannot be
correlated with its availability.
Industrial water requirements must be carefully assessed in terms of the
quantity and quality of water that can be obtained at the plant site. If the
available supply is not of suitable quality, the cost of conditioning must be
weighed against the costs of making available other water sources or other
plant locations.
CHAPTER 1 ON WATER SOURCES AND SUPPLY 17
References
[/] Nace, R. L., "Water Management. Agriculture and Ground Water Supplies," II. S.
Geological Survey Circular 415, 1960.
[2\ McGuinness, C. L., "The Role of Ground Water in the National Situation," U. S. Geolog-
ical Survey Water-Supply Paper 1800, 1963.
[3] Select Committee on National Resources, U. S. Senate, "Water Supply and Demand,"
Committee Print No. 32, 1960.
[4] MacKichan, K. A. and Kammerer, J. C., "Estimated Use of Water in the United States,
1960," U. S. Geological Survey Circular 456, 1961.
[5] Task Group Report, American Water Works Association, "Water Conservation in
Industry," Journal of the American Water Works Association, JAWWA, Vol. 45, 1953,
p. 1249.
[6\ Thomas, N. O. and Harbeck, G. E., "Reservoirs in the United States," U. S. Geological
Survey Water-Supply Paper 1360-A, 1955.
[7] Annual Book of ASTM Standards. Part 31.
STP442A-EB/Jul. 1978
Since earliest times, men have settled along the shores of rivers and lakes to
avail themselves of freshwater for their homes and industries. The American
colonists built their mills along streams which could furnish power and
supply the quality of water necessary for the manufacture of such goods as
textiles and paper.
In modern times, public awareness of the importance of water is mounting
as headlines warn of a growing problem of water quality and availability.
The expanding industry must carefully examine the limitations which water
may impose on it: How much raw water will be available ten years hence?
Can a portion of the plant's usage be reduced by recycle? What quality water
might be required by new uses? How can this quality be achieved economi-
cally while impurity levels in the raw water supply continue to rise? What
degree of waste treatment is required to preserve the stream water quality?
To help bring these problems into perspective, this chapter on the uses of
industrial water outlines general principles and practices rather than specific
details of water usage by individual industries.
There are few, if any, significant uses of water which are peculiar to a
single industry. The major uses—steam generation, cooling, and pro-
cessing—are common to all industries. Of the various categories of process
uses of water, such as conveying and washing, many appear in a variety of
plants unrelated in any other way.
These general principles and practices are presented to orient the engineer
toward good water management in his own industry. The examples illus-
trating water use in several specific plants were selected for their universal
appeal. In them, engineers in all branches of industry will find practices
related to their own operations.
Heat Transfer
Industry capitalizes on the large heat capacities of water for economical
heating or cooling of process units.
The most common method of supplying heat to various areas of an
industrial complex is by steam generation. The steam is produced from fuel
at a central generating station and distributed at relatively high pressure and
velocity throughout the plant. Temperature at each unit is easily controlled
by regulating flow or pressure.
In addition to the steam generated by direct firing of a boiler with coal, oil,
or gas, additional steam may be produced by firing waste products or by
recovering heat from a high-temperature process stream. Some typical
process heat boilers (sometimes called "waste-heat boilers") are described in
Table 1.
Although steam historically has been the major conveyance of industrial
heat because of high heat capacity and heat-transfer coefficients, hot water is
replacing it in some of the newer plants. This is due to the lower installation
20 MANUAL ON WATER
Power Generation
By far the greatest share of our total power generation comes from
steam plants. The public utilities today produce over 9 x 1012 kJ/day
(2.5 billion kWh/day) of electricity by this route. Most of these plants
recover the steam with condensers, so that the water makeup is usually
extremely low—less than 1 percent. However, some of these utility plants
have been located adjacent to industrial plants to whom they supply both
electricity and steam. This steam is often consumed or contaminated, so that
such plants may require as much as 50 percent makeup. A typical arrange-
ment of this kind involves a utility station adjoining a refinery. The refinery
supplies the utility water from its private source and fuel, and the utility
supplies its neighbor electricity and low-pressure steam.
The industrial plant generatinfflteteam for power differs from the utility
station in the relatively greater extent of water loss, with higher makeup, in
the variation and degree of condensate contamination, and in the tempera-
ture of the returned condensate.
A major reason for the relatively larger makeup rate in industrial plants is
the unfavorable cost of installing piping to return condensate from a large,
complex plant. A typical case is the petroleum refinery where some of the
steam is sent to the outlying tank farm to heat heavy, viscous oils and keep
them pumpable. Not only is it costly to run douple piping to return
condensate, but, in this case, recovery is unattractive because of the
likelihood of oil contamination. It is certain that the future will bring greater
pressure to reclaim a large share of industrial condensate which until now
has appeared not worth recovering.
The relatively high temperature of industrial process condensate is due to
the steam being condensed at high temperatures. In the utility station, steam
is expanded through a turbine to subatmospheric pressure and finally
condensed in a condenser by cooling water. The condensate returned to the
system is only a few degrees warmer than the discharged cooling water. In
the industrial plant, the condenser is the process equipment, and it usually
operates at pressures above atmospheric. Therefore, the industrial plant
typically returns condensate at 65 to 121° C (150 to 250° F) as compared to 38
to 49° C (100 to 120°F) utility condensate.
The industrial steam plant may use steam to drive machinery, to generate
electricity, or both. The paper mill is a good example of this. A typical mill
will produce steam at 6205 kPa (900 psi). This may be used through a
number of turbines to drive pumps, generators, compressors, paper ma-
chines, and auxiliary equipment. Some of the steam will exhaust to an 862-
kPa (125-psi) steam line, used to heat the large drier rolls over which the
paper passes. Other drier rolls may operate at 413 kPa (60 psi). This steam
will also go to cooking the wood chips in a digester to make pulp. Some of
the turbines in the power plant may expand the high-pressure steam all the
way down to vacuum, as a utility operation, to obtain maximum thermal
efficiency. A typical paper mill system is shown in Figure 1.
22 MANUAL ON WATER
In some geographical areas, the electrical energy cost may be so low that
the industrial plant cannot afford to generate electricity even though the
steam is available. Such is the case, for example, with a paper mill in the area
served by Tennessee Valley Authority. All turbines discharge steam at 413
kPa (60 psi) or above, none operate with condensers, and only mechanical
power is produced from the steam.
Even the tax structure plays an important part in the decision as to the
best use to make of steam in an industrial plant. Corporate tax rates tend to
favor higher operating costs as against extra capital costs which could lower
operating costs. As a result, industry tends to depreciate capital equipment
at a more rapid rate than do the utilities. Because of this, industry has not
been encouraged to install the higher-pressure (over 8274 kPa) (1200 psi)
steam generating plants which utilities are finding so economical to operate.
/The generation of mechanical power from water flowing through hy-
draulic turbines recalls the early days of the industrial revolution and the use
of the water wheel to mill grains. A number of industrial plants today
continue to use natural hydraulic power for mechanical jobs or for
generation of electricity. In some parts of Canada, the excess of hydro-
electric power and its low cost is such that at times of the year it is actually
cheaper to generate steam in electric boilers than in fuel-fired boilers.
In addition to making use of natural hydraulic power, industry also uses
CHAPTER 2 ON USES OF INDUSTRIAL WATER 23
Air must then be used to help lift the water-sulfur mixture to the surface,
since the sulfur is insoluble in water.
The mounting cost of oil exploration and oil well development has led to
secondary and tertiary recovery of remnant oil from older fields by water
and steam flooding. Specially treated water, brine, or water-steam mixture
is pumped underground to displace oil from zones where it had escaped
capture by primary methods. Water must be treated for this purpose by
rather sophisticated means to avoid plugging the underground formation
with debris.
Other examples of water's job as a conveyor can be found in such diverse
industries as food, where water carries vegetables in canning plants and beets
in the beet sugar mills, and coal, where pulverized coal is transported long
distances by pipeline as a water slurry.
To some extent, almost every industry uses water as a conveyor and
diluent for wastes, just as man does in his own society through sewerage
systems.
Even in the vapor phase, water is an effective conveyor. In steam
distillation processes, the bubbling of steam in a vessel containing an organic
liquid causes a mixture of water vapor and hydrocarbon to be discharged in
a molecular ratio equal to the ratio of the individual vapor pressures of the
two materials. Steam is also used for the evacuation of other gases from an
enclosure. An example is the use of steam jet eductors on turbine condensers
to continually remove noncondensible gases from the condenser shell to
prevent gas-binding the heat-transfer surfaces.
Water for Washing—Water is convenient and economical to use for
general cleanup of industrial equipment. Aside from the aesthetic view,
washup of equipment is important from such practical considerations as
safety (personal injury may result from slipping on debris accumulated on
the operating floor), quality (trash may find its way into the products), and
production (equipment may be damaged by dirt). The nuclear industry
probably has the most elaborate procedures of any industry for washup.
Equipment exposed to accumulations of radioactive particles is throughly
cleansed with detergents and rinsed copiously with water.
CHAPTER 2 ON USES OF INDUSTRIAL WATER 25
opposite side, flat sprays of water wash the pulp and displace the remaining
liquor through the mat to the collection pipe for recovery and reuse.
A similar displacement process is used to remove and recover caustic soda
from mercerized cotton fabric. The recovered caustic is then freed of
cellulosic material by washing it in a dialyser. In this apparatus, caustic on
one side of a membrane is extracted by water on the other side, leaving the
large carbohydrate molecules behind.
Washing by extraction is practiced in many industries. It is used in most
domestic oil refineries to remove salt from crude oil so that the salt will not
foul distillation columns. Water is pumped into the crude oil, amounting to
about 4 percent of the oil flow, and thoroughly mixed for maximum salt
extraction. Emulsion breaking chemicals may then be added, just before the
oil passes into a vessel having electrodes to break the water out of the oil and
cause it to separate by gravity.
Refined sugar is also washed by water extraction during centrifuging. The
wash water removes the film of molasses from the crystals of sugar so that
the final product will be white and free-flowing.
The widespread growth of air conditioning has led to thfc use of water for
washing debris from air. Often the temperature of the wash water will be
closely controlled to provide the correct humidity in the cleaned air. This has
become increasingly important in the aerospace industry, where entire
assembly rooms must be completely dust-free to avoid any dirt accumulation
on machined surfaces or control devices.
Hydraulic classification may be considered as a special form of water-
washing. Water acts as a medium for separation of a desired material from
its contaminants, as in the separation of slate from coal and in froth flotation
in the mining industry.
Water as a Raw Material—Many a schoolboy has been startled by the
demonstration in his chemistry class of the sputtering reaction of sodium
metal with water, evolving caustic soda and hydrogen. Mercury cell caustic
soda is manufactured in much the same way, the sodium in the amalgam
reacting thus:
In this reaction, oxygen is split from the water molecule. Coal also reacts
with steam in this way in gas producers to manufacture illuminating gas.
CHAPTER 2 ON USES OF INDUSTRIAL WATER. 27
Water of high quality becomes the bulk of the finished product in the
beverage industry. Each beverage has its own quality standards, ranging
from an exceptionally clear water for carbonated beverages (even traces of
suspended matter greatly reduce the degree of carbonation) to a fully
demineralized water for deproofing of alcoholic beverages.
Water is similarly an important raw material for the drug industry. It
becomes a part of many liquid formulas, including parenteral solutions.
Water may be considered as a convenient vehicle for many chemicals.
Many acids are aqueous solutions of acidic gases in water, such as hydrogen
chloride (HC1), sulfur trioxide (S(b), and phosphoric anpydride (P^s).
Household ammonia is a solution of ammonia gas in water. Caustic soda,
which was described earlier as manufactured by reacting sodium with water,
is kept in an excess of water and handled entirely as a solution by a number
of plants. This saves the cost of evaporation necessary to produce solid
sodium hydroxide.
Summary
Water is essential to most industries. Its value is earning increased
recognition. Each plant is becoming cognizant of the need to be alert to its
use of water and to the quality required of each use. A water balance sheet
should be prepared and kept up to date by every water-using industry both
for its own protection and as a part of its obligation as a good neighbor.
The aspects of water sources, quality standards, use, and reuse are
explored in other chapters of this manual. Of one thing we may be certain:
There will be no end to discovering new jobs for water to perform for
industry, nor will its importance in existing jobs diminish.
STP442A-EB/Jul. 1978
The word water probably has as many meanings as there are people
discussing the term. This chapter attempts to define and limit a particular
type of water called "ultrapure" water so that the reader will be in a better
position to draw up his own definition within the scope of his own use of the
material.
having been made by Adams and Holmes in England in 1936 with the
development of the synthetic gel-type anion resins. During the decade
starting in 1940, patents were issued or applied for, or both, on most of the
basic cation and anion exchange materials in use today. Similarly, appli-
cations were made on the four-bed process and the mixed-bed process of
utilizing these various materials, which formerly had been employed only in
single- or two-bed configurations.
In addition to distillation and ion exchange, the historical methods of
producing pure water include the preparation of small quantities by burning
pure oxygen and hydrogen and the use of freeze crystalization techniques.
Both of these techniques will be covered briefly later under methods of
preparation; however, neither was employed to produce any significant
quantities of ultrapure water. Over the past 20 years, numerous other
improvements have been made in the design of stills, ion exchange systems,
various membrane processes, and in the chemical structure of ion exchange
materials. However, with a few exceptions, references to these improvements
will be omitted. The reader interested in pursuing such information is
referred to Properties of Ordinary Water Substance by Ernest Dorsey,
which is not only a very valuable source of reference information, but is the
most complete compilation available of information on water properties.
Also, a review by Greppin on the preparation and preservation of pure water
produced by distillation and ion exchange contains over 100 references.
has been heavily dependent upon ultrapure water for its success since
essentially all semiconductor and microelectronic development and experi-
mentation has involved the use of ultrapure water as a cleaning agent. It is
conceded that molecular quantities of contaminants can ruin the yield of
production runs of electronic components and make the development of
others completely impossible. It has been postulated that one part of copper
in 10 million billion (1015) parts of water can be the difference between
success and failure. The reason for this critical water requirement is based on
its use as a solvent or final rinse in almost every chemical processing step
used in the production of basic electronic components. The industry has
developed to the point where complete electronic packages are much smaller
than the head of a pin. The circuits within these packages are in the
dimension range of one micrometre, which means that any particulate
matter much larger than 0.2 yum can cause failure of a device.
Prior to World War II, pure water was used in the rinsing of components
of electron tubes. However, it is well known that these tubes failed after a
relatively short life of perhaps two or three years. Following World War II,
the importance of contamination control in the production of electron tubes
became obvious and relatively large water purification plants were installed
to improve the reliability of tube production. This was particularly notice-
able in the television tube industry since each tube produced required
approximately 190 1 (50 gal) of ultrapure water. During this period, it also
became evident that contamination-free electron tubes could be produced
which would have an estimated life of perhaps 20 years. This type of life
expectancy was essential for all components being used in such systems as
the repeater stations installed in the transatlantic telephone cables. It is
important to recognize that, without a source of ultrapure water as a final
rinse for the components of these devices, their production would have been
impossible. As the industry became aware of the importance of con-
tamination-free water in the production of electronic tubes, the semi-
conductor industry was developed in the late 1950's, which added to the
requirements for much larger volumes of water of even higher quality. The
state of the art is fast approaching the point where absolute water, free of
molecular quantities of all types of impurities, will become desirable if not
essential to the production of electronic components.
Water passing this specification might then be used to grow another type of
tissue of a sensitive nature. The rinsing of standard semiconductor devices
could also be used to detect molecular contaminants and could be the basis
of a definition of molecular-free water.
Since molecular quantities of impurities may be measured by various
theoretical techniques, it is quite possible that the actual number of
molecules in the water may be used to define the grade of water. Another
measure of the purity or type of water may depend upon the polymetric
structure of the water molecule, which may vary depending upon the
preparation techniques and the previous history of the water. The various
isotypes of hydrogen and oxygen combined to form water molecules can
also be of significance and may be another basis for a series of definitions.
Classification of Impurities
Any discussion of pure water or ultrapure water must include some
parameter on the type and limit of impurity; otherwise, the entire discussion,
whether on the method of purification, the method of handling, or the
method of testing for impurities, will be meaningless. Ultrapure water to
many, especially to those involved in central power station operations and
the pharmaceutical and electronics industries, has been pretty well defined
by the industry. This chapter may, therefore, seem somewhat theoretical and
impractical; on the other hand, it is possible that individuals within the
industries may wish to revalue their definition based upon some of the
changes in the methods of preparation and preservation which are outlined.
Since any investigator considering the use of ultrapure water usually has an
idea about the types of impurities which cause difficulty to his experiment or
process, he should govern his method of preparation and preservation in
such a way as to prevent contamination from the undesirable constituents.
The preparation and preservation based on the elimination of contaminants
might be conducted considering those contaminants which can generally be
classified as liquids, solids, or gases.
In some instances the classification may be unclear. In general, however,
the physical state of the impurity can be postulated. A further breakdown of
the contaminants may be made by classifying the materials ^as organics,
which generally are all compounds containing carbon in any form, or as
inorganics, which are essentially all substances which do not contain carbon
in their molecular structure.
Generally speaking, liquid impurities are the most difficult of all to
remove if one is attempting to produce ultrapure water, particularly if the
impurities fall in the classification of miscible organic substances. Examples
of this impurity might include alcohol, liquid detergents, and organic acids
such as acetic or citric acid. Many of these substances that ionize may be
removed by ion exchange, as would be the case with acetic acid, and might
also be removed quite effectively by adsorption. Large-molecular-weight
36 MANUAL ON WATER
oxidizing agents followed by distillation, as was the foregoing case with the
organic matter. The development of reverse-osmosis membranes has made
the use of this system practical.
STP442A-EB/Jul. 1978
Corrosion
Corrosion is probably the most ubiquitous and expensive problem in
water collection and distribution systems, water treatment equipment, and
water-using equipment. Its effects range from such spectacular hazards as
boiler explosions to the downgrading of product quality as a result of the
presence of corrosion products in process water.
The total cost of corrosion in the United States has been estimated at $50
billion annually. The ruptured boiler must be replaced, as must the leaking
water pipe, but there are many other direct or indirect costs resulting from
corrosion. Among these are the increased power required for pumping, the
reduced product yields resulting from inefficient cooling, and the increased
costs from the use of equipment with heavier walls and expensive alloys to
compensate for corrosion.
Although the fundmental corrosion reactions are simple, the form and
rate of corrosion are influenced by subtle and complex interactions of
design, construction, and operation that make corrosion prevention and
control a far from simple task. Corrosion is generally understood as the
deterioration of a metal in its environment. Although nonmetallic materials
such as plastics and wood also deteriorate in their environment, this
deterioration is generally not considered as corrosion. More specifically,
corrosion is the solution of some portion of a metal in its environment as the
result of a chemical, electrochemical, or physical process.
The following tend to intensify corrosion at the metal-water interface,
either by increasing the rate or by increasing the localization of attack.
Since corrosion is essentially a chemical reaction, the rate increases as the
CHAPTER 4 ON EFFECTS OF COMPOSITION ON INDUSTRIAL USE 41
Steam Generation
More than a few micrograms per litre of any substance is regarded as an
undesirable pollutant in water to be fed to a boiler producing steam at a
pressure in the range above 13 790 kPa (2000 psi). Even for the pressures of
4137 to 10 342 kPa (600 to 1500 psi) in many contemporary power plants,
dissolved salts as well as suspended solids are often limited to the milligrams
per litre range in the makeup. At lower pressures, operation with appreciable
dissolved solids is accepted practice. General values for water quality
guidelines for boiler feedwater and boiler blowdown quality as developed by
the ASME Research Committee on Water in Thermal Power Systems are
listed in Table 1.
Processing Materials
Some industrial processing operations can be conducted with almost any
quality water. An example is the washing of fines from bituminous coal. In
other processes, only demineralized water of the highest quality is employed.
The manufacture of microelectronic components is an example often cited,
but the production of electrolytic tin plate free of pinholes requires water of
similar high purity. Between these extremes lie many special situations.
There is no standard approach to providing water for industrial operations.
Consider a few of the many criteria:
Color due to the natural decomposition of vegetation, to the oxidation of
dissolved iron or manganese, or to various constituents of municipal or
industrial wastes must be minimized in water used for processing natural and
synthetic fibers, washing and dyeing the fabrics woven from them, and
manufacturing clear plastics or quality paper of high brightness.
Suspended solids in a range of particle size from those which can be
readily removed by sedimentation to those so small that they remain
dispersed for long periods of time are an almost universal pollutant of river
water. In relation to the trouble they cause in most process operations, the
cost of their removal is sufficiently low as to justify clarification, either as an
initial step or as an additional benefit of softening by precipitation.
Dissolved salts in water that might be considered of the highest quality for
drinking must nevertheless be considered as pollutants if they cause oper-
ating difficulties, impair product quality, or impose costs for treatment to
remove them.
44 MANUAL ON WATER
Incorporation in Product
Taste and odor are vital considerations in water used for brewing beer or
bottling nonalcoholic carbonated beverages, for food processing, and phar-
maceutical industries.
Color is a critical characteristic in water for club soda.
Dissolved salts should be low in water used for making artificial ice to
minimize opaque accumulations of solids in the last water frozen.
Calcium and magnesium in water used for cooking peas and other
vegetables for canning toughen them undesirably.
mean that this water is suitable for industrial use. Further treatment usually
is needed to minimize its total cost.
While natural impurities can always cause some kind of trouble wherever
water is used by industry, man has compounded his problems exponentially
in two ways. While multiplying his numbers, he has increased tremendously
his control of power and his capabilities for manufacturing products to meet
many new wants in addition to old needs. Throughout the industrial
expansion of the past two centuries, he has conveniently flushed his sanitary
and his industrial wastes into the nearest stream or lake.
From the strictly economic viewpoint for our society as a whole, the
optimum control of this pollution would be that which leads to the lowest
total of all the costs to all the groups using and reusing the water through its
complete path back to the reservoir of the oceans. But water also has
aesthetic and recreational values which are leading us as a society to pay
more than the minimum number of dollars which would be needed for the
optimum level of control on a strictly economic basis.
Keeping water reusable provides a promising alternative to transportation
of water from a diminishing number of sources at increasing distances from
the point of use, and to the recovery of usable water from the. oceans.
However, the cost of controlling entry of the wastes of society into our
presently available water will not be small.
STP442A-EB/Jul. 1978
The purification of water for industrial use can be very complex or rela-
tively simple, depending upon the properties of the raw water and the degree
of purity required. There are many methods and combinations in use, but all
are covered in three basic processes: physical, chemical, and physicochemical
treatment.
A fourth basic process, biological treatment, is often employed where
waste water must be purified before it may be discharged. This process takes
advantage of the ability of living microorganisms to induce a variety of
chemical and physicochemical reactions. Treatment of waste water is usually
a much more complicated operation than the production of process water of
appropriate quality.
This chapter discusses these processes as they are used in the treatment of
industrial water and waste water and outlines some of the technical problems
and basic considerations involved.
Physical Treatment
Physical treatment pertains to those processes in which there is separation
of impurities from water without chemical change. The common methods
are sedimentation, straining and filtration, multiliquid phase separation,
degasification, dilution, removal of entrainment, distillation and stripping,
underground discharge, and ocean discharge.
Sedimentation
Sedimentation is the process by which the force of gravity acts on particles
heavier than water and causes them to move downward and settle out.
Surface waters contain varying amounts of suspended material, and this
process is used to clarify raw water either by simple sedimentation or with
the addition of chemical coagulants. The tanks in which this action takes
place are called sedimentation basins.
Particle size, weight, shape, frictional resistance, and viscosity play an
important part in the design of such tanks. Theoretical calculations usually
are based on modifications of Stoke's law and the assumption that the
Copyright© 1978 by ASTM International www.astm.org
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 47
particles are spheres. Many factors must be considered in design, and all of
these must be modified as judgment and experience dictate. The theory of
design will not be given here; it will suffice to state that effective clarification
can be accomplished in tanks that are properly designed and operated.
Settling basins may be constructed of earth, wood, concrete, or steel. They
may be rectangular or circular. The usual period of retention ranges from 4
to 12 h. Where the water contains large amounts of settleable solids, the
basins often are provided with mechanical scrapers which move the settled
sludge to a sump from which it is forced out by the hydraulic head of water
in the basin. In other instances, manual sludge discharge valves are provided
to remove some of the settled material; it is necessary to remove such units
from service at regular intervals for thorough cleaning.
Inlet and outlet distribution of the fluid must provide for uniform flow in
the basin if efficient operation is to be attained. In rectangular tanks, the
influent is distributed by a trough equipped with adjustable sluice gates or
plug valves, and the effluent is usually discharged over a weir or series of
weirs. Circular units are provided with a center distributor and an overflow
launder at the periphery of the tank.
Short-circuiting often plagues the operation of rectangular basins,, thereby
decreasing the theoretical retention time. This can be overcome by im-
proving the inlet distribution or by effective use of muffle boards at the inlet
and sometimes just ahead of the effluent weir.
Depending upon the character of the silt and suspended matter, plain
sedimentation may provide as much as 70 percent removal; where coagu-
lants are employed, removals may be as high as 95 percent.
Many industrial waste waters contain organic and inorganic settleable
solids that must be removed before final discharge. These solids respond to
the process just described, and settling basins of similar design are used for
the purpose. Retention periods are usually much shorter than for raw
waters, rarely exceeding 2 to 3 h. Long retention periods are detrimental
where the solids are all organic, because bacteria} action may take place.
This may result in anaerobic conditions and the generation of odors. The
settled sludge will have a tendency to float if considerable gas is evolved, and
this will tend to nullify the operation.
Air flotation is very effective for removing flocculent solids that settle very
slowly or have a tendency to float. The air is dispersed in the liquid under
pressure and the pressure released just prior to discharge into a receiving
basin. The finely divided air floats the jsolids to the surface, where they are
skimmed off. Effective separation is provided at minimum cost by this
method.
under a pressure of 207 to 345 kPa (30 to 50 psi) and air is diffused into the
liquid. The pressure is released just prior to discharge into a separating tank
where the fine air bubbles rise to the surface carrying the particles of oil with
them. A rotating skimmer sweeps the floated oil to a collecting trough from
which it flows into a receiving tank. These systems can easily produce 90
percent separation with very short retention periods, sometimes of no more
than 30-min duration [3].
Desgasification
Stripping operations, such as physical deaeration and aeration, are
processes for removing undesirable dissolved gases from water. One or more
dissolved gases, such as oxygen [4], carbon dioxide [5], ammonia, or
hydrogen sulfide, are removed by exposing large surfaces of the liquid to a
vapor phase deficient in the gases to be eliminated.
Degasifying equipment can be classified as ebullition, tray or drip, and
spray units. In the ebullition type, a suitable gas is bubbled through the
liquid for a period sufficient to change the vapor pressure equilibrium and
enlarge the liquid surface. This principle was widely used in the past for
hydrogen sulfide and carbon dioxide removal; it is now employed mainly to
separate carbon dioxide and oxygen in deaerating feedwater heaters, usually
operating under a few pounds pressure.
Tray or drip gas-stripping equipment exposes large surface areas to the
desired vapor pressure conditions by slowly flowing the water in thin layers
over plates, channels, slats, or packing and allowing it to fall or trickle in
droplets or thin sheetsy^Deaerating feedwater heaters operate on this
principle to remove dissolved oxygen and carbon dioxide from boiler
feedwater. The heaters are usually operated under a few pounds pressure and
at temperatures above 100°C (212°F). Degasifiers used to remove carbon
dioxide where alkalinity is controlled by acid addition, or by blending
hydrogen zeolite effluent with sodium effluent or after cation exchange,
operate on this principle. Closed wooden tanks containing many stacks of
trays allow the water to drip down while air blown up through the tank
escapes at the top.
Spray and spray-ebullition gas strippers utilizing atomizing nozzles,
ebullition, and entrainment to divide the water into fine droplets for
exposure to the desired vapor pressure conditions are finding wide use, not
only in deaerating feedwater heaters, but also with vacuum deaeration of
carbon dioxide and oxygen from cold water and ammonia from hot water.
Vaccum deaeration is carried on in one or two stages, usually in vertical steel
tanks where the vacuum is maintained by steam-jet ejectors.
With the exception of vacuum deaeration, some means must be employed
to maintain the partial pressure of the undesirable gases well below the point
at which stripping will cease. In a gas-stripping basin or tower, the air that is
pumped or blown through the equipment carries the undesirable gas away to
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 51
the atmosphere. Steam with a low partial pressure of free oxygen is the
stripping agent in deaerating feedwater heaters. A vent condenser is usually
included to permit the incoming feedwater to absorb most of the heat in the
stripping steam.
Dilution
High salt concentrations in waste water from the oil and alkali industries
present a difficult disposal problem. Similar problems occur in other
chemical plants where sodium sulfate and organic solids are present in high
concentrations in effluents. Regulatory agencies have set limiting concen-
trations in the receiving streams that restrict the amount of dissolved matter
and suspended matter that may be discharged.
Where inorganic salts such as sodium chloride, calcium chloride, and
sodium sulfate must be discharged, there are two methods in use. One is by
dilution with uncontaminated water, and the other is by controlled dis-
charge. In those plants where the waste stream is small and there is available
considerable uncontaminated waste water (for example, from cooling
operations), the two are blended to conform with the concentration allow-
able in the plant discharge. Where the amount of clean water is insufficient
for diluting all the concentrated waste, any surplus of the latter is held for
controlled discharge.
Controlled discharge takes advantage of the increased stream flows during
winter months or rainy seasons to dispose of concentrated wastes that would
otherwise overload the receiving water. The wastes are stored in ponds and
released during periods of heavy runoff at a rate that will not exceed the
allowable concentration in the river. This operation may require large areas
of land for storage lagoons, but it is often the most economical method of
handling the problem.
When there is sufficient flow in the receiving stream to assimilate the
biochemical oxygen demand (BOD) load from organic matter, dilution can
provide satisfactory stream assimilation and eliminate areas of heavy oxygen
depletion. This method has certain limitations but it has been used success-
fully in some areas.
The dissolved salts and sludge in evaporators, boilers, and cooling towers
are concentrated in the circulating water and these concentrations must be
controlled by blowdown. Blowdown is thus a dilution process whereby
concentrated solutions and suspensions are replaced by more dilute water.
Intermittent boiler blowdown usually discharges directly to an atmospheric
drain tank, with the result that all of the heat of the liquid and of the flashed
steam are lost. Continuous blowdown systems make it possible to recover
this heat. Heat-recovery systems are available for both high- and low-
temperature operation. Heat-recovery equipment for high-temperature
blowdown may consist of a flash tank to salvage flash steam or of a surface
heat exchanger for transferring the blowdown heat to the feedwater just
52 MANUAL ON WATER
Removal of Entrainment
One of the fundamental problems in boiler design and operation is the
mechanical separation of solutions and solids from the steam. All boilers
must include entrainment separators. The simplest method is to provide
sufficient disengaging space above the normal waterline in the steam drum.
It is economical for industrial steam generators to use dry pipes, baffles, or
special types of separating devices to reduce the size of the steam drum. Most
modern steam drums are furnished with carefully designed and proved
internal equipment. Steam separator equipment is mechanical in nature and
operates by gravity, centrifugal force, and surface tension or by a com-
bination of these forces to remove liquid and solid contamination. Pre-
liminary washing of the. steam by feedwater or steam condensate may be
done in steam separating equipment. Devices for overcoming entrainment of
liquids in gas will not appreciably separate a mixture of gases, such as steam
and carbon dioxide, or steam and hydrocarbon vapors.
Entrainment separation efficiency in a steam boiler is controlled not only
by the mechanical equipment, the steam rate, and the water level in the
boiler drum, but also by the surface tension of the dissolved solids and the
liquids in the boiler water. There is usually a limit for dissolved solids above
which, at normal steam rates, priming and carryover will occur. No general
standard for allowable dissolved solids can cover all types of steam
generators. While operators at one plant will insist that concentrations must
be kept below 1000 mg/litre dissolved solids, operators at another plant with
identical equipment, but with different water conditions, may be able to
operate satisfactorily with 5000 mg/litre.
The same general principles apply to reduction of solids carryover in the
NOTE—For boiler pressures between 689 and 5516 kPa (100 and 800 psig), use "flash" pres-
sure curves slanting from lower left-hand to upper right-hand corner and the bottom axis. For
boiler pressures above 5516 kPa (800 psig), use "flash" pressure curves slanting from lower
right-hand to upper left-hand corner and top axis.
This chart is used to calculate the percentage of boiler water discharged by a continuous
blowdown system that can be flashed into steam at a reduced pressure and recoverable as low
pressure steam for heating or process.
EXAMPLE—A boiler operates at a pressure of 3103 kPa (450 psig). Continuous blowdown
amounts to 4540 kg/h (10 000 Ib/h). What percentage of blowdown water can be recovered as
flashed steam at 5 psig pressure?
SOLUTION—Locate 3103 kPa (450 psi) on left-hand axis. Follow horizontally toward the
right to the intersection with 34 kPa (5 psi) "flash" curve (point A). Drop vertically downward
to the bottom axis and read 25.5 percent. Twenty-five and a half percent of 4540 kg/h (10 000
Ib/h) blowdown = 1158 kg/h (2550 Ib/h) of flash steam at 34 kPa (5 psig) pressure.
These curves have been prepared from the formula:
where:
HB- heat of liquid at boiler pressure in Btu/lb,
HF= heat of liquid at flash pressure in Btu/lb, and
VF- latent heat of vaporization at flash pressure in Btu/lb.
54 MANUAL ON WATER
Distillation
Distillation is the time-honored method for preparing high-quality pure
water. Both dissolved and suspended solids can be removed almost com-
pletely by this purely physical process of evaporation and condensation. The
condensate from a water distillation unit with good steam separator
equipment, and at normal evaporating rates, should contain no more than a
few milligrams per litre of dissolved solids and may contain only a fraction of 1
mg/litre. The suspended and dissolved solids of the feedwater remain in the
evaporator salines and are removed by blowdown and descaling operations.
The high quality of its product gave the distillation process an initial
advantage over other processes for the preparation of boiler feedwater.
Distillation transfers a large part of the boiler water treatment problem from
the plant boilers to low-pressure evaporators where it can be more success-
fully handled. Single-effect and multiple-effect evaporators have found wide
use in plants where large quantities of low-level heat or exhaust steam
otherwise would be wasted. Low-level, or so-called waste heat, is not
worthless; its cost is too often underestimated in the overall plant heat
balance and in the original plant design.
Compression distillation equipment may be economical where low-level
heat is not available in sufficient quantity or is being put to more valuable
use. These units, employing the heat-pump principle of salvaging the latent
heat of evaporation, have the heat economy of 15 or more effects of
multiple-effect evaporation. Compression stills may be electrically driven or
may be powered by other prime movers. Diesel-driven compression dis-
tillation units can produce from 67 to 112 kg (150 to 250 Ib) of distilled water
per pound of fuel oil.
In industries where only a few milligrams per litre of dissolved solids are
allowable in the process water, either distillation or one of the deionizing
processes (discussed later in the "Chemical Treatment" section) can be used.
The choice will depend largely upon the concentration of dissolved solids in
the raw water.
Distillation equipment should be so designed that the scale and sludge
problem can be handled with minimum labor. The problem is similar to that
of a boiler except that the temperature usually is lower. Heat-transfer rates
at lower temperatures are more vulnerable to the insulating effects of scale
and sludge deposits.
Extremely high-quality distilled water can be obtained by multiple or
fractional distillation. In the latter process, part of the product is condensed
and refluxed to scrub entrained salts and solids from the steam being
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 55
Underground Discharge
Underground discharge is a method for disposal of liquid wastes into
permeable strata in the earth. It is a satisfactory method only in areas where
other methods are extremely expensive or unavailable. The permeable strata
must be so located that the liquid waste pumped into them will not
contaminate strata used for water supply. These permeable layers are very
deep, about 1200 to 1500 m (4000 to 5000 ft) being usual. Furthermore,
injection wells are very expensive.
The waste water must be sterile and free from suspended solids. Extensive
pretreatment is essential to remove silt, suspended solids, oil, and emulsions.
Chlorination is generally provided to make sure that it is free from micro-
organisms. Additional pressure above that developed by the depth to the
aquifer is necessary to force the water into the strata; this may be as high as
14 000 to 20 000 kPa (about 2000 to 3000 psi).
This method has been used in only a few locations because of the extensive
study required and the high cost of the installation. It does have its
applications, however, and should not be overlooked.
Ocean Discharge
Ocean discharge of waste water is practiced by plants in coastal locations.
Actually, it is a dilution method. Consideration must be given to the path of
ocean currents in the area of the outfall to ensure that the waste water will
not be carried to the shore and contaminate bathing beaches. The major cost
for this method is construction of an outfall to such distance that safe
disposal will result.
Desalination
It has been estimated by many experts that by 1980 we will require nearly
2/2 X 109 m 3 /day (600 U. S. billion gallons of water per day), which is double
/ur present demand. Recognizing the need, and the benefits to be gained
from saline water conversion, Congress enacted the Saline Water Act in
1952, and extended it by amendment in 1955 to provide for a program of
research and development having as its primary objective the development
of economical methods of producing freshwater from sea and brackish
waters. The Department of the Interior, through the Office of Saline Water,
sponsors scientific research and development through Federally financed
contracts and grants, by research in Federal laboratories, and by stimulating
and coordinating private activities in this field.
In 1958, a new law authorized construction and operation of not less than
56 MANUAL ON WATER
capacity of 757 m 3 /day (200 000 gpd) and employs the controlled crystal-
lization freezing process. This process uses direct-contact heat exchange
between a secondary refrigerant and seawater, and centrifugal separation of
ice and brine.
Solar distillation of seawater as a source of freshwater is an old process
that includes all those methods in which the energy of the sun is collected
and used immediately, or after a period of time, in evaporation of freshwater
from seawater. While energy from the sun is abundant, it is intermittent and
of low intensity. In general, solar distillation units consist of sloping glass or
plastic plates covering a long, narrow, black-surfaced basin. The transparent
sloping surfaces transmit solar energy which is absorbed in the basin. The
seawater in the basin, warmed to a temperature as high as 71°C (160°F),
vaporizes into the air space, condenses on the cooler transparent cover
surfaces, and runs down the sloping cover to troughs and storage.
In addition to the processes described in the foregoing, salt removal by
reverse osmosis is being evaluated in several demonstration plants, and this
process shows considerable merit for brackish water.
Chemical Treatment
Chemical treatment pertains to those processes in which separation of the
impurities from water involves chemical alteration of the contaminating
material. It may include precipitation, ion exchange, sequestering reactions,
gas removal, oxidation and reduction reactions, chemical control of bio-
logical growths, and sterilization.
Precipitation
When certain soluble salts are added to an aqueous solution, some of the
free ions may react to form comparatively insoluble compounds. The
precipitate can be separated by filtration or by decanting the clear liquid
after settling. Precipitation occurs in accordance with definite laws govern-
ing the combining weights of the reactants and their solubility products [6\.
Many of the methods described in the following depend upon precipitation
of impurities. ,
Softening—The earliest commercial chemical precipitation process was
the addition of hydrated lime (Ca(OH)2) to water for removal of bicarbonate
hardness. Lime converts bicarbonate hardness to relatively insoluble calcium
carbonate:
Soda ash usually is combined with lime to remove both kinds of hardness in
one step. The two reactions can be carried out simultaneously, hot or cold, in
batch or continuous equipment. A coagulant generally is used to improve
the separation of the solid phase.
"Magnesium can be precipitated in a lime-soda softener by increasing the
hydroxide alkalinity of the effluent to the point at which magnesium
hydroxide is relatively insoluble. This can be accomplished with hydrated
lime or caustic soda:
Any of the phosphates may be used; they are added in aqueous solution.
Where the calcium hardness is mainly bicarbonate, phosphoric acid provides
alkalinity control as well as lower total solids in the effluent. The reaction is
carried out at a pH of 10 or higher with maintenance of a few mg/litre of
hydroxide residual. The resultant hardness in the treated water is about 1
mg/litre as CaCOx Caustic soda is used for precipitation of magnesium ion
when phosphates are used to precipitate calcium.
In the past, especially in European practice, barium carbonate was used
instead of lime for softening. This method has not found favor in America,
where it is used in only a few specific instances.
Internal Boiler-Water Softening—Usually it is unsatisfactory to depend
upon external softening alone for boiler makeup water, especially for high-
pressure boilers. Internal boiler water treatment may be required to convert
scale-forming salts to soft sludges to be removed by boiler blowdown.
Chemical compounds whose solubilities increase with a rise in temperature
can be made to form nonadherent sludges [9]; those whose solubilities
decrease with increase in temperature often form hard, adherent scale.
Internal boiler-water treatment in actual practice is far more complex than
these general principles indicate. This results from the wide variety of
compounds and mixtures of compounds that can be formed in the boiler,
and from the effects of organic matter and rates of evaporation on crystal
structure [10-13].
It is not desirable to precipitate large quantities of minerals in a boiler, and
internal boiler-water treatment preferably should be applied as a supplement
to external chemical or physical treatment. Internal treatment alone may be
satisfactory for low-pressure boilers, for which only moderate amounts of
reasonably soft feedwater are required.
60 MANUAL ON WATER
Ion Exchange
It may be necessary to remove the cations or anions, or both, from water
to provide a satisfactory supply for process and boiler feed uses. A preceding
section described removal of cations by precipitation; this process had no
effect on the anions present, and other means are required to remove them.
Certain insoluble substances possess a capacity for exchanging ions bound
in their molecular structure with other ions in water. The exchanged ions are
released by regeneration of the exchange resin. Negatively or positively
charged ions may be exchanged, depending upon the nature of the resin. A
wide variety of solid materials possess this reversible property. A charac-
teristic difference between ion exchange and precipitation processes is that
the former produces only solutions for waste disposal while the latter yields
both liquid and solids. This important difference may be the deciding factor
in a choice of process. Disposal of sludge from a precipitation process may
make it uneconomical as compared with ion exchange. On the other hand,
waste water from an ion exchange process may present a disposal problem.
Natural and synthetic substances (zeolites) have been used for many years
to remove calcium and magnesium ions from water. These ions are then
replaced by sodium ions when the zeolite is regenerated:
Softening:
62 MANUAL ON WATER
Regeneration:
The process will operate equally well if the calcium and magnesium ions
are replaced with potassium ions or with any other positive ions that can
exist in a relatively concentrated neutral solution.
In the early years of the industry, zeolites were developed from natural
greensand. Suitable treatment opened up the pores in the grains and
hardened the surface. Exchange capacity, which was dependent upon pore
area, was relatively low, about 6.4 kg/m\ Capacities of 0.292 kg were
developed by either acid or heat treatment. The natural zeolites were not
resistant to high- or low-pH water, and pretreatment of the raw water was
often necessary because they were easily fouled by iron or organic matter.
Synthetic gel zeolites were later produced and had higher capacities, but
their use was rather restricted and they have gradually been abandoned in
favor of the newer synthetic resins.
With advances in the art of ion exchange, carbonaceous and synthetic
resin zeolites were developed that would withstand both acid and alkaline
solutions and provide both cation and anion removal. Carbonaceous zeolites
are limited to about 18.3 kg/m 3 while the resins have a maximum capacity of
about 1.9 kg on the cation cycle.
In hydrogen cycle operation, the material exchanges hydrogen ions for
calcium, magnesium, sodium, and other positive ions; it is regenerated with
sulfuric or hydrochloric acid:
The effluent from hydrogen ion exchangers contains free mineral acidity,
and it may be desirable to operate such installations in parallel with sodium
cycle exchangers or to mix the effluent with untreated water to neutralize the
acidity. The combination of sodium and hydrogen cycle ion exchange makes
it possible to remove the hardness and reduce alkalinity at the same time.
The bicarbonate hardness is converted into dissolved carbon dioxide, which
can be removed by degasification.
Where the anions must be removed from the water, the process usually is
operated in two stages. The water first flows through a hydrogen-regen-
erated cation unit, and the acid effluent is then passed through an acid-
absorber anion exchanger.
In this two-step process, the acid effluent is usually degassed to remove
free carbon dioxide before passing through the acid-absorbent exchanger to
complete the deionization. The degassing step can be eliminated if a strongly
basic, acid-absorbent exchange medium is used. If the hydrogen exchange of
the first step is complete, the product from the final unit will be neutral and
low in ionized solids. If the effluent from the hydrogen cycle contains
positive ions, these ions with their negative components will pass through the
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 63
replace hardness with sodium ions and bicarbonates with chloride ions. The
two ion exchange materials need not be completely mixed; the unit can be
operated with the material in the layers that develop during backwashing.
This method is feasible, but it is not widely used. Two stages are employed
more often, the first to remove calcium and magnesium, utilizing sodium
chloride for regeneration. In the second stage, the anion material absorbs the
bicarbonate ion and replaces it with chloride ion. Here a mixture of sodium
chloride and caustic soda is used for regeneration. Although the salt
performs the regeneration, the caustic has been found to lengthen the life of
the resin, which results in higher capacity [7(5].
Ion Exchange in Waste Treatment—Ion exchange is being used to recover
chromium from waste waters. The chromic acid waste is first passed through
an anion exchanger to remove the chromium in accordance with the
equation:
The anion material is regenerated with caustic soda, which releases the
chromium as sodium dichromate:
This treatment recovers the chromic acid and concentrates it for reuse.
The chromic acid content of plating waste waters varies from 100 to 500
mg/litre CrOs. The recovered chromic acid has a concentration of about
30 000 mg/litre or 3 percent CrOa, which is sufficiently high for reuse. The
waste water has been rid of dilute chromic acid and it can be reused or
discharged to a stream.
Ion exchange has also been used for recovery of certain ionized organic
compounds. These include nicotine from water used to wash the gases from
cigarette drying, and tartaric acid from winery wastes. Nonionized fruit
sugars have been recovered from cannery wastes and citrus peels, and pectins
from grapefruit wastes, by ion exchange. These are special applications but
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 65
show the wide range of applicability of this process to the treatment of waste
waters for product recovery.
Ion Exclusion—A technique, known as ion exclusion, has been evolved
which has many possibilities in waste-water treatment and certain process
operations. It allows separation of ionic and nonionic materials, such as
sodium chloride from ethyl alcohol, sodium chloride from formaldehyde,
and sodium sulfate from glycerin. Thus, separations that were never
economically possible are now quite feasible.
The method provides for alternate feeding of the aqueous solution of ionic
and nonionic materials and water into an exchange column. One volume of
feed solution is usually followed by one or more volumes of water. An
aqueous solution of ionic material comes out of the column first, followed by
an aqueous solution of the nonionic material. The separation of the ionic
material from the nonionic material may be quite sharp.
Separations of this kind are possible because of the peculiar behavior of
an ion-exchange bead in an aqueous solution of a mixture of an electrolyte
and a non-electrolyte. In such solutions, the electrolyte tends to be more
concentrated around the bead, while the nonelectrolyte_tends to have the
same concentration within and outside the bead. This difference in con-
centration between the two solutes is the basis for the process. The ionic
material appears to be rapidly flushed through the void spaces between the
individual ion beads, while the nonionic material is retained in the column
for a longer period since it diffuses through the resin beads as well as around
them.
Resins used in ion exclusion do not need to be regenerated because they
never become exhausted; the only operating cost is for water and pumping
[17].
Ion Retardation—Another ion-exchange process for separating water-
soluble materials is ion retardation. This has resulted from development of a
resin that has both anionic and cationic exchange sites located in the same
bead. The resin will therefore adsorb both anions and cations from the feed
solution. The resin sites are so closely associated, however, that they
partially neutralize the electrical charges in each other; the adsorbed ions are
thus weakly held and may be displaced from the resin by water alone.
Ion retardation is a column operation in which alternate portions of feed
and rinse water are passed through the column, as in ion exclusion. It
permits separation of two electrolytes, such as ferrous sulfate from zinc
sulfate, sodium hydroxide from sodium chloride, and ammonium chloride
from zinc chloride. It will also separate electrolytes from nonelectrolytes,
and salts from very large nonelectrolyte molecules.
Like ion exclusion, this technique holds promise of adding another tool to
the fractionation of process streams and treatment of waste waters.
Sequestering
The foregoing subsections have been devoted to water-treating processes
66 MANUAL ON WATER
Oxidation
Surface- and groundwaters may contain odor- and taste-producing sub-
stances that make them unfit for drinking and for some process uses. These
substances are usually organic, and often they can be removed by oxidation.
Spray ponds provide one method for accomplishing this. Water is
dispersed in the air as fine droplets by spraying it over a pond through
nozzles. The intimate contact between water and air provides the desired
oxidation. Usually any dissolved gases are released at the same time. A
forced-draft degassing tower may be used in place of a spray pond; it should
provide about the same efficiency.
Oxidation with chlorine, chlorine dioxide, or ozone can be used to convert
objectionable organic matter into innocuous compounds. A short contact
period, usually not over 10 min, is required for complete oxidation. Certain
waste waters may contain taste-producing materials, such as phenol, in small
volume but high concentration. Biological treatment under these conditions
would entail a very large capital expenditure, but the operating cost would
be low. The capital investment can be reduced materially by using chlorine
or chlorine dioxide, because the operation would be the equivalent of a
waste treatment unit. The waste-water flow would be the water supply to the
chlorinator and it would be discharged as a treated effluent. The operating
cost for such an arrangement might be rather high, but the low capital
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 67
Neutralization
Neutralization of acidity or basicity may be necessary to provide satis-
factory process water or for treatment of waste water. Many groundwaters
contain such high concentrations of carbon dioxide that the water is quite
acidic. Aeration will remove most of the carbon dioxide, but not all of it, and
the pH may still be so low that the water is corrosive for general purposes.
Accordingly, neutralization is provided to raise the pH to the desired value.
Calcite filters, which consist of pressure vessels filled with pulverized
marble, can be used if the quantity of water is small. The carbonic acid is
neutralized by the calcium carbonate and the water is stabilized at the same
time. Stabilization means that the alkalinity-pH ratio is automatically
adjusted to provide a water neither corrosive nor scale-forming.
Alkali feeds are used where large volumes of water are needed. The
solution feeder comprises equipment for continuously feeding a water
solution of caustic soda, soda ash, or lime slurry. Provision is made for
controlling the rate of chemical addition to maintain the desired pH value.
The control may be manual or automatic, through a pH recorder-controller.
Neutralization is not instantaneous, and a contact period must be provided,
usually not more than 5 min. The alkali solution may be fed by gravity or by
pumping into the stream to be treated. Liquid storage tanks are usually
designed for 12- to 24-h operation between refills.
Chemicals may also be fed dry. Only soda ash or lime may be used in dry
feeders because caustic soda is too hygroscopic to permit uniform feeding.
The dry-feed machines operate either on the volumetric principle, in which a
measured amount is displaced each stroke, or gravimetric, whereby the flow
of dry material is weighed continuously. The dry chemical discharges into a
mixing box where it forms a solution or a suspension. It is then allowed to
flow by gravity, or is pumped, to the point of application. These machines
can be made to operate in proportion to flow rate or to pH response.
Hoppers over the machines provide chemical storage of 8 to 24 h.
Where lime or lime-and-soda methods of softening are employed, the
effluent will contain caustic alkalinity. This excess alkalinity generally must
be neutralized. This is done by adding acid, usually sulfuric or carbonic. The
amount of acid fed is determined by the resultant pH value desired. The
usual control is by a pH recorder-controller.
A 10 percent acid solution is normally used to treat relatively small
volumes of water. Concentrated acid is fed if the volume is large. A metering
pump is preferred for acid feed in large-volume operations. The pump can be
controlled for ratio-flow control, pH control, or a combination of both.
Acid-resistant storage tanks, piping, and pumps must be used.
Both alkaline and acidic waters are encountered in waste treatment. Free
mineral acids and free alkalies must be neutralized before discharging such
waters. This means neutralization to the methyl orange or the pheno-
Iphthalein end point, respectively. Rarely is it necessary to go above pH 4.6
or below pH 8.3. The neutralized waste water will not reduce the total
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 69
Degassing
Dissolved Carbon Dioxide—Dissolved carbon dioxide can be chemically
removed by adding lime, soda ash, or caustic soda to form soluble
bicarbonates or relatively insoluble carbonates. This method requires careful
chemical control. Approximately the same result can be obtained with less
control and supervision by passing the water through a bed of material with
which the dissolved carbon dioxide will react chemically to form a neutral or
alkaline product. The most common material for this process is crystalline or
granular calcium carbonate, such as crushed calcite or limestone. The
calcium carbonate slowly dissolves by reaction with the carbon dioxide to
form additional bicarbonate hardness in the water:
Such a unit also acts as a filter, and periodic backwashing may be required.
The initial investment is the principal cost of the process; chemical replace-
ment and operating costs are small. The additional hardness added to the
water by the process may be objectionable [25].
Chemical Removal of Dissolved Oxygen—To supplement physical dea-
eration, dissolved oxygen also can be removed from water by chemical
means. Sodium sulfite is used extensively as a final treatment to consume the
small trace of dissolved oxygen which is not removed by deaerating
feedwater heaters. Sulfite reacts rapidly with dissolved oxygen at boiler
water temperature to form sulfate:
Chemical methods usually are employed only for removing low chlorine
residuals. Chlorine gas, on the other hand, may be used to convert ammonia
or ammonium ions to chloramine, which can be removed from solution by
aeration.
experimental units have been installed in the past, but the method has not
been generally accepted.
Silver iodide has excellent disinfection properties when fed as a soluble
salt. Its high cost precludes its use except during war emergencies. It was
made in tablet form during World War II and was extensively used by the
armed forces.
Incineration
Incineration is not usually considered as a waste water disposal method,
but there are certain cases where it is applicable. When the volume of waste
water is under 40 litres/min (10 gal/min) and the soluble organic concentra-
74 MANUAL ON WATER
tion is above 4 percent, the waste can be sprayed into the boiler furnace for
evaporation of water and combustion of organics. The boiler furnace must
be large enough to handle the vapor load. Some additional fuel will be
required, and the fuel-feed and burners must be of sufficient size to handle
this increase. This "method can generally be used only with oil-fired boilers. If
the waste water contains toxic materials, a modified unit provided with its
own burner and fuel supply can be used effectively for destroying the
compounds.
A great deal of study is necessary, followed by pilot operation, before
incineration can be used effectively, but the technique does provide a
satisfactory answer for certain waste water problems.
Physicochemical Processes
Several important water treatment processes depend upon combined
chemical and physical action. These are coagulation, adsorption and
absorption, crystal growth deactivators, additives for changing surface
tension, and corrosion inhibition.
Coagulation
Most surface waters contain suspended matter and color. Much of the
suspended matter consists of particles too small to settle rapidly, even in
quiet water. Color is caused by absorption of light by suspended and
dissolved organic and mineral substances. A chemical coagulant, such as
alum, ferrous or ferric sulfate, or sodium aluminate, will cause the finely
divided and colloidally suspended materials to be gathered together into
larger particles, called floe, which will settle rapidly. A flocculertt precipitate
which has enormous surface area per unit of volume is produced by
coagulants. This precipitate removes suspended and colloidal matter from
the water by electro-physical attraction, adsorption, absorption, and phys-
ical entanglement. For example, aluminum sulfate reacts with hydroxyl ions
in water to form complex aluminum hydroxides that are relatively insoluble
in the pH range from 6 to 8. The particles of precipitated aluminum
hydroxide, with the help of suitable mild agitation, agglomerate into visible
clumps which settle by gravity. The simultaneous formation, agglomeration,
adsorption, and inclusion of the suspended matter and color into the floe is
the physicochemical process of coagulation.
Each coagulant has a pH range in which it is most effective. The addition
of the coagulant usually changes the pH of the solution at the time the floe is
formed. Acidic coagulants such as aluminum and ferrous and ferric sulfates
precipitate as basic compounds and reduce the pH of the water. When the
natural alkalinity of the water is not sufficient to maintain the minimum pH
requirement after coagulation, it is necessary to add lime or soda. The
optimum range for coagulation with aluminum sulfate is between pH 5.5
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 75
and 7.0. Above 7.0, there is a tendency for some of the alum to remain
unprecipitated, and a small amount of residual aluminum will remain in the
final filtered water. When the pH of the raw water gets above 7.2, the
amount of coagulant necessary to drop the pH into the optimum band may
be too great economically, especially if the coagulation pH is 6.3 to 6.4 for
the water. Accordingly, sulfuric acid is added ahead of or with the aluminum
sulfate to reduce the pH to the proper range for good coagulation. Sulfuric
acid will lower the pH much faster and at less expense than the coagulant.
Ferric sulfate is an effective coagulant over the wide pH range of 5.5 to 10.
It has an acidic reaction and lowers the alkalinity of the water. Ferrous
sulfate, while effective over a wide range, is generally used between pH 8.5 to
10. In addition to requiring alkalinity for coagulation, there must be an
oxidizing agent to convert the ferrous iron to the ferric state. Usually there is
enough dissolved oxygen in the water to complete the oxidation; if
insufficient, some form of aerating device is employed to increase the oxygen
content. Chlorine also is frequently added for this purpose.
Many factors affect the amount of coagulant needed for optimum results.
Among these are type and amount of suspended matter, water temperature,
rate of mixing, and retention time. Coagulant dosage may vary from 5
mg/litre for a good water very low in turbidity and color to 100 mg/litre or
more for a highly turbid one. Presettling is usually provided when turbidities
continually run over 400 to 500 mg/litre, to reduce the coagulant require-
ment.
Continuous and proportionate feeding of the coagulating chemical is
necessary for effective coagulation. In addition, control of the pH in the
optimum range is essential. The coagulant can be fed dry or in solution,
depending upon the amount to be fed and specific conditions. Usually
quantities up to 45 kg (100 Ib) per day are fed as a solution. Above this, dry-
feed machines are employed with a dissolving tank so that a dilute solution is
fed; with proper physical arrangement the dry material can be fed directly
into the water.
The coagulant should first be thoroughly dispersed in the stream to be
treated. This is accomplished in a high-speed mixing chamber having a
retention of from 0.5 to 1.0 min. After the dispersion, the finely formed floes
require agglomeration by very gentle agitation so they can develop into large
masses. Slowly revolving paddles in a chamber providing from 40 to 60 min
retention will bring the floe to maximum development and produce one that
will settle rapidly and provide a satisfactory supernatant for filtration.
Corrosion Inhibition
Water conditioning for corrosion control involves both physical and
chemical processes operating together. Protective films that inhibit metal
deterioration are physical barriers. The formation and maintenance of such
films may be the result of chemical reactions. These physicochemical
corrosion inhibition processes are briefly described in the following three
subsections.
Cathodic Protection—The electrolytic theory of iron corrosion, as postu-
lated by Whitney [28] and demonstrated by Walker and associates [29], is
essential for understanding the process of cathodic protection [30]. Ac-
cording to this theory, metals in contact with water tend to go into solution,
forming positively charged ions. Positive ions can go into solution in an
electrically neutral system only if an equivalent number of positive ions of
some other element are plated out. In the case of pure water in contact with a
metal, such as iron, hydrogen ions are plated out at the interface. The
reaction may be written:
The liberated hydrogen forms a thin, insulating film on the metal which
prevents further corrosion. Thereafter the corrosion reaction proceeds at a
rate that is a function of the rate of removal of the layer of atomic hydrogen.
The observed effects of dissolved oxygen, temperature, pH, salt concentra-
tion, and turbulence on this protective hydrogen film on iron and steel have
been found to agree with this theory [31]. Any method for maintaining the
protective hydrogen film will reduce corrosion.
Galvanizing steel provides a form of cathodic protection. Here the
protective hydrogen film is maintained on the exposed steel cathode at the
expense of the zinc anode, which slowly goes into solution. Magnesium and
zinc rods or plates suspended in water and electrically connected to the steel
tank are further examples of cathodic protection. In other forms of this
78 MANUAL ON WATER
Liquid-Phase Separation
With the steadily increasing demand for water, considerable thought has
been given to the purification of seawater, and it is here that liquid-phase
separation is being widely investigated.
The development of ion-selective membranes has led to their use in this
work. Membrane electrolysis employs a stack of alternating cationic and
ionic selective membranes which provides a series of parallel cells through
which the raw water flows. An electric potential across the stack causes the
cations and anions to move in opposite directions and to pass through the
appropriate selective membranes. As a result, ions tend to leave alternate
cells and to concentrate in the cells between them. Thus the stack con-
tinuously discharges two streams, one relatively demineralized and the other
proportionately concentrated in the abstracted ions. The process shows
promise as an economical method for desalting brackish water.
Osmoionic demineralization is another method being studied for purifying
salt water with ion-selective membranes. No electricity is required, because
the method uses osmotic pressure to move ions through the membrane. The
procedure is effective for desalting brines with chloride concentrations in the
range of 3000 mg/ litre.
Dialysis and electrodialysis have been used in the treatment of certain
waste waters. These methods separate ionizable salts from colloidal sus-
pensions. The ionized salt passes through a membrane and leaves the
colloidal material behind. Depending upon the material to be separated and
the conditions at hand, electricity may be used as an additional driving force.
These methods are being used for alkali and acid separation and recovery
from process liquors.
Biological Treatment
Interest is awakening in the time-honored process of percolation of raw
wastes through a bed of graded media.
Sand percolation is one of the oldest recognized methods of water
purification. The process had the ability to remove color, turbidity, and
bacteria by means of biological activity within a gelatinous growth on the
media grains. The biologically active material provided the major puri-
fication; the graded media, or sand, served as a support for the bio-mass
(known as schmutzdecke). Good purification resulted at application rates of
2300 to 2800 litres of filter per square metre per day (2.5 to 3.0 million
gallons per acre of filter per day). Intermittent dosing or trickle-spray fluid
application of the raw waste may be used to increase the throughput of
80 MANUAL ON WATER
percolation units, but higher rates tend to favor more advanced processes.
Influent pretreatment may also provide minor improvement in application
rates.
Biological purification is widely used for treatment of waste water
containing dissolved organic matter. Bacteria break down the complex
compounds into simple, stable ones; the usual end products are carbon
dioxide, water, nitrate, and sulfate. This change is brought about through
the metabolism and cell synthesis of the microorganisms present. Usually
these processes are carried out in the presence of excess dissolved oxygen,
and the operation is then known as aerobic decomposition. Another group
of microorganisms can thrive in an environment devoid of dissolved oxygen.
Under these conditions the process is known as anaerobic decomposition.
Although most biological treatment today is aerobic, there are some wastes
which respond better to anaerobic decomposition.
There are two broad types of bio-oxidation equipment, trickling filters
and activated sludge. The trickling filter is a bed of graded rock, usually 0.9
to 1.8 m (3 to 6 ft) deep, but sometimes as deep as 3 m (10 ft). The bed
diameter may vary from 4.5 to 61.0 m (15 to 200 ft). The rock is supported by
an underdrain system for collection of the liquid flowing over it. A rotary
distributor on the top provides for uniform spreading of the waste water on
the bed. The underdrain system has air ducts which allow air to circulate
through the bed by natural draft; this provides the oxygen necessary for
good biological action. The stone provides a large surface for growth of the
organisms that accomplish aerobic decomposition. The units are classed
high or low rate depending upon the rate of operation. Up to 4700
litres/m 2 /day (5 million gallons per acre per day) (Mgad) is considered low
rate, while 9400 to 28 200 Htres/m2/day (10 to 30 Mgad) is high rate.
Biochemical oxygen demand is the design criterion. The volume of the filter
is based upon decomposition of 0.34 to 1.72 kg/m 3 (1 to 5 Ib of BOD/yd3) of
stone per day. The diameter is fixed by the rate of application and volume of
waste water to be handled per day. Actual design should be developed only
after pilot plant studies of the waste water in question. Efficiencies of single
filter units range from 35 to 85 percent removal of BOD. Where higher
efficiencies must be provided, a second unit is installed to operate in series
with the first to provide two-stage treatment. Under such conditions, 80 to
95 percent purification can usually be obtained.
In the activated sludge process the waste water to be treated is held for a
period of time in a tank in which air is blown through the liquid. This
develops a lush bacterial suspension which brings about aerobic decom-
position. The retention time will usually range between 4 and 24 h. BOD in
kilograms per day is the design criterion for these units and the loading will
vary between 0.24 to 2.4 kg/m3 (15 and 150 Ib/1000 ft3) of aeration tank
volume. The air required is supplied by rotary compressors or centrifugal
blowers. The difuser system may be perforated pipe, nozzles, carborundum
plates, or tubes. Turbomixers of various design characteristics are also used.
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 81
operation. Low dikes are built and means provided for dosing the areas once
a day Dosing is normally equivalent to flooding to a depth of about 5 cm (2
in).
The waste is usually diluted with water to provide a BOD of 300 to 500
mg/litre and applied to give a BOD loading of 0.11 to 0.22 kg/m 2 /day (100
to 200 Ib per acre per day). Under such conditions, purification efficiencies
of 90 to 98 percent have been obtained. In the sand, biological growths
develop which utilize the soluble organic material in the waste water as food
and thereby provide purification. Air is drawn into the soil during the dosing
period; this provides the oxygen needed by the organisms.
Spray irrigation utilizes the same general principle. Rotating sprays or
fixed sprays spread the diluted waste over a large area, which can be crop
land or wooded areas. The spray period usually lasts from 8 to 12 h per 24 h.
Sandy soil is a requisite, and purification is effected by biological growths in
the soil. The sprayed waste water should be low in suspended solids to avoid
plugging of the soil. While this method has been developed primarily for
disposal of cannery and milk wastes, it is applicable to almost any easily
oxidized, nontoxic waste.
A modification of the activated sludge process is the oxidation pond. In
this adaptation, the waste water is held in a shallow pond for a period of
days. Aeration from the atmosphere takes place and bacterial growths
develop. These ponds can remove 95 percent of the BOD and kill 99 percent
of the coliform bacteria; thus purification is generally sufficient to allow
discharge of the effluent into streams. These stabilization ponds have been
quite widely used in the paper industry and they are gaining acceptance in
the textile and chemical industries. They are used as a low-cost method for
municipal sewage treatment.
Summary
An attempt has been made to enumerate the principal water treatment
processes serving industry at the present time. New processes will un-
doubtedly be developed in the future. The discussion has been limited to the
main technical and economic features. Literature references have been given
for readers desiring greater detail.
Reference
[7] Ingersol, C, Petroleum Refiner, PEREA, June 1951, p. 1064.
[2] "Waste Water Containing Oil," Manual on Disposal of Refinery Wastes, American
Petroleum Institute., Section I, 4th ed., 1949.
[3] Beebe, A. H., Sewage and Industrial Wastes, SIWAA, Vol. 25, 1953, p. 1314.
\4\ McDermet, J. R., Transactions, American Society of Mechanical Engineers, TASMA,
Vol. 42, 1920, p. 267.
[5] Amorosi, A. M. and McDermet, J. R., Proceedings, American Society for Testing and
Materials, ASTEA, Vol. 39, 1939, p. 1204.
CHAPTER 5 ON TREATMENT OF PROCESS WATER AND WASTE WATER 83
[6] McKinney, D. S., Proceedings, American Society for Testing and Materials, ASTEA, Vol.
39, 1939, p. 1191.
[7] Hoak, R. D., Water & Sewage Works, WSWOA, Vol. 100, 1953, p. 468.
[8] Feller, E. W., Power, POWEA, Vol. 91, Dec. 1947, p. 71.
[9] Hall, R. E. et al, Industrial and Engineering Chemistry, IECHA, Vol. 17, 1925, p. 283;
Ibid, Vol.21, 1929.jp.JJ26; Techinical Bulletin, Carnegie Institute, Vol. 24, 1927.
[JO] Barkley, J. F., "Questions and Answers on Boiler Feedwater Conditioning," Bureau of
Mines, U. S. Government Printing Office, Washington, D. C, 1943.
[11} "Central Boiler Plants," Technical Manual TM5-650, Chapter 4, War Department, U. S.
Government Printing Office, Washington, D. C., 1947.
[12] "Boiler Feedwater and Feedwater Apparatus," Bureau of Ships Manual, BSJA, Chapter
56, Navy Department, U. S. Government Printing Office, 1948, p. 56.
[13] McKinney, D. S. in Chemistry of Engineering Materials, McGraw-Hill, New York, 1942,
pp. 1-32.
[14] Hall, R. E. and Jackson, H. A., U. S. Patent No. 1,903,041,1933.
[15] Applebaum, S. B. and Dickerson, B. W., "Silica Removal by Salt Splitting Without
Demineralization," 16th Annual Meeting, American Power Conference, 24-26 March
1954.
[16] Applebaum, S. B., ^Experiences with Chloride Anion Exchangers for Reducing Alka-
linity Without Acid," Proceedings, 13th Annual Water Conference, Engineers' Society of
Western Pennsylvania, 20 Oct. 1952.
[17] Wheaton, R. M. and Bauman, W. C., Industrial and Engineering Chemistry, IECHA,
Vol. 45, 1953, p. 228.
[18] Hall, R. E., U. S. Patent No. 1,956,515, 1934, reissue, 19,719 1935; U. S. Patent No.
2,087,089, 1937.
[19] Industrial and Engineering Chemistry, IECHA, Vol. 29, 1937, p. 584; Vol. 31, 1939, p. 51,
Vol. 32, 1940, p. 1572.
[20] Henry, C. R., Journal, American Water Works Association, JAWWA, Vol. 42, Sept.
1950.
[21] Zimmerman, F. J., Chemical Engineering, CHEEA, 25 Aug. 1958, p. 117.
[22] Green, R. V. and Moses, D. V., Sewage and Industrial Wastes, SIWAA, 1952, p. 288.
[23] Gehm, H. W., Sewage Works Journal, SWJUA, Vol. 16, 1944, p. 104.
[24] Dickerson, B. W. and Brooks, R. M., Industrial and Engineering Chemistry, IECHA,
Vol. 42, 1950, p. 599.
[25] Ryan, W. J., Water Treatment and Purification, McGraw-Hill, New York, 1937, p. 221.
[26] Dobson, J. G., Transactions, American Society Mechanical Engineers, TASMA, April
1946.
[27] Hale, F. E., "The Use of Copper Sulfate in Control of Microscopic Organisms," Phelps
Dodge Refining Corporation, 1939.
[28] Whitney, W. R., Journal, American Chemical Society, JACSA, Vol. 25, 1903, p. 395.
[29] Walker, W. H., Cederholm, A. M., and Bent, L. N., Journal, American Chemical
Society, JACSA, Vol. 29, 1907, p. 1251.
[30] Pearson, J. M., "Fundamentals of Cathodic Protection," Corrosion Handbook, Wiley,
New York, 1948, p. 923.
[31] Speller, F. N., Corrosion, Causes and Prevention, 3rd ed., McGraw-Hill, New York,
1951.
[32] Speller, F. N., Proceedings, PDHAA, National District Heating Association, Vol. 24.
1933, p. 203.
[33] Berk, A. A., U. S. Bureau of Mines, Report of Investigation No. 3754, 1944.
[34] Kahler, H. L. and Brown, J. K., Proceedings, 10th Annual Water Conference, Engineers'
Society of Western Pennsylvania, 1949, pp. 115^126.
[35] Guernsey, E. W., Transactions, American Society of Heating and Ventilating Engineers,
TAHVA, Vol. 51, 1945.
[36] Darrin, Marc, Industrial and Engineering Chemistry, IECHA, Vol. 37, 1945, p. 741.
[37] Lehrman, L. and Shuldener, H. L., Journal, American Water Works Assocation,
JAWWA, Vol. 43, March, 1951.
[38] Hatch, G. B. and Rice, O., Industrial and Engineering Chemistry, IECHA, Vol. 37, 1945.
[39] Powell, S. T., Industrial and Engineering Chemistry, IECHA, Vol. 26, 1934.
STP442A-EB/Jul. 1978
The growing water shortage in many parts of the world has made water
reuse a popular topic of concern. However, reuse actually is an ancient
practice. Since there is a fixed amount of water on the earth, it is clear from
the law of conservation of matter that the same water must be used over and
over again to fulfill the many needs. The perpetual cycling of water from
atmosphere to earth to ocean and back again to the atmosphere of course is
not uniform throughout the world. In some places, water evaporated from
the oceans is returned rather quickly by mountain streams with little or no
use. In other cases, precipitation may percolate into groundwater systems,
from which much of it may not emerge again for thousands of years. But
sooner or later the natural laws which control the hydrologic cycle guarantee
that all water will return to a point of use. Reuse is the inevitable result of
this process.
The current emphasis on reuse of water results from the fact that water
users and water uses are increasing throughout the world. Industrialization
is responsible for the greatest increase in water requirements. Since the
amount of water is fixed, it is obvious that the available supply must be
handled more often between the time it precipitates from the atmosphere
and the time it evaporates from the ocean. Each successive user along its
path automatically becomes a reuser, and the more numerous the reusers,
the more important becomes the subject of technology of water reuse.
Considerable hysteria has been created by writers who imply that all water
drawn from a resource for a given purpose is lost to the needs of other
prospective water users. A thoughtful person will recognize immediately that
the terms "water withdrawal," "water use," and "water consumption" are not
synonymous. An industry may draw large quantities of water from a surface
stream or a well, use it only once in a closed cooling circuit, and pass it on to
the next user downstream. Another industry may draw very little water from
the source, but use it over and over again with relatively little actual water
84
Copyright© 1978 by ASTM International www.astm.org
CHAPTER 6 ON TECHNOLOGY OF INDUSTRIAL WATER REUSE 85
of water use resulted from the variety of return flow and on-site reuse
systems discussed in the following text.
Groundwater
Short-term reuse systems are not nearly as applicable for groundwater
sources as for surface-water sources. However, underground water may be the
principal, it not the only, supply in certain areas with limited rainfall and few
surface streams. This is true in parts of the southwestern United States. In
such areas, pumping groundwater at rates exceeding recharge of the
groundwater reservoir (aquifer) results in declining water tables and land
CHAPTER 6 ON TECHNOLOGY OF INDUSTRIAL WATER REUSE 87
critical use in the same industrial plant. Where the waste water is passed to
another process or cooling circuit, the system becomes a compound
multicycle-cascade type. The Dow Chemical Company's Midland, Mich.,
plant has an elaborate multiple recycle system which handles high-pressure
service and cooling water, domestic water, high-grade cooling and process
water, and demineralized boiler feedwater, in five separate supplies in-
volving many miles of distribution lines. This complex system uses eight
times as much water as it draws from the original water source. Eventually
all of the circuits are integrated to form a semicascade system and the final
waste water is mixed and treated in a central location. In such complex
operations, it is common to reclaim chemicals as by-products from the
various circuits as well as from the final cascade. It is also common to mix
the discharges to gain advantages from reactions of components. Thus an
alkaline waste might be neutralized by mixing it with an acid waste. Final
waste that cannot be reclaimed economically is discharged into a biological
waste treatment plant or into disposal wells.
Cascade System
A cascade system differs from a multiple recycle system in that a single
effluent stream flows from one process to another, increasing its waste
content as it goes until it finally is no longer useful for any part of the
operation. The water withdrawn from the source of supply first flows to the
equipment or process which requires the coldest or cleanest water, and from
here it passes to successive operations where progressively higher tempera-
tures and poorer water qualities can be tolerated. Thus, the waste of one
operation becomes the supply of the next. Either single passes or recycle
circuits may form the various steps of the cascade, but considerable recycle is
characteristic of most cascade systems. Almost every industry employs
cascade to some extent. A cascade system does not reduce water loss or
decrease the waste which eventually must be treated or discarded. On the
other hand, it generally reduces the number of water-cooling and waste-
treatment facilities required, and, of course, increases the percentage of
reuse. Its principal shortcoming is the need for designing heat exchangers
and processing equipment to tolerate the relatively poor quality of water in
the later stages. It also is more difficult to reclaim specific by-products from
the integrated waste stream that results from a cascade system. The Kaiser
Steel plant at Fontana, Calif., is the classic example of this type of reuse
system. Here a mixed plant supply of well water and local company water
is used for stepwise cooling of motors and heating furnaces; mill cooling and
scale flushing; and cooling open hearths, blast furnaces, and coke plants.
After this, it is divided into parallel streams for further cascading. These
streams handle less critical operations like gas washing, precipitative flush-
ing, and blast furnace cooling. The streams finally are mingled and used for
quenching slag. The diagram of the circuit presented in Fig. 1 shows that
some water is diverted for use in the tin mill, and that some is reclaimed from
CHAPTER 6 ON TECHNOLOGY OF INDUSTRIAL WATER REUSE 91
INDUSTRIAL
RESERVOIR
ZA MOTOR DOMESTIC
GALVANIZING ROOM AND HEATING USES
FURNACES
SEWAGE EFFLUENT
1 OPEN HEARTH
BLAST FURNACE
AND COKE PLANT
PIT RUNOFF
Kaiser's Fontana, Calif., system of multi-recycling cascade is so effective that the plant with-
draws only 5320 litres (1400 gal) of water per ton of steel produced, whereas as much as 247 000
litres (65 000 gal) are required in some plants. It can be said that the water is wrung dry in this
3000 percent reuse system.
FIG. I—Example of water reuse system.
the slag pit. Much of the final waste water is lost by evaporation from the
slag pit.
While a cascade system does not reduce the amount of water lost by
evaporation and may actually increase it to some extent, it does markedly
92 MANUAL ON WATER
increase the ratio of water used to the water withdrawn. In the case of
Kaiser's plant, each gallon of water is used 30 to 40 times, so that the plant
withdraws only 5320 litres (1400 gal) of water per ton of steel produced,
whereas as much as 247 000 litres (65 000 gal) of water per ton are withdrawn
in some plants. Such a cascade plant is more costly to build, but it has the
advantage of ability to operate in an arid zone where it might be impossible
to operate otherwise.
Examples of cascade reuse can be found in almost every industry. In
Holland power plant blowdown (boiler waste) is used for coal washing.
Stack gas wash water and mine waste are used for the same purpose. Any
number of stepwise combinations can be used to advantage where shortages
provide the incentive.
Heat Dissipation
The extent to which water can be used is determined in large part by the
effectiveness of quality control treatments in the reuse system. Since
approximately 80 percent of all industrial water is used for cooling,
CHAPTER 6 ON TECHNOLOGY OF INDUSTRIAL WATER REUSE 93
Organic Deposits
Open cooling systems are likely to develop algae and bacterial slime
growths. In the United States, organic growths generally are controlled with
chlorine or with nonoxidizing bactericides and algicides, whereas the British
chimney-like cooling towers depend on light-tightness for elimination of
some of the nuisance organisms. Antirot and fungal control treatments are
available for protection of construction materials and fill in wooden towers,
but slow deterioration is inevitable.
94 MANUAL ON WATER
References
[7] Clarke, F.. E., Industrial and Engineering Chemistry, IECHA, Vol. 54, Feb. 1962, pp.
18-25.
[2] Council, C. H., "Municipal Wastewater for Industrial Supply," presented at the Meeting
of the Process Industries Division of the American Society of Mechanical Engineers,
Houston, Tex., Oct. 4-6, 1961.
[3] Weaver, D. G., Industrial and Engineering Chemistry, IECHA, Vol. 53, Oct. 1961, pp.
773-778.
[4] Denman, W. L., Industrial and Engineering Chemistry, IECHA, Vol. 53, Oct. 1961, pp.
817-822.
STP442A-EB/Jul. 1978
Water is the most plentiful liquid on earth. It is a requirement for all life,
whether it is used in metabolic processes, as a solvent of minerals, or in the
disposal of waste. Indeed, it is difficult to name a natural phenomenon in
which water, in one form or another, has not had an essential role.
Nature has provided for the conservation of this abundant and valuable
liquid by endowing it with a considerable capacity to rid itself of foreign
substances. This process, known as self-purification, is an inherent system
for water. Man's only problem with the system is that the water does not
always clean itself quickly and completely enough for the next intended reuse.
Almost all of the processes used by man to clean the water are accelerated
natural-quality recovery mechanisms. The water may be moving in streams,or
be relatively static as in lakes or the oceans, but the natural processes of
purification are proceeding toward completion. Advantage is taken
of this intrinsic ability of water to purify itself by using it as the final
polishing treatment for all municipal and industrial waste discharges.
Streams contaminated by natural, human, or industrial wastes are
rendered stable by self-purification. Eventually, this water becomes innoc-
uous and is again reused by man or nature. This purification is accomplished
by combinations of the physical, chemical, and biological forces present in
the water environment. The extent to which each force operates is dependent
upon the contaminating substance and the particular water environment in
which it is present. Physical forces separate suspended solids; chemical forces
cause reactions which neutralize the nocuous wastes; and biological forces
stabilize the water by using the contaminating substances as nutrient sources
and by enchancing both physical and chemical phenomena. Generally, the
biological forces are the most active and the most important in the self-
purification of a stream.
droplets of water which are pure until they fall through a contaminating
atmosphere as rain, hail, or snow. The purity of the water is further affected
by contact with the soil or other surface.
The atmosphere usually contains a number of contaminants, especially in
areas of heavy air pollution. Such pollutants may be in the gaseous, liquid,
or solid state. Some solids, such as dusts, are laden with bacteria, yeasts, and
molds. In addition, the air contains the spores of microorganisms which
exist in the atmosphere without benefit of being attached to solid particles,
or entrapped in aerosoled liquids. Some bacteria and viruses, also occur in
the atmosphere as free-floating agents. Thus the atmosphere possesses a
distinct and variable microbiological flora.
The microflora of the atmosphere provide one of the sources of living
matter constituting a normal stream biota. When the water of the atmos-
phere falls to earth, the microorganisms and other matter present in the air
are washed out and settle upon the ground. Many of these microorganisms
become entrapped in the soil, while others are carried directly into streams
with the rainfall runoff. In addition, the water picks up microorganisms that
are indigenous to the soil, which nearly everywhere is teeming with these
microscopic life forms. In this manner, water accumulates a wide variety of
microorganisms by the time it flows as a natural stream. The higher aquatic
biota vary widely depending not only on the microflora but also upon the
geochemistry, temperature, and the land character of the stream banks
through which the stream flows. Thus the runoff from a mountain is totally
different chemically, physically, and biologically to the runoff from a
swamp.
After water has formed one of the surface streams of the earth, it
establishes very characteristic biological flora, chemical composition, and
physical properties. The stream continually comes to equilibrium with its
environment, or changes due to the area through which it runs. The stream
biota reflects changes in the qualities of water received by the stream. For
example, if such waters contain domestic wastes (those derived from human
populations), the stream biota will respond with increases in the population
of organisms which are able to use these substances as food until either the
food is consumed or some other growth requirement becomes limiting. As
though to rid their environment of the unnatural or unusual added material,
the complete biota of the stream changes. This ability of the stream to
change its biota, its chemistry, and its physical properties in order to restore
its original state of purity may be termed "the dynamic equilibrium." The
forces of self-purification—physical, chemical, and especially biological—are
constantly interreacting to improve the quality of the water.
Pollution
The definition of water pollution generally accepted is: Any impairment of
water quality by man that is prejudicial or injurious to its suitability for
other defined uses. Note that this definition does not require that something
be added to the water, but considers as pollution any degradation in quality
as a result of man's use of the water. Thus, a river downstream from an
impoundment may be degraded if the stored water discharged has lost its
dissolved oxygen or if its temperature is too low for summer recreational
uses such as swimming, even though its temperature possibly has improved
for a trout habitat. Pollution through increased turbidity may be caused by
withdrawal of sand and gravel from the river bottom, with the waste wash
water and silt returned to the stream.
Although the effects of temperature increase or decrease are presented in
detail in Chapter 8, it needs to be pointed out that not all temperature
changes of normal ambient river water are "thermal pollution," since the
change may not be degrading the quality for other defined uses. When a
water discharge temperature is considerably below that which is normal in a
given stretch of river, it has been observed that temperature recovery to
normal values is much slower than the concurrent rise in dissolved oxygen to
saturation in the same stretch of river. Under conditions where the dissolved
oxygen content recovers in 8 km (5 miles), the temperature of very cold
water discharged from an impoundment may require as much as 64 km (40
miles) for recovery.
Degradation in water quality may occur below impoundment discharges
100 MANUAL ON WATER
at certain times of the year, for other reasons. Water in the lower layer
(hypolimnion) of thermally stratified impoundments may become anaerobic
for several months of the year. Discharged water entering the streams below
the impoundment may be low in oxygen during warm summer months,
when dissolved oxygen content may be most critical for a waste discharge.
Because of anaerobic conditions in the hypolimnion, the stored water may
contain hydrogen sulfide, iron, and manganese. Hydrogen sulfide lost to the
atmosphere below the dam may be a nuisance there. Iron generally oxidizes
rapidly and is precipitated on underwater surfaces; these surfaces become
visible during low flow periods. Manganese creates more difficult problems
of removal or treatment for users downstream. Cold water discharge from
the hypolimnion may increase the efficiency of power plant or industrial
condensers and may promote trout fishing, but the low temperatures will
prevent swimming, and also change the balance of numbers and species of
aquatic organisms.
When mineral acids or alkalies are added to a stream, either intentionally
or accidentally, many natural factors may be involved in recovery mech-
anisms. Observations of a stream reduced to pH 2.5 by release of a mixture
of hydrofluoric and fluosilicic acids indicated surprisingly rapid recovery to
a normal pH. There was complete absence of obvious toxicity in the river a
few miles downstream from the point of hydrofluoric acid addition,
apparently because of reaction with silicates in river bed minerals. The
reaction of hydrofluoric acid with silica apparently produced silicon tetra-
fluoride, which was lost to the air. This self-purification process was
chemical, rather than biological, but development of a normal biological
pattern quickly followed disappearance of the acid, there being ample soil
organisms available for reinnoculation of the river area, once excess
hydrogen ion toxicity had been removed.
A balance of biological forms is normal for all streams. Although various
species of plant and animal life may predominate in each stream, no two
streams are identical. Clean, pure streams, however, have certain char-
acteristics in common. One property of such a stream is its ability to dispose
of a reasonable amount of pollution. This may be accomplished without an
appreciable disturbance of the normal biota. If a stream receives an
unusually large amount of waste, the biota will change in an attempt to
stabilize such pollutants. However, if the quantity of such foreign materials
exceeds the capacity of the stream biota to render them innocuous, the
higher aquatic life may be completely destroyed for a stretch of the river. As
the unusual food concentration decreases, a new and different group of
organisms develops as a response to the new levels of oxygen and food.
receiving domestic wastes such as sewage undergo the classical cycle of zonal
self-purification. The same is true, in most instances, for organic industrial
wastes. A notable exception is that some wastes are toxic and inhibit, or
prevent, the operation of stream purification processes. The same is true
of many inorganic wastes.
Acid mine drainage is a pollutant that is indigenous to bituminous coal
regions. It is characterized by being highly acidic and containing large
concentrations of ferrous iron. It is formed by the oxidation of sulfuritic
materials (represented by the formula FeS2) of both operating and aban-
doned bituminous coal mines. A chemosynthetic autotrophic bacterium
(Ferrobacillus ferrooxidans) enhances the reaction several fold where the pH
of the water is in the range from 2.8 to 3.5. Dissolved oxygen is utilized by
these ferruginous effluents through the oxidation of ferrous iron to the ferric
state. Owing to the presence of Ferrobacillus ferrooxidans, which increases
the oxidation rate, the area in which dissolved oxygen is being consumed is
kept to the shortest possible stream distance. After the deposition of iron, as
basic ferric sulfates and hydrates, the stream makes a rapid recovery and
supports most of the normal forms of aquatic life.
107
Copyright© 1978 by ASTM International www.astm.org
108 MANUAL ON WATER
Stream Sources
The physiographic features of surface streams vary greatly across the
country. Width and depth, channel configuration and gradient, size of
drainage basin and climate—all influence stream temperatures in some
degree, both singly and in combination.
Excluding heat from hot springs for the moment, all natural heat in
streams comes directly or indirectly from the radiant energy of the sun. The
effect of solar radiation can be illustrated by the fact that the summer
temperature of large rivers in western Pennsylvania rises 1° to 2°C from
morning to afternoon, depending upon the amount of cloud cover. The sun
also contributes heat indirectly by heating watersheds, thereby warming the
rain that falls on them. The addition of heat from this source is probably a
relatively minor factor because the specific heat of earth and rock is only
about a fifth of that of water. Further, the cooling effect of a higher rate of
evaporation would tend to increase the rate of heat dissipation. This is a
complex mechanism that is difficult to generalize because it depends upon
the humidity gradient above the surface.
Water flowing off the land can raise stream temperatures in some areas.
This is especially true for the irrigatedjands of the Far West. Water in
irrigation ditches is heated by the sun. A variable proportion of this water
runs off into natural streams. The effect is likely to be small where the water
drains to large rivers.
The electromagnetic spectrum of the sun covers an enormous range (0.001
to 3 X 1014 A), but practically all radiation of wavelength shorter than the
near ultraviolet is absorbed by the outer atmosphere of the earth, while
radiation beyond the near infrared is absorbed by dust and water vapor at
lower levels. The radiant energy that reaches the earth's surface is partly
reflected and partly absorbed. That which is absorbed is reemitted as long-
wavelength radiation. This dissipation of energy tends to lower the tempera-
ture of surface water and it accounts, in part, for the diurnal change in water
temperature.
Evaporative cooling is another important factor in the dissipation of heat.
The rate of evaporation of water is proportional to the air-water temperature
difference and the unsaturation of the surrounding air. When the layer of air
adjacent to a water surface is saturated with water vapor (at its dew point),
the net evaporation is zero because the number of water molecules leaving
the water surface is exactly balanced by the number condensing into it. Wind
has an important effect on evaporative cooling because it sweeps away the
CHAPTER 8 ON THERMAL LOADING OF WATER SUPPLIES 109
saturated air and replaces it with air containing less moisture. The latent heat
of vaporization of water is 580 kg-cal at 30° C (1045 Btu at 86° F). Thus
evaporation of a cubic metre (35.3 ft3) of water would absorb 580 000 kg-cal
(2.3 X 106 Btu). This would have the theoretical effect of lowering the
temperature of 580 m3 (2.05 X 104 ft3) of water 1°C (1.8°F).
Water is also cooled by loss of sensible heat through direct transfer to cool
air in contact with it. Aside from back-radiation of energy, about 20 percent
of the temperature lowering results from loss of sensible heat and the
remainder from latent heat of vaporization.
Climate has a distinct effect on surface water temperature. Stream
temperatures in summer range from about 18°C in the Northeast to 13^C on
the Northwest Coast and parts of the Great Basin to 32° C in the Southwest
and Southeast. These temperatures reflect the influence of air tempera-
ture as it varies across the country.
Groundwater Sources
It has been estimated that some 60 percent of the mean flow of streams is
contributed by groundwater discharged from adjoining aquifer systems.
Below the depth where the temperature of aquifers is unaffected by
insolation and stream infiltration, the temperature of groundwater is
practically constant in any given locality. Thus groundwater discharge tends
to ameliorate stream temperatures because it is warmer in winter and cooler
in summer. Shallow groundwater temperatures normally vary inversely with
latitude, ranging from 3°C in northern Minnesota to 22° C in the Southwest
and 25° C in southern Florida.
Below the depth at which the temperature of the earth's crust is affected by
insolation, the primary control on temperature in a particular region is the
relatively constant flow of heat from the interior. Other factors include the
thermal conductivity of rocks and their contained fluids, volcanic or
magmatic activity, and tectonic movements. The temperature of ground-
water at a few tens of feet is about the same as the mean annual air
temperature. Several authors report an average value of the geothermal
gradient, usually measured to some depth below the zone of active ground-
water circulation, of 1°C for each 30 m of depth.
Water from thermal springs can raise the temperature of streams in some
areas. There are many such springs in the United States, most of which are
west of the 105th meridian. The western springs arise from precipitation that
has percolated into the earth and come in contact with hot geological
formations. Those in the Appalachian range spring from very deep forma-
tions where the water has been warmed by heat conducted from the interior
of the earth. The U. S. Geological Survey has listed 1059 springs with normal
temperature at least 6°C above the mean annual air temperature. A few
springs have temperatures of 100°C or more. Less than a third of the thermal
springs have flows of 0.38 m3/min (100 gal/min) or more. Thus this source
110 MANUAL ON WATER
Industrial Sources
Most water withdrawn for industrial operations is used for cooling. This
water is discharged substantially unchanged except for an increase in
temperature. The effects of these discharges are highly variable. They depend
upon the temperature difference between the discharge and the receiving
water, the size and configuration of the receiving stream, the rate of heat
dissipation, the quality of the receiving water, and the downstream uses that
could be affected. There are also certain economic considerations that are
mentioned in a later section.
The generation of hydroelectric power is a special industrial use of water.
This operation merely converts the potential energy of water into electric
power, but it can adversely affect conditions downstream. In the first place,
the operation of hydro plants is highly cyclical in many areas because the
CHAPTER 8 ON THERMAL LOADING OF WATER SUPPLIES 111
Municipal Sources
Domestic sewage, with or without treatment, is usually discharged to
surface water at the most convenient location. This waste flow normally has
a temperature well above that of the receiving water. Although it contributes
measurably to the thermal load, it has consequences greater than the
physical effect of raising stream temperatures. This method of disposing of
sewage relies upon natural phenomena to render the material innocuous.
The principal natural process involves utilization of the dissolved oxygen in
surface water to oxidize the organic substances in sewage to relatively inert
compounds. The rate of aerobic oxidation varies directly with temperature.
Thus, as the temperature of the receiving water rises, the demand upon its
limited dissolved oxygen resources increases. The increase may be great
enough to use up all the dissolved oxygen. Anaerobic conditions then
develop, and decomposition of the organic matter generates foul gases. At
the same time, all aquatic life that depends upon aerobic conditions is
destroyed. This represents a condition where a rise in temperature can have a
profound effect on water quality. The situation is of course not confined to
municipal sewage; the same result can occur where a heated industrial waste
containing organic matter is discharged.
Many industries and some municipalities store partly treated waste water
in lagoons. Some lagoons are equipped with devices that provide for
discharge of the stored water in an appropriate proportion to the flow of the
receiving water. In other cases, the lagoons are drawn down only during
periods of local flood flows. These lagoons are generally shallow basins and
their summer temperature will usually be higher than that of surface streams.
112 MANUAL ON WATER
Data are not available on this source of thermal loading but the potential
effects should not be ignored.
Thermal Patterns
The rate of natural distribution and dissipation of heat is a major
consideration in deciding upon the size of a thermal load that can safely be
added to surface water.
Field tests have indicated that the die-away of temperature in streams is
roughly exponential; that is, as distance downstream from a source increases,
the stream temperature approaches the natural temperature asymptotically.
Thermal loads are dissipated in several ways, including back-radiation,
evaporative, and conductive cooling.
Heated water discharged below the surface of a stream usually mixes
rapidly with the body of water in a vertical direction. If the discharge is at the
water surface, a substantial temperature gradient may persist for a con-
siderable distance downstream, especially where the stream flow is tranquil.
Actual die-away patterns can be plotted by making a series of temperature
traverses at regular intervals along the course of a stream. In predicting
thermal patterns, it is necessary to measure solar radiation, wind velocity,
and stream flow, as well as the decline in temperature from the source. Quite
off thermal patterns are found in canalized rivers receiving a number of
heated discharges. In a survey of the Monongahela River in Pennsylvania, the
decrease in temperature was measured in terms of stream distance at several
locations at which thermal loading had raised the stream temperature to
32° C or higher. The rate of decrease ranged from 0.5° to 3°C in several 300-
m reaches. The rate of fall varied more with location than with time of year.
Systems for temperature predictions on complex thermally loaded streams
are not yet fully developed, but progress is being made.
The winter temperature pattern is isothermal in typical temperate-zone
lakes or reservoirs under open-water conditions. There is complete vertical
circulation in consequence of the uniform density of the water at about 4°C.
In spring, solar heating warms the water surface, decreasing its density
sufficiently to prevent mixing of the warm, upper water with the colder,
denser water below. As the surface becomes progressively warmer, the
density gradient steepens and the depth to which wind can mix the upper
waters is diminished. The result is a separation of the lake into two isolated
masses consisting of a circulating surface volume (epilimnion) floating above
a relatively stagnant volume below (hypolimnion). Separating the two is the
thermocline, a stratum of water of variable vertical thickness, in which the
temperature decreases rapidly with increasing depth. This stratification
usually persists until autumn, when cooling of the surface increases its
density and leads to breakdown of thermal stability. When this occurs, the
lake "overturns" under the influence of wind, and circulation of all the water
results.
CHAPTER 8 ON THERMAL LOADING OF WATER SUPPLIES 113
Wind will keep the water in circulation unless a persistent ice cover forms.
In that event, an inverse type of thermal stratification will result until it is
destroyed by warming and wind action. If winter stagnation occurs, it will be
followed by a spring overturn and a second period of circulation.
The most significant changes, in groundwater temperatures are caused by
induced infiltration of surface water or the injection of warm water.
Infiltration from shallow wells in several Central and Eastern locations has
caused an annual variation in groundwater temperature of 8° to 18°C. In
some coastal areas, it is necessary to inject water from air conditioners to
restrain the intrusion of saltwater into aquifers. An example is Long Island,
N. Y., where air^conditioner water is injected at temperatures 2° to 11°C
higher than the water pumped from aquifers.
The rate of thermal dispersion at any point in an aquifer is mainly a
function of the transmissibility of the aquifer and its extent. The thermal
conductivity and specific heat of the aquifer matrix are relatively unimpor-
tant. Heat in water discharged to an aquifer through a well, or recharged
from a surface water source, is dispersed both vertically and horizontally in
the same manner as a dissolved solid; its rate of vertical dispersion is
enhanced by convective movement due to the density contrast between the
formation water and the recharge water. The pattern of thermal dispersion is
also a function of the temperature of the recharge water, because the
viscosity of water varies about 2 percent/deg C in the range 5° to 38° C. This
causes a significant increase in the rate of groundwater flow in the thermally
affected area. The thermal loading of groundwaters results in extremely
complex hydraulic problems because both density and viscosity have
transient values throughout the affected aquifer.
ceptable where the degree of treatment conforms with the volume of diluting
water and the forces of natural purification. Aerobic biological activity is the
most important of the purification forces because it converts complex
organic matter into innocuous substances. Within certain limits, the rate of
biological activity roughly doubles with each 10° C rise in temperature. This
places a corresponding burden on the dissolved-oxygen resources of the
water. A rise in temperature is advantageous where the water contains
enough dissolved oxygen to accommodate the increased demand, because
purification will occur more rapidly. But noxious conditions will develop
wherever the demand for dissolved oxygen is greater than the supply. A rise
in temperature, however, will generally stimulate the proliferation of
photosynthetic organisms, especially the phytoplankton, which will help to
make up the oxygen deficit during daylight and cause an added deficit
during nighttime due to respiration. Warm water can therefore be beneficial
in some cases, but detrimental in others.
The ability to draw a glass of cool water from a faucet would often be
desirable, but the almost universal use of refrigeration makes this less
important than it once was. On the other hand, the warmer the supply, the
lower the cost of heating water for the laundry and other purposes. The
lower the temperature of the water entering a purification plant, the more
difficult the treatment becomes. For each 5 deg C rise in raw-water
temperature, the cost of treatment drops 30 to 50c per million gallons
processed. But warm water might promote the growth of algae that can
cause tastes and odors. Thus a rise in the temperature of municipal water
supplies has both good and bad features.
Industry is an extensive user of water for cooling purposes. This suggests
that a source of cool water would confer a benefit so valuable that it would
be a major factor in plant location. But such items as raw materials, markets,
transportation, supply of workmen, and community services are usually so
much more important to a successful enterprise that the temperature of the
local water supply becomes a minor factor. Industry resorts to well water or
refrigeration where it needs water cooler than the surface supply.
The steam-electric power industry might constitute an objection to this
generalization about the limited importance of a cool-water supply. There is
an inverse relationship between the temperature of cooling water and the
efficiency of power generation; this is a matter of real concern in some areas.
This is necessary to protect subsequent water uses, and many kinds of
specific regulations have been promulgated to ensure effective downstream
protection.
It is easy to accept the abstract principle of reasonable use of streams for
waste disposal because it represents economic logic. But problems arise in
applying the principle in specific situations because of the difficulty of
reaching agreement on the reasonableness of a particular use. This is a
consequence of limited quantitative information on the actual effects of
waste waters, especially those at elevated temperatures.
CHAPTER 8 ON THERMAL LOADING OF WATER SUPPLIES 117
Summary
This chapter has described thermal loading, and the principal mechanisms
by which the added heat is dissipated. The disparate effects that can result
from discharges of heated water have been discussed in some detail. In
particular, considerable attention has been given to the effect on fish because
this commonly provokes the greatest public distress.
Due to Federal regulations, industries have or are facing the technical and
economic problems associated with elimination of heated discharges.
STP442A-EB/Jul. 1978
Manual Sampling
Types of liquid samples are broadly classified into two major groups, one
called instantaneous, spot, snap, or grab samples; and the other integrated,
continuous, or composite samples. A grab sample is a collected single
portion of water or waste water which serves as a spot check and is useful for
investigating abnormal characteristics. A series of grab samples is necessary
for tracing constituent variations. The volume of individual samples will
depend on the analysis requirements. If samples are to be composited, the
volume collected must be more than needed for the proportional part of the
118
Copyright© 1978 by ASTM International www.astm.org
CHAPTER 9 ON SAMPLING AND FLOW MEASUREMENT OF WATER 119
Continuous Sampling
If it is necessary for sampling to extend over a considerable time, or when
a continuous record of conditions at a given sampling point is required, it
will be most practical to install automatic continuous sampling equipment.
Correctly designed and installed, a continuous sampling device will provide
more frequent samples than is practical by the manual method, will eliminate
errors due to the human element, reduce costs for supervision, and eliminate
the tedious routine work required by manual sampling.
Since the scope of this chapter does not permit complete description of the
many automatic devices suitable for continuous sampling of industrial water
and waste water, the reader is referred to other sources for additional
detailed information [7,2].'
'The italic numbers in brackets refer to the list of references appended to this chapter.
120 MANUAL ON WATER
FIG. 4—Variation in concentration with depth, Lake Mead, Arizona and Nevada (1 ft -
3.048 m).
CHAPTER 9 ON SAMPLING AND FLOW MEASUREMENT OF WATER 123
that they turn over during the fall. As the surface water cools and becomes
more dense, the lower layers, being warmer and less dense, rise and replace
the former top layers. Usually this turnover is rapid, and the resulting
changes in composition of the water may be considerable.
Shallow lakes do not vary much in composition from top to bottom
because mixing by the winds is generally good. The problem of sampling is
therefore decided by the number and composition of streams feeding such
lakes.
Reservoirs can usually be considered as lakes, but the phenomenon of a
density current frequently is characteristic of deep reservoirs and occas-
ionally of shallow basins. A density current is a stream of water that
maintains its identity, with respect to both chemical composition and
suspended solids, for long distances beneath the surface of the reservoir. It is
caused by difference in density of the flowing water, either as a result of a
difference in temperature or of the material in solution or in suspension or
both. When encountered, such a density current requires a careful sampling
schedule.
The composition of most well waters varies only slightly from year to year,
and a single sampling station is sufficient. Usually two or three samples per
year provide satisfactory coverage. There are exceptions, such as deep wells
that have been drilled through strata containing water high in mineral
content into a deeper stratum that contains water of better quality. Leaking
casings or poor construction can lead to contamination of the good water. A
shallow well receiving water by percolation from a nearby stream may
fluctuate in composition. Such conditions necessitate more frequent samp-
ling.
The groundwater in some areas varies in composition with the season.
Such cyclic changes are usually related to solution channels in limestone,
gypsum, or other soluble rock, and to variations in rainfall. Rainwater
quickly reaches the water table and dilutes the higher concentrations of
dissolved minerals. The concentration of the groundwater is thus lower
during the rainy season than during the dry season. Figure 5 shows the
composition of such a well-water supply.
A new well, or one that has been dormant for an extended period, should
be pumped sufficiently before sampling, to guarantee that the delivered
water is representative of normal conditions. This may require several days
or weeks.
For sampling water from a pipe or conduit, it is desirable to choose a
single sampling station. For example, in a cooling system with or without
cooling towers, a single sampling station is desirable for chemical-treatment
control. Satisfactory selection of the station may require a fairly extensive
124 MANUAL ON WATER
bed types, may require several sampling points for satisfactory control and
for termination of the operating run before treated water quality has
deteriorated significantly. Since this type of treatment plant lends itself to
full or semiautomatic operation, flowing samples are generally employed
together with monitoring instruments for continuously recording pH, differ-
ential conductivity, and hardness. Complete reliability in silica monitoring
instruments must be attained in terminating the service run of demineralizers
as the exhaustion point of the ion-exchange material is approached. A
practical silica recorder accurate in the range of 0.02 to 0.05 mg/litre and
manual sampling are important to the successful operation of this specific
treatment method. Manual samples taken toward the end of an operating
run and again following regeneration and return to service are usually
necessary, depending upon the type of installation and the degree of
instrumentation. The time for removing these two samples must be estab-
lished by sampling over a short-time interval or on a volume-of-water basis,
near the end of two or three demineralizing cycles and two or three rinsing
cycles. The composition of some water treated by ion exchange changes
rapidly toward the end of the service cycle and may require a sampling
interval as short as 1 min.
pressure will contaminate it. Leakage from pressure systems is visible, but
inleakage to a subatmospheric sample is not.
Deep Sampling
To facilitate collection of samples in deep bodies of water, two types of
samplers, depth integrating and point-type samplers, are in general use.
Depth integrating samplers consist only of a weighted metal frame or
other mechanical device for holding or clamping a glass bottle securely while
it is lowered at a uniform rate throughout the vertical profile of the body of
water.
For the collection of water at a specific depth, the Foerst-modified
Kemerrer-type water sampler is frequently used. The sampler is lowered to
the desired depth in the open position; then a messenger weight which trips
the closing mechanism is run down the suspension line.
The messenger weight must meet the triggering device on top of the
sampler squarely. Hence, a set of messenger weights drilled to accommodate
suspension lines of different diameters permits the use of the sampler with a
wide variety of ropes and cables.
When samples are required for the determination of dissolved gas content
and constituents susceptible to aeration, special equipment and technique
are required. The Foerst sampler can be utilized for this purpose by
transferring the sample by means of a tube connected to the outlet valve
projecting into the bottom of the sample bottle. Several displacements of
water in the bottle should be made to assure that a representative sample is
obtained. ASTM Method D 3370, Sampling Water [#], describes sampling
methods and apparatus.
Objectives
Common objectives in a sampling program should serve a number of
purposes, including the determination of quantities of industrial wastes to
be discharged, location of major sources within a plant, character of wastes,
establishment of a basis for waste treatment, potential recovery of valuable
material, and the effect of discharged wastes on the receiving stream.
Sampling Procedures
It would be rare if two waste problems were alike in all details, and the
approach to waste sampling must deviate somewhat from the procedures for
water; each must be handled as an individual case. Sampling must be
tailored to fit the operation of each manufacturing plant and the character-
istics of the waste produced. Special procedures are necessary to handle
132 MANUAL ON WATER
Sampling Points
Sampling points for waste waters are located preferably where flow
conditions encourage a homogeneous mixture, such as the downstream side
of a hydraulic jump, Parshall flume, or weir.
In sewers and deep narrow channels, samples should be removed from a
point one third the water depth from the bottom. In wide channels, the point
of collection should be rotated across the channel. In any event, the velocity
of flow at the sample point should be sufficient to prevent deposition of
solids. Creation of turbulence during collection of samples may liberate
dissolved bases and volatiles and make the sample unrepresentative. A
representative sample of a heterogeneous mixture of waste water, parti-
cularly one containing oil, is difficult to collect, but collection of a composite
and analysis of an entire individual sample will give a fairly accurate estimate
of the characteristics of the waste.
Recognized testing and precautionary measures [9] should be followed in
taking samples from deep manholes to guard against accumulations of toxic
and explosive gases.
Sampling Equipment
Figure 10 shows a diagrammatic arrangement of a continuous sampler
suitable for uniform flows of homogeneous waste water.
Sample Preservation
Considerable research on the problem of preventing chemical, physical,
and biological changes in waste water samples which might affect the
biochemical oxygen demand (BOD), suspended solids, dissolved gases,
cyanide, and phenol values has failed to perfect a universal treatment or
method, or to formulate a set of fixed rules applicable to samples of all types.
Prompt analysis is undoubtedly the most positive assurance against error
from sample deterioration.
CHAPTER 9 ON SAMPLING AND FLOW MEASUREMENT OF WATER 133
Flow Measurement
Flow measurement is an essential function in the study of water as an
engineering material. Since it involves principles of hydraulics and fluid
mechanics that are applicable to all problems of flow measurement, a
knowledge of the theory, methods, and types of equipment for measuring
flow is essential. A simple measurement of the liquid depth in a standard
container per unit of time serves conveniently for obtaining information on
the amount of precipitation on the earth as rainfall. More complicated
measurements involving rather intricate formulas and flow-measuring de-
vices are necessary for determining the volume of surface runoff and
CHAPTER 9 ON SAMPLING AND FLOW MEASUREMENT OF WATER 135
Basic Requirements
The network of piping, underground sewers, and open channels used to
convey water and waste water in modern plants presents many problems in
flow measurement. There is no universal procedure, because flows must be
measured under a variety of conditions. The measurement methods must be
applicable to specific conditions, The type of flow device, its location, cost of
installation, quality of flow data, and suitability for the service must be
considered. This discussion covers briefly the kinds of flow-measuring
devices, fundamentals of flow measurement, description and design of flow
devices, and important points to consider in their selection. These should
serve as a guide in choosing the equipment and method best suited to the
purpose and in establishing a suitable location for obtaining data. The
subject of hydraulics cannot be covered completely in this brief discussion,
and it is suggested that reference books [10] be reviewed to obtain basic
fundamental concepts.
FIG. 13— Typical installation of head area meter for V-notch weir.
138 MANUAL ON WATER
These devices are used in main-line metering and in metering flows at any
point where water moves under pressure in a confined pipe.
(b) Velocity meters consist of a device by which a vane or propeller turns
in direct ratio to the rate of flow past the propeller. These devices, similar to
the one shown in Fig. 21, are used in main-line metering, pramp discharges,
etc.
(c) Pitot tubes consist of a vertical tube with a right-angled tip inserted in a
flow, with the tip facing upstream. The height to which the fluid rises in the
tube is a function of velocity and therefore of rate of flow.
Pumps—Pumps can be used as measuring devices only if the number of
repeat cycles can be determined. Controlled-volume reciprocating pumps
can be used easily for this purpose, but centrifugal pump discharges must be
calibrated for each speed of operation, suction lift, or discharge head. Pumps
are not generally used or recommended for flow measurement and should be
considered only when other means prove to be impractical.
Displacement Meters—Displacement meters operate on the fill-and-draw
principle. Fill-and-draw measurements of reservoirs and tanks can be made
if flows into and out of the tank do not occur simultaneously. When the fill-
and-draw principle is applied to a closed device, a compartment is alter-
nately filled and emptied.
Constant-Differential Meters—Constant-differential meters, commonly
called rotameters, consist of a tapered tube, smaller at the bottom than at the
top, in which is confined a movable element termed a "float." The float rises
or falls in the tube in proportion to changes in the rate of flow of the fluid.
This device, which is illustrated diagrammatically in Fig. 22, is not used for
measuring large flows; it has its greatest usefulness in measuring gas flows.
Secondary Instruments
A secondary instrument or receiver is the device used to convert meas-
urements sensed by, and transmitted from, the primary measuring unit into
observable information on flow. Liquid level and pressure also can be shown
on secondary instruments.
Secondary instruments are classified in two ways: (a) according to the type
of information desired, and (b) according to the method of transmission
from primary to secondary unit.
References
[7] Environmental Protection Agency, Training Manual: Industrial Liquid Waste Surveys,
Cincinnati, Division of Manpower and Training, 1969.
[2] New York State Department of Health, Industrial Wastewater Discharges, Albany, Health
Education Service, 1969.
[3] Private communication from Cyrus William Rice and Company, Inc., Pittsburgh, Pa.
144 MANUAL ON WATER
[4] White, W. F., "Chemical Quality of Industrial Surface Waters of Pennsylvania," Paper
presented at the Tenth Annual Water Conference, Engineering Society of Western
Pennsylvania, Oct. 1949.
[5] "Industrial Utility of Water in Pennsylvania," Publication 17, Pennsylvania Department of
Commerce, State Planning Board, Aug. 1947.
[0] "Quality of Surface Waters in the United States," Paper 1022, U. S. Geological Survey,
1944.
[7] Dewey, E. S., Jr., "Life in the Depths of a Pond," Scientific American, SCAMA, Vol. 185,
Oct. 1951.
[g] Annual Book of ASTM Standards, Part 31.
[9] "How Sewer Manholes Are Checked for Toxic and Explosive Gases," Public Works, Vol.
85, May 1954, p. 149; "Gaseous Fuels," American Gas Association Book, 1954, p. 334.
[10] King, H. W. and Brater, E. F., Handbook of Hydraulics, 5th ed., McGraw-Hill, New
York, 1963; Russell, G. E., Textbook on Hydraulics; King, H. W., Wisler, C. O., and
Woodburn, J. G., Hydraulics, 5th ed., Wiley, New York; and Gibson, A. H., Hydraulics
and Its Applications.
[11] Symons, G. E., Water and Sewage Works, WSWOA, Vol. 101, Sept. 1954, p. 395.
STP442A-EB/Jul. 1978
Chapter 10—Water-Quality
Monitoring
Economics
The economics of automatic monitoring can be attractive. Whereas a
fairly large capital expenditure must be made for the monitoring equipment,
the operating expenses, including maintenance, are much less than the costs
of analyzing repeated grab samples in a control laboratory. Because they are
completely objective, the results are more reliable, and their accuracy can be
determined easily with the proper calibration and checks against standards.
CHAPTER 10 ON WATER-QUALITY MONITORING 147
Process Control
The monitoring of industrial process streams not only offers the direct
advantages of better products at reduced costs, but also the indirect
advantage of improved process efficiency, thus producing less waste material
that must be treated or reclaimed. An example of such process control may
be found in the steel industry, where sheet steel is pickled in acid baths. In
one typical case, it was found that continuous monitoring and control of free
acid concentration and iron content of the pickling baths led to an improved
product, with reduced acid consumption. The decrease in acid usage meant
that less excess acid had to be neutralized when the spent pickling baths were
treated to precipitate ferric hydroxide, and clarified, before the effluent
could be discharged to a natural body of water.
rivers and tributaries could be used for material balances and could permit
evaluation of the effect of a stream on another river or body of water!
Types of Measurements
The types of measurements used in evaluating water characteristics fall
into two major classifications, physical and chemical.
Physical measurements can be considered broadly (with some ambiguity
and overlap) to encompass properties of temperature, density, conductance,
surface tension, refractive index, radioactivity, pH, redox potential, and
some others employing chromatography, colorimetry, turbidimetry-nephel-
ometry, and specific ion electrodes. Some of these determinations are made
simply by immersing a sensor in the water, while others require a portion of
the water to be taken as sample and diverted through the sensor portion of
the instrument.
The second major category of measurements is those involving chemical
analysis procedures. Here, chemical analysis is defined as the addition of
reagents, causing chemical reactions to occur, before a measurement can be
obtained. Examples of chemical analysis measurements are all those that
add reagents and employ various sensors which respond to pH, redox
potential, color, turbidity, or conductance changes to read out the result. A
brief description of these methods is presented later in this chapter.
Sample portions are collected and measured at programmed intervals
when a continual analyzer is used. The time between continual analyzer
results can vary from seconds to hours.
It must be understood, however, that the type of sampling system required
is dictated to a great extent by the type of instrument to be used and by
stability of the component to be measured. Furthermore, the instrument
output or readout can be no more accurate or representative than is the
sample supplied. If the instrument does not receive a representative sample,
it cannot produce representative data, regardless of how well it is designed or
operates.
When an instrument is to be used for direct control of water or process
streams, as well as for monitoring, the delay interval between the time of
sample collection and detection of the signal must be accounted for and
offset by varying the modes of a process controller.
When an instrument is to be used for process control, the delay interval
between the sampling time and the detection of the analytical result must not
be significantly greater than the time required for the sampled flow to reach
the control point.
Environmental Considerations
Misapplications, such as installing a monitoring instrument in an environ-
ment where it cannot function properly, will lead to unsatisfactory operation,
150 MANUAL ON WATER
Sampling Considerations
Preparation for the installation of an instrument consists of much more
than (1) speculating on what analysis will suffice, (2) obtaining bids from
several vendors and accepting the lowest one, and (3) setting the instrument
on a concrete pad and flipping on the switch. It is alarming to learn that this
is typical in far too many applications. This type of philosophy is normally
associated with ill-defined measurement objectives and may be the result of
pressure from a regulatory agency to provide immediate data on a particular
pollutant.
Beginning with the premise that the correct analyzer has been chosen for a
given application, the following aspects of sampling require in-depth
consideration if a functional support package is to be assembled.
1. Measurement objective
2. Sample point
3. Sample probe
4. Pumping system
5. Transfer lines
6. Sample conditioning
7. Analyzer interface (stream selection)
Measurement Objective
The definition of measurement objectives may appear to be elementary;
however, in numerous instances, measurement systems are incorrectly
applied. An example of a misapplied measurement system is the use of a
highly sensitive analyzer when something less sophisticated with a high-level
alarm device is all that is required. The majority of environmental analyzers
are used for either record-keeping or alarming, while only a few are used for
control purposes. Illustrations of control instruments would be automatic
titrators, biological activity monitors, and smoke monitors. The analyzer
used for record-keeping should be sensitive and extremely reliable if the
recorded data are necessary for demonstrating compliance.
CHAPTER 10 ON WATER-QUALITY MONITORING 151
Sample Point
The location of the sampling point is a direct outcome of the decision on
measurement objectives. Sampling for the purpose of determining the total
carbon discharge into a river is at a completely different location than that
intended to detect a leak at a tank farm. Questions of major importance in
locating a sample point are:
(a) Can a representation sample be obtained at this location? The more
representative sample will be obtained immediately downstream from a
turbulent area. When several streams flow together, causing minimal
agitation, it is best to induce turbulence if a representative sample is to be
obtained. In Fig. 1, three sewers are depicted flowing into a common sewer,
one of which is partially submerged. Note the location of the sample point in
relation to the area of turbulence.
(b) Can a measurement at this point quickly isolate the problem? Do not
expect an analyzer located downstream from the junction of three sewers to
be capable of identifying, during a period of high discharge, which sewer is
responsible.
(c) Is the measurement to be used for determining the magnitude of
discharge, to alarm in case of abnormal discharge, or to control pollution
abatement equipment?
(d) Is the sample point only one of several which will be monitored by a
single, centrally located analyzer?
(e) Will the sample point location allow sufficient lead time for ap-
propriate action?
Sample Probe
The type and positioning of the sample probe are to some degree dictated
by the measurement objective. If the measurement is not concerned with
solids, particularly heavy solids, then the probe should not be located too
near the bottom of a sewer. The reverse applies if you do not desire to
encounter oils, greases, etc., which normally are surface materials.
Probe design should not be taken lightly. A well-designed probe not only
can minimize the maintenance cost, but also reduce the frustation of trying
to operate an analyzer without an adequate sample.
Stream contents should dictate how the probe is built! If the sewer has a
low level of solids and is pressurized, it is possible to use an enlarged version
of a gas sample thief. When a high concentration of randomly sized solids is
present in an unpressurized sewer, it is best to mount vertically a large-
diameter probe. The suction velocity should be low enough to permit the
heavier objects to fall back down through the probe.
The use of relatively fine screens at the probe inlet is not recommended.
This practice usually results in a high incidence of plugging.
Vertical water probes used with low-pressure safety switch protection on
the pump are capable of self-cleaning. When the probe inlet becomes
plugged, the pump automatically shuts off, permitting the column of water
to backflush the probe. This procedure is not always adequate; if plugging
becomes frequent, it may require the use of pressurized backflushing.
Pumping System
A cursory market survey on pumps will be sufficient to confuse the most
inquisitive individual. Pumps vary in operating principle, dimensions,
specifications, and price.
Experience has demonstrated that price should be the last factor con-
sidered when attempting to establish if a pump can perform the desired task.
The following items require consideration when searching for that "right"
pump for the job.
(a) Does the application demand explosion-proof equipment?
(b) Must the pump be submersible?
(c) Must the pump be self-priming, or will it have a flooded inlet? What is
the suction lift height?
(d) What are the discharge pressure at the desired elevation and the
distance to where the sample is to be delivered?
(e) Is the pump required to handle solids, strings, rags, wood, stones,
sand, etc.?
(/) Are the materials of construction suitable for the waste material the
pump will be handling?
Although open impeller pumps lack efficiency as compared to a positive-
displacement pump, they are far less apt to foul or clog. Also, some sewers
CHAPTER 10 ON WATER-QUALITY MONITORING 153
Transfer Lines
Selection of the proper transfer line requires more thought than merely
using some surplus tubing that happens to be available. The diameter of the
line should be considered in relationship to the length in order to minimize
the pressure drop across the line. The line should have adequate size to
provide sufficient sample to the analyzer without an excessive amount of
discharge pressure. The stream velocity should be high enough to maintain
solids suspension, help reduce wall buildup, and minimize transfer time.
Specific corrective action might be required to reduce or periodically
eliminate biological growth lining the pipe. Backflushing or the use of a
bactericide might be necessary to keep the line open. Again, the materials of
construction should be properly selected.
while the remaining sample is deflected to a return sewer line. The solids-
liquid separator uses the principle of surface tension. The water adheres to
the curved plate while the larger solids continue their free fall through the
pipe.
Use of the simple and inexpensive dropout pot can greatly improve a
sample conditioning system. This device is not as maintenance-free as the
others, but it can greatly reduce the loading on a filter system if operated
correctly.
Dilution—Sample dilution can serve a threefold purpose. It can reduce
the solids concentration in a sample, relieving the load on the filter; it can
reduce the incidence of valve plugging; and it can provide analyzer range-
ability on high-concentration streams.
This approach has been used for the past several years in total carbon
measurements in an effort to overcome the nonlinear response of infrared
analyzers. If the carbon content in the sample can be held below 200
mg/litre, the response of the analyzer is reasonably linear. The calibration
curves in Fig. 3 show the degree of nonlinearity that is encountered when the
carbon concentration increases from 100 to 1000 mg/litre.
than separate them should not be used in analytical methods unless the filter
is guaranteed selective.
Five different filtering assemblies are shown in Fig. 6. The Cuno Auto-
Clean, which utilizes a stack of metal disks, has been reasonably successful in
past applications. The second type of Cuno is a cartridge filter, and it offers
no mechanism for self-cleaning other than replacing the cartridge. The sand
filter has been and is still being used in many locations. If a periodic
backflush is employed, it can do a fair job of solids separation, particularly
on silty solids. The Swirlklean offers an entirely different approach to
filtration from the other ones shown. The sample is injected tangentially into
the chamber between the two side membranes. By differential pressure, a
certain volume of sample is forced through the filtering membrane. This
system can be backflushed by reversing the filtered sample flow through the
membrane, permitting the swirling action of the incoming sample to remove
the solids from the membrane surface.
The single-pass system is an approach similar to the sketch. By sequencing
a filter tape, a small volume of sample, for example, 100 to 500 ml, can be
filtered periodically without consuming a large amount of tape. In this
system, each sample would be filtered through a clean section of tape. This
technique appears frequently in air pollution instrumentation.
No filter can perform indefinitely without some form of maintenance. It
must be either cleaned periodically or changed periodically. Dependence on
human performance for maintaining a clean system never seems to work
satisfactorily. If the cleanup can be automated, by all means do it.
158 MANUAL ON WATER
FIG. 6—Filters.
Analyzer Interface
Interfacing single or multiple streams into a single analyzer is no problem
if two important rules are followed.
(a) Never deadhead a stream; keep it flowing all the time.
(b) If a manifold is used to gather multiple streams, keep it close to the
analyzer. This will reduce the amount of sample required to flush out the
previous sample and thereby minimize the chance of cross-contamination.
Both of these points are illustrated in Fig. 7 with a simple three-stream-
manifold arrangement. The manifold is short and is mounted vertically to
ensure drainage. The valves are always three-way, providing a constant flow
all the time.
CHAPTER 10 ON WATER-QUALITY MONITORING 159
Readout Systems
Instrument readout systems are many and varied in concept. They range
from simple "Go-No go" lights or the calibrated scale of a thermometer to
the typewritten results of a digital computer, as well as to signal outputs and
160 MANUAL ON WATER
impulses which directly change the parameters of the system being mon-
itored. The basic types of outputs used are analog, digital, alarm, and
process control signals.
The analog readout systems involve the indication or recording of a
varying signal from the monitoring instruments. A wide variety of indicating
meters for monitoring instruments is available. In many cases, indicating
meters are built into the instrument, and the buyer has no choice of
manufacturer or type. This type of indicating readout can be used only
where an operator is available to observe the results.
Analog recording devices are available as an option for most instruments
producing some kind of electrical output. Recording furnishes a permanent
record of the system being monitored and allows evaluation of the results at
any time, without introducing subjective human errors. There is an option
and selection of recorder style to be determined by the user, depending on
how he plans to evaluate and store the data.
Digital readout systems differ from analog systems in that the readout
data are displayed as numbers. Digital indicating instruments also may be
supplied with some type of printer or recorder. Digital records vary from the
electrically actuated mechanical counter, with embossed digits for stamping
numbers on a paper tape, to high-speed magnetic tape systems which store
the information in code, to be read out or retrieved by a computer whenever
desired. Digital recorders not only have the advantage of numerical display,
but also offer the further potential of facilitating data use, in conjunction
with a digital computer, for process control or for storage and future
evaluation of the data by a computer.
Alarm systems can be built in, as they are in the less-expensive "go-No go"
type of instruments. Also, they can be attached to any other kind of readout
device to give an audible or visible signal at the instrument or at a remote
location when a preset maximum or minimum value is reached.
Surveillance Systems
Surveillance systems in the broadest terms are used for the collection of
water-quality data. Automatic monitoring instruments can be used effec-
tively to gather continuous or continual data on water systems under
observation, determining short-term discrete changes that are not obtainable
by composite sampling and laboratory analysis techniques.
Surveillance systems for data collection on surface waters such as rivers
determine changes in stream quality; the nature, location, and degree of
change; and pinpoint within monitoring system limits the cause of radical or
undesirable changes. Within industrial plants, surveillance systems have
been used to detect spills or leaks that would result in losses of expensive
product or raw materials. In other applications, monitoring instruments are
used to protect costly equipment (such as high-pressure boilers) or processes
(waste treatment plants) from harmful waterborne constituents.
CHAPTER 10 ON WATER-QUALITY MONITORING 161
Effluent Systems
Effluent monitoring systems have resulted from the regulations and limits
established by the pollution control laws noted early in this chapter. The
effluents considered here are the ultimate discharges from industrial or
municipal facilities to public watercourses.
The purpose of effluent monitoring is to control contaminant discharges
to public watercourses. The monitoring system may be installed for de-
fensive or punitive purposes.
Parameters measured vary with each specific effluent. For some param-
eters such as total nitrogen or chlorinated hydrocarbons, specific process
monitors are not available. In these cases, composite or grab samples must
be taken and analyzed in the laboratory with the associated hazards of
sampling accepted.
In the case of many parameters, instruments are available for continuous
or continual monitoring. These include mercury, chromate, temperature,
dissolved oxygen, conductivity, pH, turbidity, total organic carbon, and
total oxygen demand.
The monitors are capable of a good degree of reliability with low
FIG. 8— Use of TOD-GC system.
CHAPTER 10 ON WATER-QUALITY MONITORING 163
Process Systems
Physical and chemical parameters that are important to the operation and
control of industrial processes or to the protection of the process equipment
are automatically monitored by many industries. Typical physical param-
eters include temperature, pressure, flow rate, and liquid level. Chemical
parameters are pH, specific anions and cations, along with general and
specific organic compounds. Techniques employed in measuring the re-
quired parameters include, among others, automatic titrators, selective ion
electrodes, chromatography, spectrophotometry, radiography.
Monitoring systems for power plant water quality was one of the pioneer
applications for automated analytical equipment. Several different systems
specifically designed for such service have been introduced and are giving
excellent service, with minimum maintenance expense and substantial
savings in technical manpower costs. Being automated and internally
rechecked against standards, and automatically recalibrated at frequent
intervals, they produce data free from human bias and subjective errors.
Since results are recorded automatically, they are continuously available for
inspection to determine causes of observed variations, and are essentially
tamperproof. Samples can be analyzed as often as needed, at minimum
expense. Moreover, control systems for chemical feed, blowdown, and other
adjustments can be tied into the analytical system and used to activate these
subsystems whenever necessary, or to adjust feed and blowdown rates in
accordance with steam demand and water quality.
Some of the parameters now being monitored by automated systems
include silica (in boiler water, steam, and makeup), Fig. 10; hardness, pH,
conductivity and silica in demineralizer effluents or evaporator output;
phosphate and alkalinity in boiler water; pH, chromate, residual chlorine,
phosphate, and zinc in recirculating cooling water; dissolved solids or
conductivity of boiler water and cooling water; trace metals in boiler
makeup; dissolved oxygen in deaerator effluent and feedwater; hydrazine
residual in boiler water; ammonia in condensate; and corrosion rates.
Nuclear power plants place even greater emphasis on monitoring, and must
add radioactivity detection and measurement to the parameters listed earlier.
Obviously, it would be impractical or too costly to set up such an
extensive analytical control program based on manual grab sampling and
analysis. Only the availability of rugged, continuous monitoring systems at
reasonable cost has permitted the degree of sophistication and control of
water analysis currently being employed in modern power plants. The
monitoring equipment must perform all the necessary functions, including
continuous metering of sample and reagents, mixing, purification (by
dialysis, filtration, etc.), heating, digestion, or reaction, measuring, and
continuous reporting or recording of results, plus adjustment or control of
processes, where indicated. It is a tribute to the skill of those who design and
develop monitoring systems that they are able to incorporate the necessary
sensitivity, accuracy, and reproducibility in units that are sufficiently rugged
and maintenance-free to permit continuous service in severe industrial
applications where they are operated by relatively unskilled personnel or
technicians with minimum background experience.
Specific process applications in other industries include on-line titration of
acidity and iron content in pickling operations to maximize the efficiency of
the operation while minimizing acid dumping and associated neutralization
costs.
Continuous control of rinse tanks with backflow cycling in multirinse
stages reduces water usage and minimizes metal loss and pollution in the
electroplating industry.
FIG. 10— Typical flow diagram for automated silica determination on demineralized water supply.
166 MANUAL ON WATER
Temperature
Temperature-measuring instruments probably have been available longer
than any other type. The several types of thermometers are well known; they
are manufactured in many rugged versions designed for industrial applica-
tions. Recording thermometers generally are actuated by expansion or
contraction of an enclosed gas or liquid. In deforming its container, the
enclosed fluid provides energy to operate a mechanical linkage connected to
a pen writing on moving paper driven by a clock motor. The pen also can be
actuated by the bending of a bimetallic strip.
Temperature can be measured electrically, or determined by measuring
the voltage generated at the junction of two wires of different metals, as in
the common thermocouple. Outputs of thermocouples are measured either
on millivolt meters or on potentiometric recorders equipped with the proper
type of reference junctions. More recent devices in the electrical tempera-
ture-measuring field are resistors made of a ceramic material on which
electrical resistance varies with temperature. These are called thermistors
and, in general, have a much higher sensitivity than other temperature
FIG. 11 — Waste treatment plant.
168 MANUAL ON WATER
FIG. 12—Automatic control loop for a typical phosphate removal system in a sewage
treatment plant.
Conductivity
The conductance of water is another very common direct measurement. It
is defined as the reciprocal of the resistance in ohms, measured between
opposite faces of a centimetre cube of an aqueous solution at a specified
temperature. It is normally expressed in micromhos per centimetre. Pure
water has a theoretical minimum conductance of approximately 0.05 yum /cm
CHAPTER 10 ON WATER-QUALITY MONITORING 169
Density
The density of water is the basis of direct methods for monitoring the
amount of dissolved or suspended solids in water samples. Techniques
employed include the use of hydrometer floats in overflow chambers, chain
balance float units, liquid purge differential-pressure units, or air bubbler
systems. With these basic approaches, electrical position detectors or
differential-pressure sensors are used to initiate and transmit signals to
indicators or recorders. Since density varies with temperature, industrial
monitoring instruments for water density also must have temperature
compensation. Careful study of the specifications of available equipments
will be necessary to decide upon the type of instrument best suited to a
specific application.
Refractive Index
The extent to which fluids of different optical densities will bend or refract
light (their index of refraction) is the basis of another monitoring system.
Refractive index measurements can be used to monitor water characteristics
and to give direct indications of dissolved liquids and solids in water
samples. This method applies mainly to binary mixtures of liquids, but also
can be used to determine the total impurities in water. The measurement of
refractive index is temperature-sensitive, so industrial monitoring devices
using this principle must have proper temperature compensation. Various
photometric means are used to detect the extent to which the light beam is
refracted and to send the appropriate signal to an indicator or recorder.
170 MANUAL ON WATER
There are specific applications in which this type of instrument can be very
accurate and sensitive.
Surface Tension
Certain organic impurities such as modern detergents have a measurable
effect on the surface tension of water, and this effect can be used as the basis
for monitoring contamination. Surface tension effects are measured by
determining the force necessary to lift a special platinum-iridium ring off a
liquid surface. This type of tensiometer device is very sensitive to impurities
collecting on the equipment, so the metal ring and vessels must be kept
scrupulously clean, and turbid samples must be carefully centrifuged.
Information on surface tension measurement may be found in the ASTM
Test for Surface Tension of Water and Waste Water (D 1590) [2].
Suspended Solids
Suspended solids can be monitored by turbidimetric or nephelometric
analyzers, depending upon the sensitivity required. A turbidimeter measures
the amount of light passing directly through a sample, while nephelometry is
based on light-scattering properties (Tyndall effect) and measures the
amount of light scattered by suspended solids at approximately 90 deg from
a light beam passing through the sample. Nephelometry is the more accurate
procedure, especially in low turbidity ranges. These instruments are affected
by variation in particle color and size, but can give accurate results for
specific suspended materials. Information on turbidity measurement may be
found in the ASTM Tests for Turbidity of Water (D 1889) [2].
Color
Flow-type colorimeters can be used to monitor variations in colored
components and impurities in water. These instruments are available for
measuring the absorption of light rays, from ultraviolet through visible and
into the infrared wavelengths. Industrial monitoring colorimetry instru-
ments usually are nondispersive. That is, they do not use a grating or prism
to reflect light into its spectrum. Instead they use interference or colored
glass filters which allow only the wavelength band of that filter to pass
through the sample. Nondispersive infrared instruments also can have filters
of standard liquids or gases to isolate wave bands and to compare samples
with a reference standard. The wave bands to be passed by given instruments
are selected at a wavelength where the colored components of interest absorb
the maximum light. The amount of light absorbed at the selected wavelength
then will be a function of the concentration of the component of interest in
the sample. Photoelectric detectors of various designs are used to sense the
amount of light transmitted. A number of different electrical circuits may be
CHAPTER 10 ON WATER-QUALITY MONITORING 171
Oxidation-Reduction Potential
Another electrochemical measurement uses a platinum electrode in con-
junction with a standard reference electrode to measure the oxidation-
reduction potential of industrial water supplies and aqueous process streams.
The readout system is similar to that used for a pH meter except that the scale
reading is in millivolts (+ or -). The sign of the potential is important in this
case, as it indicates whether the solution has an oxidizing or reducing
potential. These monitoring units are classified as direct-measuring
instruments and, in general, are simple and maintenance-free. At the same
time, they usually cannot provide the specificity necessary to monitor
individual components. In other applications, oxidation-reduction systems
may comprise the detector section of more complex chemical analysis
instruments. The ASTM Test for Oxidation-Reduction Potential of Water
(D 1498) [2] describes the apparatus and procedures for this measurement.
Colorimetric Analyzers
The first of the basic instruments to be described is the colorimetric
analyzer. Such units include systems for adding color-forming reagents to
the sample. For maximum accuracy, the colorimetric analyzer should
incorporate the additional features of a comparison cell, a system for
reacting and measuring comparison reagents (or blanks), and an automatic
zero or calibration reset. Provisions for necessary pretreatment such as
heating, extraction, filtration, digestion, or dialysis can be provided. In
many applications, the colorimetric chemical analyzer has the potential of
being the most specific and sensitive water-monitoring instrument available
(see Fig. 13).
Coulometric Analyzers
Coulometric instruments are based in principle on Faraday's law, which
states that a definite quantity of direct current will cause a valence change in
a specific number of ions in a solution. If the amount of current passed is
known, then the number of ions changed also is known. Instruments based
on this principle have an absolute calibration rather than relative calibration
methods based on standards, typical of most other instruments. The
174 MANUAL ON WATER
generation of the new valence state can be accomplished either directly in the
sample solution, or in a separate vessel, in a pure chemical reagent precursor
which is then reacted with the sample. The latter allows some freedom from
interferences by other ions in the sample which also may undergo a change
of valence state when they are near the generating electrodes.
The coulometric instruments include a liquid section containing gen-
erating and detecting electrodes which indicate to the circuit that sufficient
current is passing to react with the ions in the solution. The readout section
includes indicating or recording instruments which measure current sent to
the electrodes. The instrument can use either a flow cell or a fixed-volume
measuring cell that performs batch-type analysis. The batch type more often
are laboratory rather than field monitoring instruments.
Coulometric instruments require periodic cleaning, depending upon the
sample stream. In some types, where generating electrodes are the material
for the formation of the reacting valence state, the electrodes must be
replaced at regular intervals. The electrical generating and measuring circuits
require the normal maintenance for circuits of these types, and maintenance
problems may vary according to the electrical components used.
Corrosion Measurement
The corrosivity of water is measured by the chemical action of the water
on a standard sample of a given material sensitive to the corrosive substances
of interest. The amount of chemical reaction occurring in a period of time
may be estimated by several different methods, with various instruments. In
one case, the current generated by solution of the metal is measured; in
another, the change in the resistance of a metal element due to reduction in
cross section of the metal probe is measured. The primary maintenance
problems with this type of instrument are requirements for periodic re-
placement of the standard sample units or probes, and leakage, which
permits internal resistance changes or short-circuiting of probes.
Titrators
One type of chemical analysis instrument having a broad field of
application is the titrator. These units are based on conventional volumetric
analysis methods. Such methods are adequately covered in ASTM standards
and in many other texts on analytical chemistry, so the details of analytical
procedures will not be discussed. The titrator-type instruments include
devices for measuring the volume of a standard solution or titrant added to a
measured volume of sample, and systems to determine when the added
volume of standard solution has provided enough reagent to be equivalent to
the component it is reacting within the sample.
The titrator instrument most often is an intermittent or batch type;
however, continuous units are available. A continuous titrator instrument
CHAPTER 10 ON WATER-QUALITY MONITORING 175
References
[7] Sugar, J. W. and Brubaker, J. H., "Development of Sample Conditioning Systems for
Automatic Environmental Instrumentation," presented at the 19th Annual Instrument
Society of America, Analysis Instrumentation Symposium, St. Louis, Mo., April 1973.
[2] Annual Book of ASTM Standards, Part 31.
Bibliography
Considine, D. M., Ed.-in-Chief, Process Instrument and Controls Handbook, McGraw-Hill,
New York, 1957.
Siggia, Sidney, Continuous Analysis of Chemical Process Systems, Wiley, New York, 1959.
Minnar, E. J., Ed., ISA Transducer Compendium, Instrument Society of America, IFI/
Plenum Data Corp., New York, 1963.
Holzbock, W. G., Instruments for Measurement and Control, 2nd ed., Reinhold, New York,
1962.
Liptak, B. G., Ed., Instrument Engineers' Handbook, Chilton, Philadelphia, Pa., 1969.
STP442A-EB/Jul. 1978
Water quality is a function of both the source of the water and its
intended use. The quality of a given stream can be defined only in terms of
the requirements of the system in which it is being received or from which the
water is discharged. The waste from one use may well be the water supply for
another use. Before one can control water quality for a use, a great deal must
be known about both the chemical and physical characterizations of the
possible water sources, and the exact requirements for the planned use.
Knowing these data, one can set out to develop the proper treatment for the
selected water supply. Once the treatment program is started, analytical data
are needed to determine its effectiveness. Overtreatment causes unnecessary
expense, and undertreatment also will cost money because of equipment
inefficiency or failure, plus resulting downtime, maintenance expense, and,
potentially, reduced product quality. One may conclude that analytical data
are needed for effective planning of the system and for monitoring per-
formance of the system subsequently. The Annual Book of ASTM Stand-
ards, Part 31 [7],1 presents a wide variety of analytical methods to determine
the various constituents and characteristics of significance to water quality
evaluation.
This chapter provides the analyst with criteria necessary for the selection
of the best method to check for each constituent, and guidance to properly
interpret results of the analyses, in relation to the water system under
consideration. To accomplish this goal, the chapter discusses (1) the value of
a well-defined, systematic program of analysis; (2) sampling methods for
various needs; (3) the basis for selection of the test methods to achieve the
desired results; (4) the cross-checking of analytical data; and (5) the
interpretation of results.
Although the determination of water quality is done to select the proper
treatment program, the description of specific treatment methods is beyond
the scope of this chapter. (Treatment methods are discussed in Chapter 5.) In
selecting sites for new plant construction, where water is required for plant
operations and for use in manufacturing products, the quality and quantity
'The italic numbers in brackets refer to the list of references appended to this chapter.
177
Copyright© 1978 by ASTM International www.astm.org
178 MANUAL ON WATER
of water available, and its analysis, play important parts in the economics of
plant operation.
In order to design an effective and comprehensive treatment program, it is
necessary to determine all the variables which may be important in the use of
the finished water. At first, a complete analysis would be wise, including
consideration of seasonal changes; thereafter, perhaps, only selected tests
would be necessary on a routine basis to monitor the more important
variables and maintain the water treatment program. Variations in certain
characteristics often can be predicted on the basis of the source of water. For
example, deep well water would not be expected to vary appreciably in
organic matter or hardness, while river water may vary rapidly and widely in
organic matter, ammonia, and other constituents, depending the nature of
water use upstream. Lake water will vary in organic loading depending on
depth and size of the lake, changes in temperature, microorganism growth,
and pollution factors.
Rivers represent the most commonly used water sources. The impurities
encountered can come from diverse sources, including agricultural runoff,
municipal wastes, mine drainage, industrial waste, and natural forest runoff.
A survey upstream will show several of the specific impurities and often the
contributing sources which affect the water quality at the plant site.
Treatment required for a river water, depending on the proposed use, may be
extensive or minimal as indicated by interpretation of the analytical data.
For example, a river water for cooling tower purposes may require as little
treatment as a chromate corrosion inhibitor and only minimal control
analyses. The same water source used for boiler feedwater may need
coagulation, sedimentation, filtration, de-ionizing and de-oxygenation to be
sure that corrosion and deposit formation are minimal. Frequent sampling
and extensive analysis will be needed for proper operation. A municipal
water supply form this same source may require softening filtration,
activated carbon treatment, and chlorination to meet the drinking water
standards and other end-use criteria.
In many cases, comparisons are made between two or more potential
supply sources to determine which source offers the best possibility of
efficient and economical operation. A comprehensive analysis of the water
from each source is the key to the selection. The economic evaluation must
consider all treatment costs, as well as the costs of obtaining and ensuring
continued availability of an adequate volume for the needs today and for
some time in the future.
only four or five items on samples taken once per day or once per shift from
a single sampling point, with sensitivity requirements on each analysis falling
in the milligram-per-litre range. On the other hand, control of boiler water in
a high-pressure steam generator may require eight or ten determinations of
items measured in micrograms per litre, on samples taken at various spots
throughout the system, every hour or two. The difference in the cost of these
two control programs would be substantial. Time and money can be saved
by designing the analytical program to collect only essential data. However,
the program must be complete enough to ensure protection of expensive
equipment from corrosion or deposit formation.
There are several factors to consider when selecting an analytical method,
including the sensitivity required, the interferences present, and the varia-
tions in precision and accuracy that can be tolerated. Even the background
of the analyst to perform the test must be considered, since many procedures
are satisfactory only in the hands of a skilled operator. The discussion of
water analysis methods in this chapter primarily is designed to assist in the
proper selection of individual procedures for specific applications. The test
methods described in the latter part of the chapter are grouped according to
the constituents for which tests are to be made. For example, all the methods
for dissolved oxygen in water are discussed together; so also are methods for
iron, and methods for silica. This is done to emphasize the importance of
recognizing differences between the various methods available for deter-
mining individual constituents, and to illustrate the importance of selecting
the proper procedure for a given application. The discussion of methods also
includes a brief review of the relative importance of each element in different
water treatment and water use situations, to direct the analyst to the
selection of the proper method. For example, a series of samples to be
analyzed (for hardness, silica, alkalinity, iron, and oil) from a once-through
cooling system would be handled differently than similar samples from
boiler feedwater. The hardness that can be tolerated in cooling water
ordinarily will be high compared with the allowable hardness in boiler
feedwater. Thus, one must select a very sensitive hardness test for boiler
feedwater, whereas a less sensitive but accurate procedure is adequate for
most cooling systems. The amount of silica in a feedwater for a high-pressure
boiler ordinarily is kept below 1 mg/litre, and the test method must be very
accurate in this low range. Silica in cooling water is not as critical with
respect to sensitivity requirements, but the high degree of accuracy still is
required for optimum operation. While the test for alkalinity is equally
important in both systems, the method used for boiler feedwater may not be
applicable to treatment programs used in cooling systems. Cooling water
from open recirculating systems often is maintained with pH below 7, and
corresponding alkalinity levels, whereas boiler feedwater normally is alka-
line.
The concentration range and possible interferences such as highly colored
materials present in the sample because of treatment will have to be
180 MANUAL ON WATE R
methods are dictated in the regulation, with the option of proving another
method equivalent or better. Methods appropriate for the receiving water
may not be useful for waste waters, because of concentration differences,
interferences, and other factors.
The foregoing discussions show that one must determine not only the
specific constituents tests, but also the type of water system being con-
sidered, and the required tolerances of the method with respect to precision,
accuracy, sensitivity, and interferences.
SEPARATE POR-
SEPARATE TIONS OF A SEPARATE
FLOW SAMPLES SAMPLES SINGLE SAMPLE SAMPLES
(See Table 2) (See Table 3) Separate portions of Samples for the de-
Flow samples shall be Samples for which a single sample may termination of extract-
used in determining these properties and be used for determin- able matter and floating
these properties and constituents are to be ing these properties liquids must be collected
constituents at the determined require and constituents in- separately in glass-
sample source. This that the sample con- dividually or, in some stoppered flasks of
information may be tainers be sealed cases, in a sequence chemically resistant
continuously and au- against air contact of analyses. The cus- glass. Samples may also
t o m a t i c a l l y deter- during the interval tomary precautions be collected in cork-
mined, indicated, and between sampling and against contamina- stoppered flasks, pro-
recorded. analysis; or the sam- tion by a i r b o r n e vided the stoppers are
ples must be chem- solids, or too long wrapped in metal foil.
ically fixed immediate- storage in unsuitable
ly after sampling. containers (Note 1),
must be observed in
the case of samples
to be analyzed for
these constituents.
NOTE 1—If the property or constituent to be determined may be affected by reaction of the
sample with the sample container, a separate sample should be collected in a special container
that will not itself contaminate the sample.
be used and the color comparison made visually. If sensitivities down to 0.02
mg/litre are needed, a filter photometer is required. Below 0.02 mg/litre, a
spectrophotometer will be required. It will be noted that the greater the
sensitivity need, the more costly the instrumentation becomes. However, the
instrument also becomes more versatile. The spectrophotometer in this case
can be applied to the upper ranges as well, which may be a consideration in
other procedures that must be run. Convenience also may be a considera-
tion. In the example just given, when the iron concentration of interest is
greater than 0.1 mg/litre it still may be profitable to use photometer instead
of visual comparison methods. The frequency of tests required may make it
a considerable waste of time and effort to prepare the series of standards
needed each time for visual comparison. A photometer, with a standard
curve, then can be a timesaving convenience.
The choice between manual and automatic or semiautomatic instrumenta-
tion will be governed primarily by the frequency and speed of analysis
required. The needs of the analytical program will determine the choices of
Laboratory Practices
Another important aspect of laboratory practice is the quest for new and
improved methods. The analyst should not cease to search once he has found
a satisfactory one. Methods offering greater specificity and reliability are
continually being developed. He should be aware of these, evaluate them,
and introduce them, if they are improvements over existing procedures.
Since the analyst is an important part of any method, safety must be
considered in laboratory practices. Knowledge of potentially dangerous
reactions and conditions is essential, and due precautions should be part of
the laboratory routine.
Analytical Sampling
The best analytical methods are of no value if poor sampling techniques
are employed. The sample must be representative of the water to be
examined, and the concentration of the constituent of interest must remain
the same until the analytical tests are made. The technique of sampling
varies, depending on the type of water and its use.
After the program of analysis is planned, consideration must be given to
obtaining representative samples. In this respect, the proper location of
sampling points and auxiliary equipment such as cooling coils or degassers is
important. Several methods in the Annual Book of ASTM Standards, Part
31, cover the equipment and general techniques of sampling:
D 1192, Specifications for Equipment for Sampling Water and Steam.
D 1066, Sampling Steam.
D 887, Field Sampling of Water-Formed Deposits.
D 3370, Practices for Sampling Water.
These range from the selection of valves, fittings, and equipment to the
methods of sampling of specific waters, such as steam and boiler waters.
Method D 3370 discusses the sampling of water and includes a list of sample
volumes required for various determinations. All of these methods should be
consulted when setting up the sampling procedures and locations, and the
appropriate method consulted when sampling. A complete discussion of
sampling principles is presented in Chapter 9.
Many samples require special techniques and containers. For example,
trace iron or copper analysis requires specially cleaned containers and
acidification; samples for silica analysis should be taken in plastic bottles;
each sample for dissolved oxygen must be flushed through the bottle with at
least ten times its volume of sample and then carefully stoppered to prevent
air entrapment. Each ASTM method will specify the technique of sampling
required and should be followed accurately to ensure meaningful analytical
results.
Discussion of Methods
A variety of methods is generally available for each determination. In
addition to the use to be made of the results, the choice of procedures is
188 MANUAL ON WATER
TABLE 4—Continued,
(a) ORGANIC CONSTITUENTS (continued)
Specific Constituents Continued
Waterborne Oils
D 3415-75 T Identification
D 3325-74 T Preservation of Samples
D 3326-74 T Preparation of Sample for Identification
D 3327-74 T Analysis for Selected Elements
A. Nitrogen
B. Sulfur
C. Nickel and Vanadium
D 3328 - 74a T Petroleum Oils, Comparison of, by Gas Chromatography
D 3414-75 T Infrared Analysis
TABLE 4—Continued,
(b) GENERAL PROPERTIES (continued)
D 1498-76 Oxidation-Reduction Potential
D 1252-67 (1974) Oxygen Demand, Chemical (Dichromate)
D 3250 - 77 Oxygen Demand, Total, by Combustion
D 1293-65(1970) pH
Solids (see Matter, Paniculate and Dissolved)
D 1429-76 Specific Gravity
A. Pycnometer Method
B. Erlenmeyer Flask Method
D 1590 - 60 (1972) Surface Tension
D 1345 - 59 (1977), Toxicity, Freshwater Fishes
D 2037-68 (1973) Toxicity, Inhibitory, to Diatoms
D 1889-71 (1976) Turbidity
A. Jackson Candle
B. Nephelometric
C. Absolute
(c) RADIOACTIVITY
Measurement of Radioactivity
D 3085 - 75 Activity, Low-Level
*D 1943-66(1971) Alpha Particle Radioactivity
D 3084 - 75 Alpha Spectrometry
*D 1890 - 66 (1971) Beta Particle Radioactivity
*D 1690-73 Gamma Radioactivity
*D 2459 - 72 Gamma Spectrometry
*D 2470-70 (1975) Neutron-Emitting Fission Products
Specific Radkmuclides
*D 2038 - 74 Barium
*D 2577-72 Cesium
*D 2334-73 Iodine
A. Heterogeneous Exchange
B. Distillation
C. Extraction
*D 2461 - 69 (1975) Iron-59
*D 2039 - 74 Manganese
D 3357-74 T Nickel
D 2460 - 70 (1975) Radium, Radionuclides of
D 3454 - 75 T Radium-226
*D 2476-75 Tritium
E 318 - 69 (1975) Uranium, Colorimetric
D 2907 - 75 Uranium
A. Direct Fluorometric
B. Extraction
D 3315-73 T Zirconium
Heavy Water
TABLE 4—Continued,
(d) BACTERIOLOGICAL
Adenosine Triphosphate (ATP) Content of Microorganisms, proposed
D 3508 - 76 T Fecal Coliform Recovery, Evaluation of Membrane Filters
D 1128-60 (1974) Microorganisms, Microscopic Matter, Identification of
F 60-68 (1973) Microbiological Contaminants, Detection and Enumeration
D 932 - 72 Iron Bacteria
D 993 - 58 (1976 Sulfate-Reducing Bacteria
A. lodimetric
B. Lead Acetate Paper
TABLE 4—Continued,
(e) INORGANIC CONSTITUENTS (continued)
D 512^67(1974) Chloride
A. Mercurimetric Titration
B. Silver Nitrate Titration
C. Colorimetric with Ferric Thiocyanate
D 1253-76 Chlorine, Residual, in Water
A. Direct Amperometric Titration
B. Starch-Iodide Titration (Direct and Back Titration)
C. Amperometric Back Titration
D 1427 - 68 (1974) Chlorine, Residual, in Waste Water
A. Starch-Iodide Titration
B. Amperometric Titration
D 1687 - 77 Chromium, Total
A. Permanganate Oxidation
B. Hypobromite Oxidation
C. Alkaline-Persulfate Oxidation
D. Atomic Absorption
D 2576-70 (1976} Chromium by Atomic Absorption Spectrophptometry
D 2576-70 (1976> Cobalt by Atomic Absorption Spectrophotometry
D 3558 - 77 Cobalt by Atomic Absorption Spectrophotometry
A. Atomic Absorption, Direct
B. Atomic Absorption, Chelation Extraction
D 1688-77 Copper
A. Colorimetric with Neocuproine (High Range)
B. Colorimetric with Neocuproine (Low Range)
C. Colorimetric with Cuprethol
D. Atomic Absorption, Direct
E. Atomic Absorption, Chelation Extraction
D 2576-70 (1976) Copper by Atomic Absorption Spectrophotometry
F 57-68(1973) Copper in High-Purity Water
D 1179-72 Fluoride
A. Photometric SPADNS
B. Ion Selective Probe
D 1385 - 67 (1972) Hydrazine, Colorimetric with p-Dimethylaminobenzaldehyde
D 1588-60 (1974) Hydrogen, Dissolved and Gaseous
A. Thermal Conductivity
B. Volumetric
D 514 - 67 (1974) Hydroxide, Titrimetric
D 1246-77 Iodide and Bromide
A. Iodide, Chlorimetric-Catalytic
B. Bromide, Colorimetric-Catalytic
C. Iodide and Bromide, Volumetric
D 1068-77 Iron
A. Photometric, Orthophenanthroline
B. Photometric, Bathophenanthroline
C. Atomic Absorption, Direct
D. Atomic Absorption, Chelation Extraction
D 2576-70 (1976) Iron by Atomic Absorption Spectrophotometry
D 2576-70(1976) Lead by Atomic Absorption Spectrophotometry
D 3559 - 77 Lead by Atomic Absorption Spectrophotometry
A. Atomic Absorption, Direct
B. Atomic Absorption, Chelation Extraction
Lead and Cadmium by Atomic Spectrophotometry, proposed
D 3561 - 77 Lithium, Potassium, and Sodium in Brackish Water, Seawater, and
Brines by Atomic Absorption Spectrophotometry
D 2576-70 (1976) Magnesium by Atomic Absorption Spectrophotometry
D 511-76 Magnesium and Calcium
A. Gravimetric
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 193
TABLE 4—Continued,
(e) INORGANIC CONSTITUENTS (continued)
B. Complexometric Titration
C. Atomic Absorption Spectrophotometric
D 858 - 77 Manganese, Colorimetric as Permanganate
A. Colorimetric
B. Atomic Absorption, Direct
C. Atomic Absorption, Chelation Extraction
D 2576-70(1976) Manganese by Atomic Absorption Spectrophotometry
D 3223 - 73 Mercury by Cold Vapor Atomic Absorption Spectrophotometry
D 2576-70 (1976) Metals by Atomic Absorption Spectrophotometry
D 2576-70 (1976) Metals by Atomic Absorption Spectrophotometry
A. Cadmium, 0.05 to 5 mg/ litre
B. Calcium, 0.3 to 15 mg/litre
C. Chromium, 0.2 to 20 mg/litre
D. Cobalt, 0.25 to 50 mg/ litre
E. Copper, 0.1 to 20 mg/litre
F. Iron, 0.1 to 20 mg/litre
G. Lead, 0.34 to 40 mg/litre
H. Magnesium, 0.05 to 3.5 ing/lit re
I. Manganese, 0.04 to 10 mg/litre
J. Nickel, 0.08 to 20 mg/ litre
K. Zinc, 0.02 to 3 mg/litre
D 3372 - 75 Molybdenum by Atomic Absorption Spectrophotometry
D 1886-77 Nickel
A. Photometric, Carbamate
B. Photometric, Glyoxime
C. Atomic Absorption, Direct
D. Atomic Absorption, Chelation Extraction
D 2576-70(1976) Nickel by Atomic Absorption Spectrophotometry
D 992-71 Nitrate, Colorimetric with Brucine-Sulfanilic Acid
D 1254-67(1974) Nitrate
A. Colorimetric by Diazotization
B. Volumetric with Permanganate
D 1589-60(1974) Oxygen, Dissolved in Waste Water
A. Alsterberg (Azide)
B. Rideal-Stewart
C. Pomeroy-Kirshman-Alsterberg
D. Polarographic
D 888-66(1977) Oxygen, Dissolved in Water
A. Colorimetric-Indigo Carmine
B. Dead-Stop End Point
C. Potentiometric End Point
D. Thiosulfate Titration
E. Thiosulfate Titration-Starch Indicator
D 515-72 Phosphorus
A. Colorimetric, Ascorbic Acid Reduction
B. Colorimetric, Amino Reduction
C. Colorimetric, Molybdovanadophosphate
D 3561 - 77 Potassium, Sodium, and Lithium in Brackish Water, Seawater, and
Brines by Atomic Absorption Spectrophotometry
D 1428-64(1971) Potassium and Sodium by Flame Photometry
A. Analysis of Water
B. Trace Amounts of Sodium in Low-Solids Water
C. Analysis of Water-Formed Deposits
D 3081-72 T Selenium, Colorimetric with Diaminobenzidine
Continued.
194 MANUAL ON WATER
TABLE 4—Continued,
(e) INORGANIC CONSTITUENTS (continued)
D 859-68 (1974) Silica
A. Gravimetric
B. Colorimetric as Molybdenum Blue
C. Colorimetric as Molybdenum Yellow or Blue
D. Colorimetric, Sulfite Reduction
Spectrochemical Analysis by Rotating Desk Technique Using An
Optical Emission Spectrometer, proposed
D 3561 - 77 Sodium, Potassium, and Lithium in Brackish Water, Seawater, and
Brines by Atomic Absorption Spectrophotometry
D 1428-64(1971) Sodium and Potassium by Flame Photometry
A. Analysis of Water
B. Trace Amounts of Sodium in Low-Solids Water
C. Analysis of Water-Formed Deposits
D 2791 - 77 Sodium, Continuous Determination by Ion Selective Electrode
A. Sodium Ion-Electrode
B. Flame Photometry
D 3352 - 74 Strontium, in Brackish Water, Seawater, and Brines
D 516-68(1974) Sulfate
A. Gravimetric
B. Turbidimetric
C. Volumetric
D 1339-72 Sulfite, Volumetric
A. 0.1 to 6 mg/litre NaaSOs
B. 6 mg/litre Na2SO3 or higher
C. 3 mg/litre Na2SO3 or higher
D 2333-68 (1974) Thorium, Colorimetric with l-(o-Arsonophenylazo)-2-Naphthol-3,6-
Disulfonic acid
D 2907-75 Uranium
A. Direct Fluorometric
B. Extraction
D 3373 - 75 Vanadium, Colorimetric-Catalytic
D 1691-77 Zinc
A. Colorimetric with Zincon, High Range
B. Colorimetric with Zincon, Low Range
C. Atomic Absorption, Direct
D. Atomic Absorption, Chelation Extraction
D 2576-70 (1976) Zinc by Atomic Absorption Spectrophotometry
New techniques which are required for analysis are being developed and
standardized rapidly. Chromatography methods are being used to separate
the constituents for identification by infrared, ultraviolet, and mass spectro-
scopy. Solvent extraction and activated carbon adsorption have been used to
separate and concentrate the organic substances from water. Thin-layer and
paper chromatography are helpful in separating the organics that cannot be
separated by gas-liquid chromatography. Identification of specific organic
compounds is limited to the compounds for which there are pure standards
to compare elution times in gas and liquid chromatography. Even these
identifications must be considered only tentative until confirmed by at least
two other columns or, in liquid chromatography, two different developing
conditions. It is advisable to further confirm the organic structure by
spectroscopy. Fluorescent spectroscopy has been used as a detector with
paper and thin-layer chromatography. The chromatographed spots are
caused to fluoresce by ultraviolet light excitation, and the spectrum of the
fluorescent emission is used to identify the compound. The intensity of the
fluorescence can be related to the concentration of the compound present in
the spot.
Analysis of organic contaminants in water in nanogram- and picogram-per-
litre concentrations is receiving much attention, and new techniques are
being developed. Table 4a shows the methods published in the Annual Book
of ASTM Standards, Part 31, for organic constituents of water and waste
water.
Sources of Alkalinity
The anions that may contribute to alkalinity are those which form acids
that are only weakly dissociated in solution, and which thus enter into
hydrolysis reactions. Chloride, sulfate, and nitrate ions do not affect the
alkalinity. Cations that form weakly dissociated bases take part in hydrolysis
reactions which tend to produce acidity rather than alkalinity. The presence
of certain organic materials may have a considerable effect upon the
alkalinity determination.
Because of the relative abundance of carbonate minerals and because
carbon dioxide, which enters into equilibria with them in water solution, is
readily available, bicarbonate and carbonate are to be expected in most
waters. The presence of hydroxide ions in natural water in amounts
sufficient to affect the alkalinity determination directly is very rare, unless
artificial contamination has occurred.
2
Much of the following discussion is taken from Ref 2.
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 197
Hydroxide may occur in water that has been softened by the lime or lime-
soda process. Water in contact with fresh concrete may have an excessively
high pH and apparent hydroxide alkalinity, due in part to silicates. Concrete
may be a source of hydroxide alkalinity in samples from wells that are under
construction.
Under any system of reporting titrated alkalinity now in use, all the effects
of the anions entering into hydrolysis reactions are lumped together and
reported as an equivalent amount of a single substance, or as two more or
less postulated ions. Thus, although alkalinity data may suggest the presence
of definite amounts of carbonate, bicarbonate, or hydroxide, the ions have
not been directly determined as such and the results may include the
equivalent of all or part of such other anions as may tend to hydrolize. These
ions include silicate, phosphate, borate, and possibly fluoride. Some other
ions not ordinarily found in natural water, such as arsenate, aluminate, and
certain organic anions which may occur in colored waters, also could
increase the alkalinity.
content. The amount required for Step 2, when corrected for any HCOy
produced in the carrying out of Step 1, is a measure of the original HCOjT
content. Waters containing OH~ require more acid for Step 1 than for Step 2
and the magnitude of this difference is a measure of the OH" concentration.
It is assumed throughout that OH~ and HCO.r cannot exist in the same
solution.
. . No matter what ions may be involved, if they are titrated stoichio-
flietrically by lowering the pH to 4.5, alkalinity values in equivalents per
million (epm) which give a cation-anion balance are obtained. Silicate in the
form SiO>~ should not be present in waters in measurable amounts unless
the pH is at least 11. The HSiO.r form, however, might represent about half
the silica present at a pH of 9 and about a tenth of it at pH 8.
Dissociated silica can contribute to titrated alkalinity between pH values
of 8 and 9, but the magnitude of the effect in this range is uncertain. Silicate
ions in either of the foregoing forms would be fully titrated in the regular
alkalinity determinations. They would then be reported in terms of equiva-
lent quantities of bicarbonate or carbonate. Other types of silicate ions also
might affect the alkalinity.
Orthophosphate may occur in water in three forms, PO4=, HPO4=, and
H2PO4~. The trivalent form is present in appreciable amounts only above a
pH of 10. The HPO4= ion predominates from a pH of 7 to a pH of 2. The
phosphate ions are not fully converted to orthophosphoric acid even at a pH
of 1, but practically all the HPO4= ions would be converted to H2PO4" ions
in an alkalinity titration stopped at a pH of 4.5. Waters that contain enough
phosphate to affect the alkalinity appreciably are rare in nature. If such a
water were titrated for alkalinity in the usual way, a part of the phosphate
(about a third) would appear as an equivalent amount of bicarbonate or
carbonate.
Borate ions also hydrolyze in water to affect the pH. Theoretically these
ions should all be converted to boric acid in the regular alkalinity titration.
The form of such ions in solution in natural waters is not certain, however,
and the effect of berates on alkalinity titration is difficult to evaluate fully.
Waters are seldom found in which measurable alkalinity is contributed by
borate ions, because boron concentrations in water are normally very low.
Borate in the dihydrogen form (H2BO3~) is theoretically possible in the ratio
of 1 part to about 17 parts of the undissociated acid at a pH of 8. At a pH of
7 and lower, dissociated ions are essentially absent.
Fluoride ions hydrolyze, but weakly, and probably they are rarely present
in large enough amounts to affect the alkalinity.
The values given for dissociation constants in the literature hold for dilute
solutions of single salts. Natural waters are not so simple, and exact
conformance with theoretical behavior, therefore, is not to be expected. The
computations, however, do give useful indications of the behavior of various
ions that can take part in hydrolysis and contribute to alkalinity.
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 199
Relation to pH
Many users of chemical analyses are confused by the distinction between
pH value and titratable alkalinity (because the titration for alkalinity is
carried to a pH of 4.5, whereas at the same time a pH of 7 is stated to be the
neutral point).
If all the hydrolysis in a water is assume^ to be due to the system CO3 =
-2LLHCO, JtLHzCOj; the pH provides a means of deciding how far to the left
the reaction is displaced. A pH below 8.2 indicates the absence of the normal
carbonate phase and a pH below 4.5 indicates the absence of both the
normal carbonate and bicarbonate phases, but otherwise the pH is only
qualitative. By titration of the system with acid, a quantitative determination
of the amount of each phase can be made, if the original assumption as to the
ions present is correct. To complete this determination the equilibrium must
be shifted all the way to the right and the pH lowered to 4.5. In pure water at
neutrality the pH is 7, but this represents an absence of ions that would take
part in hydrolysis and is an entirely different condition.
Range of Concentration
Alkalinity reported as hydroxide is ordinarily absent from uncontam-
inated natural water. Alkalinities reported as carbonate are common,
particularly in groundwaters, or concentrated surface waters that have a
large amount of sodium in proportion to calcium and magnesium. The usual
stream water has no apparent carbonate alkalinity and should have a pH
below 8.2 if it contains an appreciable amount of calcium. Some surface
waters have a pH greater than 8.2, either from CO?= or as a result of silicates
or other anions in solution.
Alkalinity reported as carbonate usually is present in small amounts,
generally less than 10 mg/litre. In waters high in sodium, higher values are
sometimes encountered, but concentrations over 50 mg/ litre are extremely
unusual.
In acid waters, there is no bicarbonate alkalinity. In alkaline waters (all
those whose pH is 4.5 or over), the range in alkalinity reported as
bicarbonate is from zero up to more than 1000 mg/ litre, although concentra-
tions much higher than 500 mg/litre are unusual. Waters highly charged
with carbon dioxide may contain large amounts of alkalinity as bicarbonate.
The reduction of sulfate to sulfide with the assistance of certain types of
bacteria produces carbon dioxide as a by-product, and may cause high
bicarbonate concentrations in waters associated with petroleum.
Acidity
As a corollary to the property of alkalinity, there is the opposite property
of acidity which is found in some natural waters. If the usual alkalinity end
200 MANUAL ON WATER
point is used, a water would not be reported as having acidity unless its pH is
below 4.5.
Range of Concentration
Acidity can range from zero at the pH level that is taken as neutrality to
several hundred milligrams per litre for pH levels around 2.5. Springs and
waters strongly affected by mine drainage or industrial wastes may at times
have lower pH values. The total acidity has some significance in terms of
treatment needed, but is of less value in the representation of actual
conditions in the water than reporting of alkalinity as carbonate and
bicarbonate is for alkaline water.
Methods
In ASTM Methods D 1067, the high-precision procedure involves elec-
trometric titration with 0.02 N hydrochloric acid or sodium hydroxide either
to specific pH end points, or by developing a titration curve for the sample
and noting the pH values at the inflection points of the curve. The latter
procedure is used for evaluation of the buffering capacity of water if the
buffering salts are other than carbonates and bicarbonates.
Three routine procedures were included in Methods D 1067. Method A
involves titration to a predesignated pH, the end point being determined
electrometrically or by color change of an internal indicator. In Method B,
the end point is determined by comparison of the color developed by an
added indicator with the color of a standard buffer solution containing the
same added indicator. In routine Method C, particularly applicable to acid
waste waters, the sample is boiled to attain equilibrium, then titrated to a
designated pH, the end point being determined by color change of an
internal indicator. The latter procedure is applicable for waters highly
polluted with acid industrial wastes, containing slowly hydrolyzable or
buffering materials, or materials that will interfere by reason of color,
precipitation, and other factors.
Alkalinity or acidity in the intermediate range between pH 3.5 and pH 9 is
arbitrarily regarded as resulting from the presence of weak bases or weak
acids. Alkalinity above this range, or acidity below it, is considered to be due
to the presence of relatively strong bases or strong acids, respectively.
Special procedures said to be sensitive and accurate to 0.05 mg/litre have
been developed for measuring extremely low alkalinities [3].
Chlorine Requirement
Often it is desirable to establish the quantity of chlorine required to
achieve a specific objective in the treatment of a water by chlorination. This
objective might be elimination of tastes and odors; reduction of biochemical
oxygen demand by destroying or modifying decomposable organic sub-
stances; separation of grease in waste water; or destruction or modification
of oxidizable constituents in waste water.
ASTM Method D 1291 provides a procedure for finding the chlorine
requirement of process water and waste water. It involves adding a chlorine
solution of known strength, in increasing increments of chlorine concen-
trations, to different portions of the sample water. The contact time and pH
are maintained as specified for the particular object of chlorination. The
chlorine requirement of the water is found by interpolation of a plotted
curve of chlorine dosages against the results of chlorine residual tests or
other tests which determine whether the specific object of the chlorination
has been reached in the different sample portions. The chlorine requirement
is the amount of chlorine, expressed in parts per million, required to achieve
the objectives of chlorination.
Color
Color is a common constituent of many natural waters. It generally results
from natural metallic ions, and from lignins, humic acids, and other
vegetation products thought to be in colloidal suspension. In drinking water,
color is objectionable for aesthetic reasons, but in several manufacturing
processes, virtually colorless waters are required. Occasionally, pollution by
industrial wastes will impart unusual or unnatural colors to water supplies.
Artificial color scales, using standards prepared from potassium chloro-
platinate and cobaltous chloride solutions, are often used to measure natural
color in water [4\. Suspended matter must be removed by centrifuging before
the comparisons are made. Addition of calcium chloride [5] to assist in
centrifuging is desirable with some types of turbidity. Spectrophotometric
and photometric methods have been developed [6], some especially for
industrial waste water \4}.
Continuous measurement of color has been practiced to a very limited
extent. Methods for measuring color, with particular emphasis on photo-
metric methods which offer greatest promise for continuous analysis, are
discussed by Staats [7].
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 203
Electrical Conductivity
Electrical conductivity has special significance because it is a quick and
convenient method for measuring electrolyte concentration. The specific
conductance of a dilute solution of an electrolyte is almost directly propor-
tional to the ionic concentration of the electrolyte, and the total conductivity
of a given water is equal to the sum of the several conductivities resulting
from the electrolytes present. Because of the unusually high conductance per
weight unit of the hydrogen or hydroxide ion, samples frequently are
neutralized before the electrical conductivity is measured. Conductivity
measurements can therefore be related to dissolved solids concentration.
Also, they sometimes are required for special investigations of corrosion in
water.
ASTM Method D 1125 describes the apparatus and procedures for
determining electrical conductivity of industrial waters. The high-precision
procedure included requires careful control of temperature, all measure-
ments being made at 25° C. The procedure designed for more routine use
incorporates a temperature correction chart.
Conductivity is a useful guide to the purity of distilled water and is much
used for evaluation of steam purity in the power industry. It is important to
note, however, that dissolved gases (particularly carbon dioxide and am-
monia) have an important effect on conductivity. When determining steam
purity by this method, it is generally necessary to reduce the concentration of
these gases and to correct for the residuals present [8,9]. Special apparatus is
available for removing gases from the water before the conductivity
determination is made [10,11]. A good approximation of the dissolved solids
in distilled water and condensate can be made by boiling a sample down to
less than half the original volume to drive off the dissolved gases, deter-
mining the conductivity of the cooled remainder, and by correcting this
value for the reduction in volume [72,73].
Electrical conductivity cannot be precisely related to dissolved solids
because some dissolved substances such as silica and certain types of organic
matter contribute little or nothing to the conductivity.
Continuous measurement of conductivity of flowing samples is often used
for monitoring process waters [14], and is essential in monitoring quality of
high-purity supplies, such as demineralized water.
Hardness
Hardness is now generally accepted as representing the total concentration
of calcium and magnesium ions. Originally hardness was understood to be
the capacity of a water for precipitating soap. It was measured by the
amount of a standard soap solution required to produce a stable lather.
Therefore, other polyvalent ions (in addition to calcium and magnesium)
capable of precipitating the soap were included as part of the hardness.
204 MANUAL ON WATER
Odor
Odor is a characteristic of many natural waters and can be the result of
many contributing factors. Among these are pollution by sewage and trade
wastes, the presence of living matter (bacteria, fungi, algae, and animal life),
the decomposition of various forms of living matter, and the presence of
colloidal vegetable or earthy matter.
Odor tests can be useful in many respects. For example, they may be used
in checking the quality of raw and treated waters, in determining the
effectiveness of deodorizing procedures, and as a method of tracking sources
of contamination or leaks in industrial processes. Odor is difficult to
measure quantitatively.
ASTM Method D 1292 is a method for measuring odor in waters for
comparative or control purposes. The threshold odor number of water is
determined by using the sense of smell and a series of dilutions of the sample
with odor-free water. The odor threshold of a sample represents the number
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 205
Oxidation-Reduction Potential
The oxidation-reduction potential of a solution is defined as the elec-
tromotive force (emf) developed by a platinum electrode immersed in the
water, referred to the standard hydrogen electrode. Every oxidation-
reduction reaction involves an exchange of electrons; the emf necessary to
oppose this flow of electrons gives a measure of the oxidation-reduction
potential. ASTM Method D 1498 describes the apparatus and procedure for
measuring the oxidation-reduction potential of all types of industrial waters.
It does not deal with the interpretation or application of the results.
Empirical testing is necessary to adapt this method of measurement to
specific ions in a particular application.
Some of the applications of oxidation reduction potential measurements
in water have been summarized by Rosenthal. In one stage of the seawater
bromine process, the concentration of free bromine in acidified seawater
treated with chlorine is obtained by measuring the oxidation-reduction
potential. A similar measurement on a plating plant waste is used as a gage
of dichromate ion concentration for controlling the addition of a reducing
agent. Continuous measurement of low chlorine concentrations is possible
by this method.
Specific Gravity
Specific gravity is the ratio of weight of a given volume of sample to the
weight of an equal volume of water, under a fixed set of conditions. It is
rarely an important property of industrial supply or process waters, but may
be significant in waste analysis. It can be used to estimate the concentration
of certain solutions used in industrial processes such as caustic or brines, and
the concentration of dissolved solids in waters by evaporation.
ASTM Method D 1429 covers an accurate gravimetric determination
using a specific-gravity bottle (pycnometer) in which a known volume of
water is weighed at a temperature of 15.5°C (60° F). This method has an
accuracy of ±0.0005. A less-precise method is included for determining the
specific gravity of sludges and muds. This is done by weighing an Erlenmeyer
flask filled first with water and then with the sample, and comparing the two
net weights.
206 MANUAL ON WATER
Specific gravity also has been determined to the fourth decimal place with
a balance of the Westphal type which measures buoyancy of the water on a
totally immersed plummet. Specific gravity of concentrated brines and
caustic solutions can be measured with appropriate hydrometers with
sufficient accuracy for control purposes. A quick approximation of the
specific gravity of any water solution can be made by weighing a pipetted
sample and comparing it with the weight of the same volume of distilled
water at the working temperature.
Surface Tension
Surface tension is a little-used property in the investigation and control
analyses of industrial waters. Occasionally, it is used to indicate contamina-
tion by some water-soluble organic solvent or as an indication of the
presence of surfactants. This can be helpful, for example, in locating a
possible cause of boiler water foaming.
ASTM Method D 1590 uses a ring tensiometer to measure the surface
tension of a liquid. It measures the amount of force required to lift a
standard platinum-indium wire ring from the surface of the sample. The
method does not disclose any direct relationship between the surface tension
and the concentration of surfactant solutions.
A rough indication of surface tension can be obtained with a slender glass-
stoppered glass tube which is filled to a standard mark with the sample. The
tube is stoppered and placed in a horizontal position, and the length of the
air bubble is compared with the length of the air bubble when distilled water
is used in place of the sample. With samples of lowered surface tension, the
bubble is longer than that obtained with distilled water. The tube is
calibrated by filling to the standard mark with distilled water, stoppering,
placing a horizontal position, and marking the tube at the two ends of the air
bubble.
Turbidity
Turbidity in waters is due to the presence of suspended solids dispersed
throughout the water, resulting in a reduction of its transparency. Measure-
ment of turbidity is therefore a measure of opacity or light-scattering by
suspended solids, and is reported in arbitrary units. ASTM Method D 1889
covers the determination of the turbidity in industrial water and industrial
waste water. Three procedures are presented, the Jackson candle, nephelo-
metric, and absolute turbidity methods.
A Jackson candle turbidimeter consists of a graduated glass tube, a
standard candle, and a support for the candle and tube. The water being
tested is poured into the tube until the image of the candle flame just
disappears. The depth of water at this point is related to'turbidity values by
standardization of the apparatus; usually it is converted directly into
turbidity values by reference to tables supplied with the instrument. Waters
of high turbidity, more than Jackson turbidity number 1000, are diluted
before the test is made.
When turbidity is lower than Jackson turbidity number 25, it is desirable
to use a relative turbidity method such as nephelometry. This is based on the
light-scattering properties (Tyndall effect) of the suspended solids. Nephelo-
meters are available commercially, and most of these instruments measure
light scattered at approximately 90 deg, or at 90 and 270 deg. Turbidity
standards have been prepared by thoroughly mixing suitable amounts of
finely divided titanium dioxide into partially polymerized polystyrene.
Calibrated commercial standards in sealed tubes can be purchased. Results
are reported in terms of turbidity units.
Neither of the preceding methods measures absolute turbidity. Instru-
ments are commercially available for measuring absolute turbidity and are
based on an integrating sphere which sums up most of the source light that
has been scattered by the sample. This method is not subject to particle size
limitations. Absolute turbidity is defined as the fractional decrease of
208 MANUAL ON WATER
Iron Bacteria
Iron bacteria is a general classification for microorganisms that utilize
ferrous iron as a source of energy and are characterized by the deposition of
ferric hydroxide in their mucilaginous sheaths. The process is continuous
with these growths, and over a period of time large accumulations of slimy
brown deposits can occur. Iron bacteria may clog water lines, reduce heat
transfer, and cause staining; objectionable odors may arise following death
of the bacteria. The organic matter in the water is consequently increased,
and this in turn favors the multiplication of other bacteria.
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 209
ASTM Method D 932 describes the procedure for the detection and
identification of iron bacteria by examination under a microscope. Several
genera are characterized, and photographs are provided to aid in their
identification.
Microorganisms
An examination of a water supply for microorganisms is done for one or
more of the following reasons: to detect contamination; to identify and
estimate the amount of algae, bacteria, mold, protozoa, and other plankton;
to elucidate the results of chemical examination and microbicidal treatment;
and to ascertain the causes of undesired odor, color, or turbidity. Chapter 5,
Treatment of Process Water and Waste Water, mentions the effects of, and
treatment for, various microorganisms occurring in water.
ASTM Method D 1128 covers the identification, by microscopic examina-
tion, of bacterial cells, mold filaments, algae, protozoa, and other small
animals, and such particles of inert material as may be found in process
water and waste water.
Sulfate-Reducing Bacteria
Sulfate-reducing bacteria are microorganisms capable of reducing sulfate,
or other fonris of oxidized sulfur, to hydrogen sulfide. This reaction takes
place only under anaerobic conditions; thus, the bacteria may be found in
quantity in anaerobic deep wells, lake or marsh bottoms, reservoir bottoms,
in the soil, and beneath deposits or other bacterial growth in aerated
systems. Their proliferation and the amount of hydrogen sulfide produced
depend upon the sulfate concentration. Because of the production of
hydrogen sulfide, these bacteria cause corrosion of metals and deposition
problems.
ASTM Methods D 993 include a procedure for identification and
estimation of sulfate-reducing bacteria, based on iodometric determination
of the hydrogen sulfide produced by the bacteria in a suitable medium under
anaerobic conditions. A simplified procedure provides for qualitative deter-
mination based on the use of lead acetate paper to detect the hydrogen
sulfide produced.
Aluminum
The control of aluminum in industrial waters is desirable because of its
potential scale- and sludge-forming characteristics. Its presence may be due
to suspended clays which are present in the raw water or from coagulants
used in the pretreatment of raw waters. Corrosion and erosion of aluminum
tubing in condensers and feedwater heaters also can be a source of
aluminum. While the corrosion-erosion rate of these tubes is low, the large
surface area involved eventually can lead to sizeable concentrations in
boilers.
Aluminum in the form of alumina or the aluminum ion can be trouble-
some in boilers. If hardness treatment of the feedwater is not properly
controlled and maintained, scale deposits of calcium and magnesium
aluminate may form. Also, in carbonate- or phosphate-treated feedwaters,
the presence of aluminum in excess may cause hard adherent aluminum-
silica complex deposits in the boiler. This sodium aluminum silicate scale
called analcite sharply reduces the heat-transfer ability of boiler tubes. Thin
films of analcite deposits can lead to several overheating and metal failure.
Alumina can be troublesome in cooling waters, because it precipitates at
pH levels usually maintained. Alumina may be present because of carry-over
from coagulation and clarification procedures. Dissolved aluminum may
also react with cooling water treatment chemicals, such as phosphates, to
form precipitates.
When analyzing raw waters for aluminum, attention should be given to
the presence of insoluble clays and other aluminum-containing suspended
matter. In boilers, these clays will become soluble forms of alumina at
normal operating levels of alkalinity and temperature, and so will become
available to contribute to deposition.
Fluorometric and spectrophotometric techniques both offer extreme
sensitivity for determining trace amounts of aluminum. One rapid method
[75] based on the fluorescence of aluminum 8-hydroxyquinolate in chloro-
form solution is capable of detecting 5/ug of aluminum per litre of water
solution. Another micrograms-per-litre range test [75] for aluminum in high-
purity waters uses morin reagent. In this test for aluminum concentrations of
0.25 to 2.0 /xg/litre, the standard deviation ranges from 0.09 to 0.06. These
two methods now are included in ASTM Methods D 857, Methods B and A,
respectively, Spectrophotometric Method C using Perron (8-hydroxy-7-
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 211
pollution. The organic nitrogen can be determined directly with the Kjeldahl
method if any ammonia present is first removed by distillation from a
buffered sample.
In all of the foregoing procedures, after digestion, the resulting ammonia
is distilled from an alkaline medium and can be measured as given in ASTM
Test of Ammonia on Industrial Water and Industrial Waste Water (D 1426),
or titrated if the amount is large.
Bicarbonate, Carbonate,
Carbon Dioxide
Carbon dioxide dissolves in water in varying amounts depending upon
temperature, pressure, and mineral content of the supply. In water, free
carbon dioxide increases corrosivity, causing acid attack upon metals with
which it comes in contact. In naturally occurring waters, dissolved carbon
dioxide is responsible for the dissolution of many minerals picked up by the
water in its percolation through the ground. Limestone, for example, is
dissolved in this manner, resulting in soluble calcium bicarbonate. Free
carbon dioxide present in process waters causes corrosion to the system. In
steam condensate, carbon dioxide forms carbonic acid; it is very corrosive
and appropriate steps must be taken for its elimination or neutralization.
The total available carbon dioxide content of water is considered to be the
sum of that combined as carbonate and bicarbonate, and free carbon
dioxide present. These ions exist in equilibrium with each other, their
relative concentrations depending upon the pH. Procedures for carbon
dioxide determination are given in ASTM Methods D 513. In the most
precise method, all the carbon dioxide, whether present originally in
combined form as carbonate and bicarbonate, or as free CCh, is separated
from the sample and collected in standard barium hydroxide; the excess of
the base is found by titration and calculated to carbon dioxide. In a more
routine method, the sample is treated to convert all carbon dioxide to
strontium carbonate; the carbonate is then dissolved in hydrochloric acid
and the excess is titrated and related to the original carbon dioxide content.
Curves are included to enable estimation of the percentage composition of
the sample in terms of carbonate, bicarbonate, and free carbon dioxide at all
pH levels.
Free carbon dioxide can be estimated very quickly by titrating a sample
with standard sodium carbonate or sodium hydroxide until only bicarbonate
is present in the solution (phenolphtalein end point); this procedure is much
used for carbon dioxide in well waters. Standard sodium hydroxide solution
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 215
must be used for free CO: determinatons on acid waters such as de-
mineralizer cation exchanger effluents; sodium carbonate is not an accept-
able titrant in this case. Alkalinity titrations and pH determinations along
with the use of nomographs can also be used to determine the concentrations
of the various forms of carbon dioxide.
Carbonate and bicarbonate ions are the chief sources of alkalinity in
naturally occurring waters, and are important when considering such waters
for plant use. Major quantities of soluble calcium and magnesium hardness
will be present as the bicarbonates. However, when such supplies are heated
sufficiently to drive off part of the combined COz, forming carbonates,
precipitation of calcium carbonate may occur. The scale-forming character-
istics of calcium carbonate may be useful at times. A thin layer laid down
inside metallic piping can provide a protective coating, preventing corrosion.
In such cases, the control of alkalinity (carbonate, bicarbonate, and carbon
dioxide content) is very important.
In boiler water applications, knowledge of the carbonate and bicarbonate
content of the water supply is essential for proper treatment. The concen-
trations of these ions must be accurately controlled and adjusted to obtain
optimum removal of hardness in lime or lime-soda ash pretreatment
systems. In low-pressure boilers, maintenance of a properly controlled
carbonate reserve in boiler water is desirable to prevent deposition of
calcium sulfate, which forms a very hard scale. Since calcium carbonate is
much less soluble than calcium sulfate at boiler water temperatures, the
presence of the carbonate ion ensures that residual calcium will be precipi-
tated as the carbonate, rather than sulfate.
In feedwater of higher-pressure boilers, control of the bicarbonate content
is essential to minimize breakdown and release of carbon dioxide, which will
go off with the steam. Carbon dioxide will dissolve in condensate to form
carbonic acid, which is corrosive to steam-condensing equipment and to the
condensate return system.
The concentrations of carbonate and bicarbonate alkalinity in water
supplies can be calculated, if the total carbon dioxide and pH of the supplies
are known. ASTM Methods D 513 include procedures for the determination
of total carbon dioxide, and provide graphs and tabular data for estimation
of carbonic acid, carbonate, and bicarbonate ions at all pH levels from 2.0 to
13.0.
For control purposes, approximations of reasonable accuracy can be
made from alkalinity and pH determinations using data compiled in the
form of nomographs [34]. These nomograph methods are not applicable
when the water supply contains appreciable concentrations of phosphates,
silicates, sulfites, and certain kinds of organic matter.
There are additional methods of somewhat restricted accuracy. The
titration of samples successively to the phenolphthalein and methyl orange
(or other suitable indicator) end points [4] can be used to indicate carbonate
and bicarbonate concentrations. The interfering ions mentioned in the
216 MANUAL ON WATER
foregoing also affect this titration method. On boiler waters, color from
tannins or lignin derivatives will interfere with detection of the titration
end points. A variation of this approach [35] in which the sample is titrated
between definite pH limits, before and after the carbon dioxide has been
boiled off, avoids principal titration errors and eliminates corrections by
coupling them with the blank determination.
Another quick method for approximating carbonate in boiler waters
depends on the insolubility of barium carbonate and barium phosphate in
alkaline solution. An aliquot of the sample is titrated to the phenolphthalein
end point, and the titration is then repeated on a second aliquot, to which the
difference between the two titrations represents carbonate and phosphate
alkalinity and may be calculated to carbonate if the phosphate concentration
is known.
Chloride
Chloride is present (generally as sodium chloride) in practically all waters.
Occasionally chloride will be present in combination with magnesium or
calcium, although higher concentrations of these salts suggest contamination
by seawater, brines, or industrial wastes. The concentration of chloride in
natural waters varies from a few milligrams per litre, or less, to several
thousand milligrams per litre in some groundwaters. Reasonable amounts of
chlorides can be tolerated in many industrial waters and in potable supplies.
Although chloride usually is not the direct cause of corrosion, the chloride
ion is small, highly mobile, and will accelerate corrosion reactions in
proportion to its concentration, because of its ability to penetrate and
increase solution rate of iron, and its contribution to electrolyte content. For
this reason, brines can corrode a system at a rapid rate. Chlorides can
accelerate stress corrosion of stainless steel alloys, so chloride concentration
must be carefully controlled in systems where these metals are used. In low-
pressure boilers and cooling waters, chlorides present few problems.
Chloride remains unchanged in process water, and this property makes
chloride analysis very useful. Chloride concentrates in boiler waters and
evaporative cooling waters in an exact ratio to the amount of evaporation
that takes place. Thus, a chloride analysis of makeup water compared with
that in the boiler water or cooling water gives a simple procedure for
estimating the amount of concentration that is occurring. Comparative
chloride analyses in conjunction with nitrate analyses also can be used to
indicate contamination of groundwater by sewage wastes.
ASTM Methods D 512 include three high-precision procedures. The first
is a mercurometric titration applicable to high-purity industrial water and
water relatively free of heavy metal ions. The second is a silver nitrate
titration for use with low-purity industrial supplies, process, and waste
waters; and the third, a mercuric thiocyanate colorimetric method. In
Method A, dilute mercuric nitrate solution is added to an acidified sample in
the presence of mixed diphenylcarbazone-bromphenol blue indicator. The
end point of the titration is the formation of the blue-violet mercury
diphenylcarbazone complex. In Method B, the sample is adjusted to pH 8.3
and titrated with silver nitrate in the presence of potassium chromate
indicator. The end point is indicated by persistence of the brick-red silver
chromate color. In Method C, mercuric thiocyanate reacts with the chloride
present, releasing an amount of thiocyanate ion that is equivalent to the
chloride. Added ferric iron forms a red color with the thiocyanate ion, which
is measured photometrically or by visual comparison.
Method A without sample concentration is for chloride concentrations
220 MANUAL ON WATER
Chlorine
The determination of chlorine is important because an increasing pro-
portion of industrial water is chlorinated. In addition to use for sterilization
of potable water, chlorine treatment is used for control of algae and
prevention of bacterial slime growths throughout cooling systems. In cooling
towers, continuous contact with free chlorine can cause some deterioration
of lumber; in large concentrations, chlorine can accelerate corrosion of
metals, especially in the presence of oxygen.
Chlorine in solution exists as free available chlorine such as hypochlorite
ions (OC1) or hypochlorous acid (HOC1), and as combined available
chloride, consisting of chlorine combined with ammonia nitrogen or nitro-
genous compounds. The sterilizing action of combined chlorine is not as
potent as that of free chlorine, but it possesses a longer residual time in
water; that is, it is more stable. In a given contact period, about 25 times as
much combined chlorine as free chlorine is required to yield the same
sterilization effect. Thus, the ammonia content of water is an important
consideration in chlorination treatment.
Chlorine residuals may be present in some surface waters where chlori-
nated industrial and sewage wastes are discharged.
Two methods for chlorine determination are presented in the Annual
Book of ASTM Standards, Part 31 [7]: Methods D 1253; and D 1427.
Method D 1253 includes a high-precision and two more routine methods for
determining total available chlorine residual. Two of these methods are
suitabi' ~ differentiating between free and combined residuals. The high-
precision method is an amperometric titration with phenylarseneoxide.
Routine Method A (which also differentiates between free and combined
residuals) is used for rapid control determinations of chlorine residuals up
to 10 mg/litre, but is most sensitive below 1 mg/ litre. Routine Method B
is applicable for chlorine residuals above 1.0 mg/ litre, and is particularly
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 221
useful for measuring high residuals (10 to 300 mg/litre). Both routine
methods are colorimetric procedures using orthotolidine to form a yellow
color.
The two methods of D 1427 permit determination of chlorine residuals in
the presence of most interfering constituents found in industrial waste water.
Method A is a starch-iodide titration, and Method B is an amperometric
titration. Both cover total chlorine measurement, but only the latter is
applicable to determination of free available chlorine.
A rapid method for determining free chlorine residuals above 1.0 mg/litre
in cooling waters involves titration of an acidified sample with a standard
methyl orange solution. Free chlorine decolorizes the methyl orange until
the chlorine residual is exhausted; then the color of the methyl orange
persists, indicating the end point. Chromate in low concentrations does not
interfere, but at higher levels masks the end point. Xylene cyanole has been
used instead of methyl orange, giving a readily discernible green end point in
high-chromate waters.
Samples to be analyzed for chlorine should be kept away from direct
sunlight prior to analysis. The analysis should be made as soon as possible
(not more then 5 min after sampling), because a chlorine residual may
decrease with time as a result of any chlorine demand of the sample.
Chromium
Chromium in water is of interest principally in the hexavalent form, in
connection with its use as a corrosion inhibitor. It also is a frequent
component of industrial wastes, in which it may be present in either the
trivalent or hexavalent form, or both. It is of minor importance, however, in
water supply for power plants. If introduced as a contaminant into boilers,
chromate will be reduced to trivalent chromium and precipitated as chromic
hydroxide.
Chromate and dichromate are not found naturally in water, but may be
present because of industrial contamination. The presence of chromium
compounds in surface water supplies usually indicates discharge of metal
plating solutions and similar industrial wastes, or the use of chromate and
dichromate-based corrosion inhibitors in cooling water. Obviously, the
manner of disposal of blowdown water from cooling towers using chromate
inhibitors presents a problem. Discharge of chromates into surface waters
should be avoided to prevent potential contamination of irrigation and
drinking water supplies, damage to aquatic life and other adverse effects.
The U. S. Public Health Service (USPHS) limit for hexavalent chromium in
drinking water is 0.05 mg/litre maximum.
Alkaline chromates and dichromates have long been used as corrosion
inhibitors in cooling systems. In ferrous metal systems, the chromate or
dichromate ion reacts with ferrous ions released at anodic areas, hexavalent
chromium being reduced to trivalent chromium and precipitated to form a
222 MANUAL ON WATER
Copper
Copper is rarely found in natural waters and, when it exists, is usually
derived from industrial wastes. Copper sulfate and stabilized copper com-
pounds now are being used extensively in the treatment of reservoir water to
control the growth of algae and diatoms, providing another source of copper
in various waters.
Knowing the copper content of industrial waters is important mainly
because of corrosion and deposition processes in which it is a factor. Copper
can be deposited in metallic form in pipes and boiler tubes, presumably with
the dissolution of an equivalent amount of iron. So far, the role of copper in
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 223
Cyanide
Cyanide does not occur naturally in water, but is the result of contamina-
tion. Waste waters from certain chemical processes and metal plating
industries are the chief source of the contaminant in surface waters. Residues
for insecticides and rodenticides can also be a source.
The chief reason for concern with cyanide in water is its highly toxic
character. In low concentrations it can kill marine life and useful bacteria,
thus upsetting the natural purification abilities of streams and promoting
buildup of other organic pollutants. Cyanide also may be detrimental to
sewage treatment processes.
The major problem in analyzing for cyanide is the removal of interfering
substances. ASTM Methods D 2036 include procedures for removing
interferences and making the determination. Methods for removal of
sulfides, fatty acids, and oxidizing agents are outlined, followed by distilla-
tion procedures for removing most other interferences. After interferences
are removed, cyanide is determined either by a modified Liebig titration
method using p-dimethylaminobenzalrhodanine internal indicator, or by a
colorimetric method using pyridine-pyrazolone if the concentration is below
226 MANUAL ON WATER
Fluoride
Fluoride is present in almost all natural water supplies. The fluoride
content varies considerably with the source, and with the extent of con-
tamination by waste discharges. Flourine has little significance in industrial
waters, but in drinking water in amounts of 1 to 1.5 mg/litre it is an effective
preventive of dental caries, if ingested during the period of permanent tooth
development. Above this amount, fluorine may cause mottling of teeth. For
potable water supplies, fluoride in excess of 1.0 to 1.5 mg/litre should be
removed by appropriate treatment processes.
Fluoride occasionally is used in cooling water treatment to prevent
precipitation of aluminum ions. In this application it functions by forming a
soluble complex, and can be considered a deposit inhibitor or antifoulant.
Fluoride also will precipitate in the presence of higher concentrations of
calcium and magnesium. In waters containing fair amounts of the fluoride
ion, the fluoride content will be significantly reduced during lime-soda
softening.
ASTM Methods D 1179 provide two procedures for the determination of
fluoride. Precision Method A [56] based upon the bleaching effect of the
fluoride ion on zirconium-organic complexones uses SPADNS reagent
(sodium 2-(p-sulfophenylazo)-l ,8-dihydroxy-3,6-naphthalene disulfonate).
This method tolerates many interferences and determines fluoride in the
range from 0.00 to 1.40 mg/litre. No waiting period is involved for color
fading; the reaction is immediate, color is stable and follows Beer's law in the
concentration range mentioned. The high-precision method provides for the
elimination of interferences by incorporating a distillation procedure, and
should be the method of choice on unknown waters.
If interferences are known to be absent, or present in sufficiently low
concentrations, the distillation may be omitted, and routine Method B used.
Method B depends upon the bleaching effect of the fluoride ion on
zirconium alizarin color.
A direct photometric method [57] using the wine-red cerium (Hl)-alizarin
complexone to produce a blue color with fluoride also can tolerate relatively
high amounts of interferences.
Hydrogen
Hydrogen occurs in the atmosphere in very minute quantities but is found
free in nature in significant amounts in the gases of volcanoes and fumeroles.
It has also been found occluded in rocks such as granite and has been
reported to be sometimes present in natural gas. Hydrogen dissolved in
natural waters is practically nonexistent and in the past was not regarded as
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 227
Iron
The presence of iron in water is objectionable because it contributes to
problems of taste, discoloration, turbidity, and deposits. For many uses,
such as high-pressure boiler feedwater, process waters for fabric dyeing and
paper making, photographic film manufacture, icemaking, and food proc-
essing, the water must be almost entirely free from iron.
The occurrence of iron in water varies widely depending on source of the
supply. The iron content of some deep wells and industrially contaminated
streams can be very high, while other sources may be iron-free. Iron, if
present (uncomplexed) in natural waters, normally is found in the form of
ferrous salts; however, upon contact with air it is readily oxidized to ferric
salts, which precipitate to give characteristic rust-colored deposits. Ferric
iron in many instances will remain in suspension in water, because of
occasional difficulty in coagulating ferric hydroxide. It can be removed by
energetic flocculation followed by filtration.
Corrosion is the chief source of the iron in boiler water. The iron often
creates serious problems in high-pressure steam-generating systems. Cor-
228 MANUAL ON WATER
rosion of metals in boiler and preboiler systems releases iron in ionic form,
and iron oxides which circulate with the water and may not be removed by
blowdown. Such oxides form adherent coatings and can lead to tube failures
by overheating, caustic gouging, and hydrogen damage. On surfaces of high
heat transfer, ferric iron complexes with sodium silicate, if present, to form a
very hard, strongly adherent deposit called acmite.
Cooling waters containing suspended or dissolved iron also can develop
serious fouling problems due to deposition of iron oxide or reaction
products of iron with treatment constituents such as chromate and phos-
phate. Dissolved or suspended ferric and ferrous iron also can foul ion
exchange resins used for water softening.
The analysis of iron in water usually is done spectrophotometrically or
colorimetrically, although a few titrimetric procedures exist for milligrams-
per-litre concentrations. ASTM Methods D 1068 are based upon the
intensity of an orange-red color produced by the reaction of ferrous iron
with orthophenanthroline or bathophenanthroline. Method A uses ortho-
phenathroline, and is designed for iron concentrations in excess of 0.05
mg/litre. It also is capable of distinguishing the distribution of iron between
the ferrous and ferric states. The proportion of soluble and suspended iron
can be obtained by difference from determinations made on filtered and
unfiltered samples. Method B uses the more sensitive color reagent batho-
phenanthroline, and is capable of detecting less than 1 jug/ litre of iron. It is
particularly applicable to high-purity water and steam condensates. Table 6
indicates areas of applicability of the three iron methods.
Good results also have been obtained with a 2-2' bipyridine [60], 2,2',2"
tripyridine, and with thioglycollic acid (mercaptoacetic acid) [61]. The
principle of the bipyridine method is the formation of a pink complex with
ferrous iron at a pH of 3 to 4. Tripyridine develops a reddish purple color
with iron over a wide pH range. The use of this reagent along with
ethylenediamine to complex heavy metals is the basis for a standard method
[4\. The reaction between thioglycollic acid and iron gives a relatively stable,
reddish purple color. 'A thiocyanate [62] method also has been used.
Comparative results on samples of low iron concentration using batho-
phenanthroline, orthophenanthroline, bipyridine, arid thiocyanate methods
have been reported [63], and Herre [64] made a detailed comparison of
thioglycollic acid, potassium thiocyanate, sulfosalicylic acid, ferron, and o-
phenanthroline. The bathophenanthroline method has been modified to
eliminate the extraction step, the lower limit being 5 /ug/litre iron [65]. Ethyl
alcohol is added to effect the solution of the iron-bathophenanthroline
complex in water. Grat-Cabanca [66] has studied interferences in the
bipyridine method with particular attention given to cobalt, nickel, and
manganese. He found that no interference from these ions resulted if the
ratio of the interfering ion to the iron concentration did not exceed 15,22, or
80, respectively.
Several colorimetric agents exist for iron and a number of new reagents
TABLE 6—Iron determinations.
Method D 1068 Precision Method A Precision Method B
Basis of measurement colorimetric, o-phenanthroline colorimetric, bathophenanthroline
Range concentrations of iron above 0.05 mg/ litre in indus- low concentrations of iron (200 yug/litre and under)
trial water and industrial waste water in industrial water
Application Industrial water and industrial waste water. For dis- industrial water with low iron concentrations. Total
solved and total iron iron
Summary of method the ferrous iron, solubilized with acid, forms an orange- for total iron the iron is reduced with hydroxylamine
red complex with 1,10-phenathroline. The intensity of hydrochloride and reacted with bathophenanthro-
the color produced is proportioned to the amount of line to form a red ferrous complex. The complex is
ferrous iron in the water. Ferric iron is converted to extracted with n-hexyl or isoamyl alcohol and color
ferrous with hydroxylamine hydrochloride for total intensity measured
and dissolved iron
Interferences interference if Cu, Co, Cr, Zn are ten times Fe concentra- if the pH is between 3.3 and 3.7, a I-mg/ litre concentra-
tion; Ni when in excess of 2 mg/ litre; Bi, Ag, and CN- tion of the following ions does not interfere: Cu, Mn,
must be absent; methods given for removal of inter- Al, Zn, Mg, Na, SiO2, NO3-, PO4=
ferences
Instrumentation or special Nessler tubes, filter photometer, or spectrophotometer Nessler tubes, filter photometer (green filter), or spec-
equipment capable of reading at 510 nm trophotometer capable of reading at 533 nm
230 MANUAL ON WATER
Load
Lead is practically nonexistent in natural waters; in cases where lead is
present, it is directly due to corrosion reactions or waste contamination.
Mine waters and wastes from metal plating industries are the most common
sources of contamination in raw-water supplies. Most instances of lead being
present in water may be traced to contact with lead piping or lead-bearing
jointing compounds used with threaded piping. The character of the water
determines its plumbo-solvency. Naturally occurring waters that are highly
acid or contain large amounts of carbon dioxide and are low in calcium and
magnesium bicarbonates are apt to dissolve significant amounts of lead.
Organic content in acidic waters also increases the plumbosolvency.
The lead content is primarily of interest in potable water supplies because
it has a cumulative poisoning effect in the human body. For industrial uses,
lead is not usually a significant problem.
Lead, especially in small amounts found in waters is usually determined
with dithizone [67]. The lead dithizonate precipitate is soluble in chloroform
or carbon tetrachloride and imparts a red color to the solution. A method
using a preliminary dithizone extraction and reextraction into an acidified
aqueous phase [4] isolates the lead for subsequent determination. Only
bismuth, thallium, and stannous tin interfere, and a procedure is proposed
for the elimination of bismuth and tin interference [4]. The method
determines from .0.01 to 0.05 mg of lead.
Before the introduction of dithizone, small amounts of lead were deter-
mined by comparing colloidal precipitates of lead sulfide with standards
similarly prepared. Electrolytic methods for small amounts of lead have also
been used, but they do not compare favorably with dithizone.
Polarigraphic methods for low concentrations of lead have been de-
veloped. Ullman [68] and co-workers devised a procedure using a quiet
mercury pool cathode cell to determine down to 0.01 mg/litre lead in waste
waters. The method is also capable of determining like concentrations of
cadmium, copper, nickel, and zinc on the same sample.
Manganese
Manganese occurs in soil and rocks as manganese dioxide and can be
dissolved in natural waters by the action of bacteria under anaerobic
conditions [69]. The presence of complexing agents such as carbon dioxide,
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 231
Nickel
Nickel is very seldom found in natural waters, but has become significant
in industrial supply or process waters because of the increasing use of
stainless steels and other nickel-containing alloys in water systems. Aside
from the presence of nickel as an indicator of corrosion-erosion of such
alloys, this determination is of importance in water chemistry for high-
pressure boilers. Nickel behaves much like copper in this environment and
may be precipitated as the oxide or as metallic nickel. Its possible role in
corrosion of other metals has not yet been elucidated.
In ASTM Methods D 1886 nickel is determined with both sodium
diethyldithiocarbamate and dimethylglyoxime. Method A, using sodium
diethyldithiocarbamate, is subject to more interferences than Method B,
using dimethylglyoxime, but is more sensitive, being able to detect 0.001
mg/litre. The nickel diethyldithiocarbamate is extracted with carbon tetra-
chlorid,e in the presence of citrate, as in the copper salt. A correction for
copper is made by reading the absorbance of the sample at two wavelengths,
one the maximum for nickel and the other the maximum for copper.
232 MANUAL ON WATER
Nitrate
Nitrate in low concentrations occurs in most natural waters and ranges in
concentration generally from 0 to 70 mg/litre, the extremes being rare. It is
mostly derived from nitrogenous organic matter of animal origin; decay of
vegetable matter in soil yields very little nitrate. For this reason, significant
concentrations of nitrate in water may be indicative of water sources
polluted at some earlier time with sewage or animal wastes. The strata
through which the water percolates can also be a source of significant
amounts of nitrate. Nitrate in water generally is of serious concern only
where the supply is used for potable purposes. Nitrate in concentrations
above 20 mg/litre has been reported as the cause of methemoglobinemia in
infants, a disease characterized by blood changes and cyanosis, in which the
hemoglobin apparently becomes incapable of transporting oxygen.
Nitrates find applicability in water treatment in corrosion-inhibitor
compounds for cooling systems; in low-pressure boilers, nitrate alone or in
conjunction with certain organic compounds gives effective control of
intergranular corrosion (embrittlement) of boiler metal.
ASTM Method D 992 is a rapid, simple, and precise colorimetric
procedure. A yellow color is developed in the sample by the reaction of
nitrate ion with concentrated sulfuric acid and a chloroform solution of
brucine alkaloid. An accuracy of 0.5 mg/litre is obtainable in the 0 to 50-
mg/litre range.
One method [74] purported to be very reliable is based on the formation of
4-nitroso-2,6-xylenol by reacting the nitrate in the sample with 2,6-xylenol in
a highly acidic medium, in the presence of ammonium chloride. The
concentration of the 4-nitroso-2,6-xylenol which is directly related to the
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 233
Nitrite
Nitrite in natural water is generally regarded as evidence of sewage
pollution. Its presence indicates that nitrogeneous organic matter from
sewage or animal wastes is undergoing active oxidation or nitrification and
that the process is not complete. The occurrence of nitrite is also possible if
nitrate-containing water supplies come in contact with certain reducing
materials.
Nitrites are occasionally used for corrosion control in closed cooling
systems. Discharge of nitrite-treated cooling water into surface supplies may
create pollution problems, or be mistakenly interpreted as indicative of
sewage dischargers. When sampling waters for nitrite analysis, the bottle
should be sterile, and the determination should be made as soon as possible
after collection of the sample.
The ASTM Test for Nitrite Ion in Undustrial Water (D 1254) provides
two procedures for determining nitrite ion. The most accurate method is
colorimetric and is based upon the diazotization of sulfanilic acid by the
nitrite ion, followed by coupling with alpha-naphthylamine. The reaction
takes place at a pH of 2.0 to 2.5 to produce a reddish purple color which can
be measured photometrically at 520 nm or by visual comparison. Its
application is to samples that contain less than 0.5 mg/litre nitrite and are
not highly polluted. This range can be extended by dilution. A thorough
discussion of interferences is also included.
234 MANUAL ON WATER
Nitrogen
Dissolved nitrogen is not ordinarily of interest in industrial water. In
pressurized water nuclear power reactors, the concentration of dissolved
nitrogen in the primary water is sometimes important because of the
possibility of radiation-induced reactions of nitrogen with dissolved oxygen
to produce nitric acid, or with dissolved hydrogen to produce ammonia.
These reactions can produce wide variations in the pH of the primary water.
Nitrogen has been determined with the gas transfer and Blacet-Leighton
apparatus. Dissolved oxygen and hydrogen are removed from the total gas,
and the remainder reported as inert gas, most of which is nitrogen.
Oxygen
Oxygen is dissolved in varying amounts in most waters. It is essential to
the life of fish, and other aquatic organisms. In pure water at room
temperature, oxygen dissolves to concentration levels of approximately 8.5
mg/ litre. The solubility decreases as the dissolved solids and temperature
increase, but increases with increasing pressure. In industrial waters, dis-
solved oxygen is primarily of interest because of its relation to corrosion
reactions. Minute amounts of oxygen in boiler water and feedwater can
cause severe corrosion. Experience has shown that the dissolved oxygen
content should be below 0.03 mg/litre, and preferably below 0.005 mg/litre
in feedwater for high-pressure boilers.
In other waters, dissolved oxygen may not be the direct cause of
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 235
Phosphate
Phosphate occurs in certain rocks and sands, municipal sewage, animal
manure, and in soil, and consequently may be expected in water. Aside from
naturally occurring phosphates, additional phosphates eventually are added
to water supplies through agricultural runoff, and the widespread use of
phosphate-built detergents. In groundwaters, phosphate is found in minute
quantities, the amount dependent upon the original pollution of the water
and strata through which it has percolated. This suggests the utility of
phosphates as additives to underground waters, to conveniently trace their
flow.
236 MANUAL ON WATER
Silica
Silica concentration can be a very important consideration in some
industrial installations such as steam generation and cooling-water systems.
The silica is brought into these systems in the makeup (raw or partially
treated) water, or by airborne dusts. Natural (raw) waters may contain more
than 100 mg/litre of silica in solution. The silica and other materials in the
makeup water will concentrate in the boiler or cooling water system due to
evaporation, and form deposits when solubility limits are exceeded. It is
therefore important to determine that the silica concentration in the boiler or
cooling water increases in proportion to the concentrations of other
constituents present in the makeup water. If the silica in the boiler or cooling
water is less than expected, the formation of siliceous deposits in the system
may be indicated.
Silica is of special importance in steam generation, because under certain
conditions it can form troublesome scales of silica and complex silicates in
the boiler, or siliceous deposits in turbines. Because of the very low heat-
transfer characteristics of these materials, extremely thin layers can cause
metal overheating, corrosion, and failure of boiler tubes, as well as reduced
heat transfer. The silica in high-pressure boilers can be carried over with the
steam. As the boiler pressure increases above 2758 kPa (400 psi), the
tendency for silica to be selectively carried into the steam increases; with
constant pH and boiler pressures, carry-over is proportional to the amount
of silica in the boiler water. As pressure rises, the ratio of silica in steam to
silica in boiler water increases rapidly. This silica deposits hard, glassy scales
on turbine blades, resulting in pluggage of small passages and imbalance of
the rotor. Investigations have shown that the key to minimizing silica scales
is to keep the silica in the boiler water at a sufficiently low level to maintain
silica in the steam at not more than 0.02 mg/litre [86\.
Silica can also cause formation of deposits in cooling-water systems, but
here it usually is considered of minor importance unless the concentration is
beyond the solubility limit (usually 150 mg/litre or higher), or if the
magnesium content and pH value are high.
In other industrial applications, silica may be added as part of the
treatment program (example: corrosion control in potable water distribution
systems). Silica analysis is frequently used to maintain proper treatment
levels in systems of this type.
Procedures for the determination of silica are included in ASTM Methods
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 239
D 859. Table 8 gives a summary of the important aspects of the methods,
and will aid in the selection of the proper procedure applicable to specific
problems.
Colorimetric Method B of Method D 859 has been suggested for the
determination of silica in high-pressure boilers, where silica, even in very low
concentrations, is of high importance. Special precautions [87] must be
taken during sampling to avoid loss of silica to the sampling equipment. In
sampling steam, errors are said to result if the pressure of the steam is
reduced ahead of the condenser.
Sulfides
Sulfide is present in water generally as the result of industrial waste
contamination or decomposition of sulfate by anaerobic bacterial action.
Sulfide can be very damaging to equipment and industrial processes. In
relatively high concentrations, it will attack normally resistant alloys such as
stainless steel and brass and cause rapid deterioration. Sulfide can be
substantially removed by acidification followed by aeration. Complete
removal can be accomplished by subsequent chlorination.
Hydrogen sulfide is a toxic gas with a characteristic offensive odor and
taste, and is fairly soluble in water. In water it reacts as an acid and can be
actively corrosive. Under certain conditions in the presence of oxygen, it
may even be oxidized to sulfuric acid. In addition, hydrogen sulfide reduces
and precipitates constituents of many cooling-water treatment chemicals,
causing unwanted deposits. Because of these objectionable characteristics, it
is desirable to remove it from process and potable waters.
Hydrogen sulfide is found occasionally in surface waters, resulting from
miscellaneous pollution or anaerobic decomposition of organic compounds.
It occurs most commonly in well waters located near "sour gas" oil fields, or
as a result of anaerobic bacterial reducing action on inorganic sulfur
compounds such as sulfate. It may also be produced in soils by bacterial
action, and is a consideration in the corrosion of buried metal piping.
Hydrogen sulfide may be produced in sodium sulfite-treated boiler waters
with operating temperatures of 274° C (525° F) and above. On high-
temperature surfaces (superheaters, etc.), the sulfite breaks down to sodium
sulfide and sodium tetrathionate. The sodium sulfide is then hydrolyzed to
hydrogen sulfide and passes into the steam, where it is very corrosive.
Quantitatively, and semiquantitatively, odors indicating hydrogen sulfide
in water can be confirmed with lead acetate paper, which is quickly darkened
by exposure to the vapor from a slightly acidified sample. In ASTM Method
D 1255, hydrogen sulfide is determined as part of the total and dissolved
sulfides, and the concentration can be calculated from the concentration of
dissolved, sulfides and the pH of the sample.
It is best to analyze sulfide-containing samples immediately. When this is
not possible, the sulfide content should be fixed by adding a suitable
TABLE 8—Silica methods.
ASTM Designation
D 859 Precision Method A Precision Method B Routine Method C Routine Method D
Test for total silica (colloidal and crys- crystalloidal silica crystalloidal silica crystalloidal silica
talloidal). When used with
Method B, C, or D, colloidal
silica can be determined by
difference.
Range as low as 1 mg/ litre below 1 000 Mg/ litre below 10 mg/ litre below 10 mg/ litre
Precision 0.4 mg/ litre 1.3 jug/ litre + 3 percent of 0.1 mg/ litre 0.1 mg/ litre
concentration determined
Type of water raw water, cooling water, boiler steam condensate, ion ex- raw water, cooling water, boiler raw water, cooling water, boiler
water, waste water change bed, nuclear reactor water, waste water water, waste water
Interference no interference no interfering material present turbidity, color (tannin, Cu+ same as C, except tannin does
jon), chromate ion inter- not interfere
ferences
Applicable to need for total silica content system containing very low rapid control analysis where rapid control analysis where
silica no color is present due to color is present due to
tannins or other organics. tannins
Instrumentation none spectrophotometer 815 nm or same as B or use matched same as C
filter photometer 640-700 Nessler tubes or Duboseq-
nm or 815 nm type color comparator
Theory silicon compounds dissolved or reactions of soluble silica with (a) utilizes yellow silicomolyb- in the presence of a reducing
suspended in water are concen- molybdate ion, blue color de- date color complex for com- agent such as sodium sulfite,
trated and precipitated as veloped with l-amino-2- parison or (b) alternative, to soluble silica reacts with mo-
partially dehydrated silica by naphthol-4-sulfonic acid. increase sensitivity and lybdate ion to form a blue
evaporation with either per- The color is read photo- eliminate color interference, complex. The color is read
chloric or hydrochloric acid, metrically and compared l-amino-2-naphthol-sulfonic photometrically and com-
followed by HF treatment with standards acid is added providing blue pared with standards
color for comparison
measurements
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 241
Sulfate
Sulfate ions are relatively abundant in natural waters, especially in hard
waters. In industrial waters, sulfate is of interest mainly where evaporative
processes introduce potential scaling problems and where control of total
dissolved solids is a major consideration. Sulfate often is a constituent of
boiler deposits and heat exchanger scales, softening and other treatment
procedures being required for deposit control. The determination of sulfate
for regulation of allowable concentrations in boiler water and in cooling
towers (where sulfates often are increased by addition of sulfuric acid for
alkalinity reduction and pH control) can be useful. The determination of
sulfate is also useful in the estimation of total dissolved solids.
Sulfate concentration in potable water supplies also deserves considera-
tion. High amounts of sulfate impart a faintly bitter taste to the water, and
cause laxative effects, especially on children. While the human body usually
can adjust to relatively high sulfate waters, certain environmental conditions
may indicate their use to be inadvisable.
242 MANUAL ON WATER
ASTM Methods D 516 provide three tests for determining the sulfate
concentration of water samples. These methods and their applicability to
various types of water are listed in Table 9.
There are several other titrimetric procedures for determining sulfate. In
the benzidine procedure, an addition product of benzidine and sulfate is
precipitated from an acidified solution, washed, redissolved in hot water,
and titrated with standard sodium hydroxide. This method, while not highly
accurate, is especially useful for determining sulfate in the presence of
relatively high amounts of sulfite. In another procedure [89,90], the sulfate is
precipitated with barium chloride, filtered, and the barium sulfate re-
dissolved in a known volume of 0.05 M EDTA. The EDTA is then back-
titrated with standard barium chloride solution using a suitable metal
phthalein as indicator. Several other variations of this approach exist.
Sulfite
The occurrence of sulfite salts in natural waters is rare, because sulfite is so
readily oxidized by air. Because of this ease of oxidation, sulfite finds
widespread application as an oxygen scavenger in boiler waters to prevent
corrosion. At high temperature and boiler pressure, sulfite can break down
to yield sulfur dioxide, and, in the presence of alkali, hydrogen sulfide to the
steam. In such instances, the sulfite concentration must be carefully con-
trolled. It is desirable to limit the use of sulfite to as low a concentration as
practicable for complete oxygen removal, including necessary residuals.
Sulfur dioxide is formed when sulfur-containing compounds are burned
or when certain metallic sulfides are strongly heated in air. It occurs
naturally in the gases emanating from volcanoes and fumaroles and is
present in the air surrounding manufacturing areas or cities, because of the
combustion of fuels and other sulfur-containing materials. It is readily
soluble in water, where it becomes sulfurous acid or salts thereof, and has
been found in hail, snow, and especially frost in the neighborhood of cities
and towns. Sulfurous acid has also been found in numerous mineral waters
and in springs near active volcanoes. In other naturally occurring waters,
both dissolved sulfur dioxide and sulfite, because they are readily oxidized
by the oxygen in the air, are unlikely to occur except in very special cases.
Sulfur dioxide has many uses in manufacturing, but in water and waste
treatment its use is confined mostly to dechlorination procedures and to
chromate-reduction waste treatment applications. In dechlorination, sulfur
dioxide reacts with chlorine to form sulfuric acid and hydrochloric acid,
both of which are neutralized by the natural alkalinity of the water being
treated.
Total sulfur dioxide in water includes free sulfur dioxide, bisulfite, and
sulfite ions. Like carbon dioxide, the relative concentrations of the three
ionic species depend upon the pH of the solution. The determination of
sulfur dioxide usually is based upon its reducing properties in solution, the
same approach used for determining sulfite ions.
TABLE 9—Sulfate.
ASTM Method D 516 Precision Method Routine Method A Routine Method B
f
Basis of measurement gravimetric turbidimetric volumetric
Range 20 to 100 mg/ litre SO4'=(can be 10 to 100 mg/ litre SO4= 5 to 1000 mg/ litre SO4=
extended)
Precision 1 percent of amount present as good as 5 percent or 2 mg/ litre, which single operator — 0.5 mg/litre
ever is greater. Depends on inter-
ferences and skill of analyst.
Application all types of industrial water and rapid routine testing of industrial rapid determination of SO4= over wide
industrial waste water waters range in industrial water for routine
Summary of method sulfate ion is precipitated and sulfate ion is precipitated as barium or control tests
weighed as barium sulfate after sulfate and a suspension made sulfate ion is titrated in alcoholic solu-
removal of silica and other in- Glycerin and sodium chloride are addedtion with standard barium chloride
soluble matter. to stabilize suspension and minimizeusing thorin as the indicator. End
interferences point change: yellow to pink, rela-
Interferences SOf? may oxidize and precipitate insoluble material — must be removed tively sharp
S= \ SO4'= dark color cations: removed by ion exchange
water quality affects suspension of above 2 mg/litre F~
barium sulfate 50 mg/litre NO;T
2 mg/litre PO 4 = /can be elimi-
SOi", CrO4=, S = Jnated
1000 mg/litre Cl at low SO4= concen-
tration
Instrumentation or special analytical balance photometer suitable for measuring microburet
equipment between 350 and 425 nm ion exchange column
cell path of 40 nm magnetic stirrer helpful
244 MANUAL ON WATER
ASTM Methods D 1339 list three volumetric methods for the deter-
mination of sulfite in industrial waters. Two precision methods, A and B, fix
the sulfite in the sample by adding hydrochloric acid, potassium iodide, and
potassium iodate before it is exposed to the air. The iodine chloride formed
reacts with the sulfite present, and the excess is then back-titrated with
sodium thiosulfate.
Method A uses a special sampling apparatus to exclude air and allow
addition of the fixing reagents before the sample is exposed to the air. After
fixing, the sample is drained into a beaker and titrated using an electrometric
dead-stop apparatus. The technique allows determination of 0.0 to 6.0
mg/litre sulfite as Na2SO;i.
Method B is a simplification of Method A. The sample is collected in a
manner to exclude air, fixed immediately upon opening, and titrated to a
starch indicator end point. It is designed for 6 mg/litre Na2SO? and up.
Routine Method C is a direct titration of the sample with potassium
periodate after addition of hydrochloric acid and potassium iodide. It is
designed for control tests where good precision is not required and where the
sulfite concentration exceeds 3 mg/ litre.
Zinc
Zinc is found in small quantities in most industrial waters, resulting from
corrosion of galvanized iron and brass in condensing, cooling, and dis-
tributing systems. A determination for zinc may be made as an indication of
deterioration of particular equipment, for identification of the source of this
constituent in water-formed deposits, to determine the concentration of zinc
in systems using zinc salts as corrosion inhibitors, or to determine zinc as a
pollutant in waste water.
The nephelometric procedure [92], in which interfering substances are
removed by hydrogen sulfide and turbidity is then developed with ferro-
cyanide, has been used successfully. The most suitable range for direct
comparison with standards is 1 to 10 mg/litre. Since the zinc content is
concentrated during the procedure, the lower limit in the original sample is
about 0.05 mg/litre and the optimum comparison level about 0.2 mg/litre.
A turbidimetric method using sodium diethyldithiocarbamate also has
been reported. [93, 94].
Zinc may be determined with dithizone (diphenylthiocarbazone). The
reaction product is red when extracted into carbon tetrachloride, and this is
used to measure the zinc content photometrically. There are several pro-
cedures that use various complexing agents to eliminate interferences.
Among these, bis (2-hydroxyethyl) dithiocarbamate is purported [95] to be
the best. Zinc in the amount of 0.01 mg/litre can be determined.
A direct method using zincon to develop a blue color with zinc, in which
heavy metals including the zinc are complexed with cyanide, has been
reported [96]. The zinc is released selectively with chloral hydrate and reacts
directly with the zincon reagent. This procedure is the basis for ASTM
Methods D 1691.
pH 6.83
Aluminum as Al, mg/ litre 0.25
Nitrate as NO3, mg/litre 6.5
These values tell the reader something about the methods that were used.
The pH reading of 6.83 indicates the use of a precise potentiometric
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 247
pH
The pH of water is a measure of its hydrogen ion activity. It is used to
indicate the acidity or basicity of aqueous solutions, which includes natural
waters, and is the result of the dissociation properties of the solutes. Both
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 249
lamination. On the other hand, such an analysis might help determine what
type of analysis is needed, and what sample treatment or precautions are
necessary for future analyses. In the first case, an interpretation that is too
extensive may lead to an erroneous picture and future trouble. As noted,
proper interpretation of a single sample can serve as a useful, although
limited, tool in guiding future work.
The amount of time elapsed between sample collection and the actual
analysis is another important factor to consider when interpreting data.
Chemical and physical changes can take place after a sample is drawn, and
such possibilities must be considered.
Choosing significant data is an important part of interpreting results. In a
well-planned program of analysis, only the significant constituents will be
analyzed. Therefore, in interpreting the results, only the significance of the
concentrations reported and their interrelation remain to be translated into
meaning. Past analysis also will have an influence on interpreting a current
analysis.
An example will help illustrate the interpretation of significant data.
Suppose heat exchangers in an evaporative, open recirculating cooling
system are to be protected from corrosion by controlled deposition of a thin,
impervious layer of calcium carbonate. If the water supply is amenable to
this approach, such deposition can function as an inexpensive but effective
corrosion control procedure. However, close regulation of certain important
constituents must be maintained. If the circulating water is too acidic
(relatively speaking; not necessarily in the free-acid range), corrosive con-
ditions will prevail and the protective scale will be removed, or its formation
prevented. On the other hand, conditions too favorable for scaling will
permit excessive buildup of calcium carbonate deposition. An equilibrium
condition is the desired state. To maintain this equilibrium (in actual
practice, very slightly scaling) several factors must be known and regulated.
These are the calcium concentration, the methyl-orange alkalinity, total
dissolved solids, temperature, and pH. By utilizing Langelier Saturation
Index data (available in the form of nomographs, charts, and tables),
appropriate calculations can be made to determine the scaling or corrosive
nature of the cooling water. Adjustments in scaling or corrosive tendencies
can then be made by altering the alkalinity and pH of the circulating water.
Similar analyses and interpretations must be made on the makeup water
added to the cooling system. In maintaining such a corrosion control system,
frequent interpretations must be made about the significance of changes in
concentration of the various constituents. Each change in concentration
must be considered in relationship to the other constituents. An increase of
20 mg/litre in calcium content of makeup water may or may not signal the
need for control adjustment. If the alkalinity or total dissolved solids also
change appropriately, no adjustment in chemical feed may be necessary. The
importance of proper interpretation, which in this example involves a special
calculation, is apparent. The various constituents are interdependent, and
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 251
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252 MANUAL ON WATER
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[50] Besev, A. I. and Ivaryitin, M. I., Vestnik Moskovskogo Universiteta, Seriya Matematiki,
Mekhanki, Astronomii, Fiziki i Khimii, VMUMA, Vol. 13, No. 2, 1958, pp. 177-181.
[5/] Nemodruk, A. A. and Stasynchenko, V. V., Zhurnal Analiticheskoi Khimmi, ZAKHA,
Vol. 16, 1961, p. 407-411.
[52] Bowles, P. F. and Nicks, P. F., Analyst, ANALA, Vol. 86, 1961, pp. 483-485.
[53] Abbott, D. C. and Harris, J. R., Analyst, ANALA, Vol. 87, 1962, pp. 497-499.
[54] "Methods for Analysis," Journal, Association of Official Agricultural Chemists, JOACA,
6th ed., 1945, p. 638.
[55] ASTM Method E 53, Chemical Analysis of Copper (Electrolytic Determination of
Copper), Annual Book of ASTM Standards, Part 32, American Society for Testing and
Materials, 1969.
[56] Bellach, E. and Schoubae, P. J., Analytical Chemistry, ANCHA, Vol. 30, 1958, p. 2032.
[57] Yamamura, S. S., Wade, M. A., and Sikus, J. H., Analytical Chemistry, ANCHA,
Vol. 34, 1962, pp. 1308-1312.
[55] "Power Station Chemistry," Publication H-ll, Edison Electric Institute, 1960.
[59] Rummel, J. K. in Symposium on Continuous Analysis of Industrial Water and Industrial
Waste Water, ASTM STP130, American Society for Testing and Materials, 1952, p. 42.
[60] Moss, N. L. and Mellon, M. G., Industrial and Engineering Chemistry, Analytical
Edition, IENAA, Vol. 14, 1942, p. 862.
[61] Swank, H. W. and Mellon, M. G., Industrial and Engineering Chemistry, Analytical
Edition, IENAA, Vol. 10, 1938, p. 7.
Standard Methods for the Examination of Water and Waste Water, American Public
Health Association, New York, N. Y., 12th ed., 1965, pp. 154-163, 482-485.
[62] Woods, J. T. and Mellon, M. G., Industrial and Engineering Chemistry, Analytical
Edition, IENAA, Vol. 13, 1941, p. 551.
[63] Andres, R. F., Proceedings, 14th Annual Water Conference, Engineering Society of
Western Pennsylvania, PEWPA, 1953, p. 106.
[64] Herre, E., Brennstoff- Wareme-Kraft, BRWKA, Vol. 13, 1961, pp. 456-459.
CHAPTER 11 ON ANALYSIS OF WATER AND WASTE WATER 253
[65] Nakashima, F. and Sakai, K., Bunseki Kagaku, BNSKA, Vol. 10, 1961, pp. 89-93.
[66] Grat-Cabanca, M., Analytica Chimica Acta, ACACA, Vol. 19, 1958, p. 108 (in French).
[67] Sandell, E. B., Colorimetric Determination of Traces of Metals, Interscience, New York,
3rd ed., 1959, Chapter 23.
[68] Ullman, W. W., Pfeil, B. H., Porter, J. D., and Sanderson, W. W., Analytical Chemistry,
ANCHA, Vol. 34, 1962, pp. 213-216.
[69] Ingols, R. S. and Milroy, R. D., Journal, American Water Works Association, JAWWA,
Vol. 55, 1963, pp. 282-290.
[70] Gates, E. M. and Ellis, G. K., Journal of Biological Chemistry, JBCHA, Vol. 168, 1947,
p. 537.
[71] Sandell, E. B., Colorimetric Determination of Traces of Metals, Interscience, New York,
N. Y., 3rd ed., Vol. 3, 1959, p. 612.
[72] Hooker, D. F. and Banks, C. V., "Preparation, Properties, and Applications of Some
Substituted Alicyclic vic-Dioximes," Ames Laboratory, Iowa State College, ISC-597,
Ames, Iowa, March 1955.
[73] McDowell, B. L., Meyer, A. S., Jr., Feathers, R. E., Jr., and White, J. C., Analytical
Chemistry, ANCHA, Vol. 31, 1959, pp. 931-934.
[74] Montgomery, H. A. C., and Dymock, J. F., Analyst, ANALA, Vol. 87, 1962, pp.
374-378.
[75] Goldman, E. and Jacobs, R., Journal, American Water Works Association, JAWWA,
Vol. 53, 1961, pp. 187-191.
[76] Hora, J. B., and Webber, P. J., Analyst, ANALA, Vol. 85, 1960, pp. 567-569.
[77] Shinn, M. B., Industrial and Engineering Chemistry, Analytical Edition, IENAA, Vol.
13, 1941, p. 33.
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[79] Fisher, F. L., Ibert, E. R., and Beckman, H. F., Analytical Chemistry, ANCHA, Vol. 30,
1958, pp. 1972-1974.
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1955, p. 1401.
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pp. 54-56; Chemical Abstracts, CHABA, Vol. 57, 1962, p. 3214.
[83] Robertson, R., Journal, American Water Works Association, JAWWA, Vol. 52, 1960,
pp. 483-491.
[84] Bell, R. N., Analytical Chemistry, ANCHA, Vol. 19, 1947, p. 97.
[85] Jones, L. T., Industrial and Engineering Chemistry, Analytical Edition, IENAA, Vol.
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pp. 29-31.
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STP442A-EB/Jul. 1978
Panelists
Any sensory testing program is doomed to failure if the persons involved
lack interest or are not properly trained. Greater flexibility exists for
selecting panel members in research than in field operations. Research
panelists may be screened for their sensitivity to taste and odor stimuli, and
the panel may be tailored to specific needs. This is not the case in water and
waste treatment plants or field survey crews. Field personnel are selected for
254
Copyright© 1978 by ASTM International www.astm.org
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 255
abilities other than their sensory response. Often, very few persons, or
perhaps only one, are available for these measurements. In such circum-
stances, they must be trained to best utilize their sensory, skills. Complex
interactions of mixed stimuli and person-chemical interactions well be
operating. It is necessary to get relative response data to specific standard
stimuli from personnel concerned with sensory measurement.
Individuals without prior sensory panel testing experience are sometimes
preferred in research. They do not have prejudices about methods or
responses. All persons require adequate training. Persons vary considerably
in the time required for training before their responses to reference
substances become stabilized. Some persons report reproducible, uniform
threshold values almost immediately. Others gradually improve their sensi-
tivity over a period of training. A confidential record summarizing such
personal facts as age, physiocardiac and allergy history, smoking habits, and
calibration test results has been found to be helpful in long-range studies.
Individual results or comparative performance data among panelists should
not be discussed; comparison tends to discourage less-sensitive persons,
instills a false competitive undertone to panel testing, and may bias
subjective testing results.
Good morale and motivation must be maintained. One method which has
been successful is an informal newsletter. Newsletters summarize the ob-
jectives and overall results and describe how the results fit into the scheme of
water quality control. This has been very effective. Panelists have volun-
teered comments and useful suggestions, and there has been no difficulty in
keeping them interested. Temporary physical discomfort caused by allergies,
colds, etc., will affect sensory response. Panelists should be excused during
these periods. A change in personal habits may permanently affect sensory
acuity. Persons who stop smoking have been found to have increased odor
sensitivity to reference materials. This is quite obvious if calibration records
are maintained, but it is otherwise difficult to discern.
Persons show marked differences in response to various tastes and odors.
These differences cannot be reconciled or estimated by a single reference or
substance. Only long-term experience with several references will permit
reasonable evaluation of individual acuity. The differences between indi-
viduals must also be considered. The ultimate purpose of the sensory tests
will determine the panel make up. If only persons with average sensory
responses are used, the results will not be representative of the general
population and may be misleading in water quality control. Persons
representing an extreme of the general population are the ones who most
often register complaints. It may be necessary to use supersensitive persons if
quality control limits are sought. If a general response range is sought, then a
broader-response panel must be used. Obviously, the larger the panel, the
more it is likely to represent the general population.
In some cases, sensory studies are begun with a large number of panelists
and these are gradually reduced in number without any significant loss in
256 MANUAL ON WATER
Testing Laboratory
Measurement of taste and odor should be made in a controlled environ-
ment. Very few laboratories have such facilities, but they are necessary if
reproducible, meaningful results are to be obtained. Background odors
interfere with the ability to distinguish the intensity and character of sensory
response. Excessive heat, humidity, or distracting activity also influence
responses. These extraneous conditions explain the discrepancy of taste and
odor results reported by various laboratories.
An odor-testing laboratory used in research on taste and odor in water
will be described as an example of the considerations involved. The
laboratory is divided into two areas devoted, respectively, to sample
preparation and sensory testing. The areas are separated to prevent bias in
the panelists' judgment which might arise from their observing sample
dilutions being prepared. Guessing tendency is reduced. Samples are passed
between the analysts and the panelists via sheetmetal pass throughs (Fig. 1).
The panel area has separate automatically controlled humidity temperature
'The italic numbers in brackets refer to the list of references appended to this chapter
CHAPTER 12 ON SENSORY EXAMJNATION OF WATER 257
units. Safelights which may be fitted with various monochromatic filters are
provided over each booth (Fig. 2). This is important if the samples being
tested are colored. Color bias is eliminated by selecting a filter that will mask
the color. This prevents the panelists from estimating the sample concentra-
tion or differentiating the sample from odor-free blanks by color intensity.
The atmosphere is kept odor-free by activated-carbon filters on the exit
ducts of the dehumidifier and air conditioner and a separate wall-hung
carbon filter. Normally ambient conditons are 21° C (70° ± 2°F) and 40 to 45
percent relative humidity. Panelists making odor measurements in the
laboratory are shown in Fig. 3.
The sample preparation area contains a water bath for sample tempera-
ture adjustment. The bath, controlled at 40° ± 1°C, is kept in a hood to
minimize odor or water volatility in the working area. Great care is taken to
see that these areas are kept clean and odor-free. All primary dilutions of
odorants are made in another laboratory. No odorous materials are stored,
and both smoking and eating are prohibited in this area. Glassware for the
sensory tests is not used for any other purpose. It is thoroughly cleaned in
chromic acid and detergent with numerous tap and odor-free reagent water
rinses after each use. Reagent or dilution water is prepared by first distilling
tap water, then passing the distillate through fresh columns of activated
carbon. The carbon is changes regularly, and reagent water is always freshly
prepared prior to use. Odor tests are made with 500-ml wide-mouth
258 MANUAL ON WATER
Erlenmeyer flasks covered with watch glasses. These flasks were chosen
rather than the often-used, ground-glass-stoppered flasks because the latter
are difficult to free from trace odors and they do not provide as large an
opening for the nose during odor testing. Details of construction and
operating practices and precautions are given in the original reference [2],
Mathematical Evaluation
Statistical methods of testing are important in evaluating sensory testing
information. They provide a basis for experimental design and facilitate
interpretation of findings.
Analysis-of-variance procedures are generally used to test for the signifi-
cant elements contributing to experimental results. This technique is ex-
cellent if the basis and limitations are recognized. It assumes that the variate
(results) is normally (Gaussian) and continuously distributed. In odor
testing, the results are based on stepwise dilutions in discrete intervals, hence
the continuity assumption is not strictly valid. But if the dilution intervals
are not greater than that corresponding to the accuracy of the tests plus the
variations in personal response, this deviation is not too important. There
are other important assumptions in analysis-of-variance tests. Whether these
assumptions preclude valid use of the technique for data interpretation
depends on the intent. If the interest is only in evaluation of data on hand,
these assumptions are of no concern. But if statistical inferences are to be
drawn from the data and the findings are to be extended to other
applications, the limiting assumptions apply.
Certain limitations in subjective testing might occur in the scoring
systems, the time of judging, the analytical systems, etc. These invalidate
conventional analysis of variance. The limitations dictate the use of larger
samples and nonparametric techniques for evaluation of the results. The
results of organoleptic testing may be classified in two forms, (1) quantal
responses and (2) scalar responses, which represent continuous distributions.
Quantal responses are those in which the criterion is acceptability and the
answer is yes or no. There is no intermediate value or extension. Quality
characteristic ratings, on the other hand, can often be described by
continuous scales in which intermediate values are possible. Quantal or
preference ratings are used to select materials or characteristics that deviate
slightly from small sample lots. A good example would be the tests for odor
preference of several substances by the use of the method of ranked pairs.
Each substance is given a preference rating against every other substance.
The ratings are ranked and the ranks analyzed by a procedure based upon
maximum-likelihood statistics.
Many subjective qualities are measured by a system of ranking. Thus an
array of samples is arranged by the tester in ascending (or descending) order
for such things as intensity of taste or odor. Scoring is a similar procedure
except that samples are assigned some value from a prearranged scale. These
260 MANUAL ON WATER
scoring methods depend upon familiarity of the testers with the samples. The
smaller the differences between samples, the greater the panelists' training
must be to denote these differences and the greater the chance of low
precision. Ranking methods are fast and allow many samples to be tested in
a reasonable time.
The number of steps or grades in the scoring scale to be used must be
developed from experience and the precision of the test. Five- to ten-point
scales are usually used in sensory testing although fewer and more steps have
been used. The common 0 to 5 scale denotes "no odor" to "intense or
objectionable odor" for the respective extremes. At times, several qualities
may be rated and multiple scoring systems may be assigned. The food
industry uses such systems routinely. It is necessary that those conducting
the test indoctrinate the testers thoroughly, select a useful scale, make trial
runs, and refrain from implying a degree of accuracy or acceptability not
inherent in the system.
Rating scale results are incorporated in standard experimental, statistical
designs. The number of tests is determined by the number of samples, panel
size, and consideration of the type of error (I or II). Type I error rejects the
null hypothesis when it is true. Type II error accepts the null hypothesis
when in fact it is false. The null hypothesis is the basis of the test. Detailed
mathematical explanations are available [3]. Commonly, scoring scales are
prepared in which the panelists rate the acceptability on some prescribed
scale such as 1 for extremely poor to 9 for excellent.
Odor references may be rated by various scales. Sometimes, quality
characteristics are described as acrid, sour, sweet, etc., and in other cases
these are translated into a numerical or weighted value. It has been
recognized that the odor type is important in considering both odor
classification and odor threshold. Condequently, the "hedonic index" has
been recommended for mitigating the differences between these two systems.
Briefly, the geometric value of odor threshold is assigned to one scale and a
numerical value of the quality (characterization) to another scale. The
product of these has been suggested as an index (hedonic) for rating odor in
water. Although this is a gross simplification, it denotes the nature of the
problem and an attempt to facilitate communication between investigators
in the water field. An acceptable system would allow everyone to evaluate
odor values with the same degree of objectiveness.
The hedonic index [4] operates on the assumption of a continuum of
physiological preference and a superimposed scale of successive categories of
response (like and dislike). In characterization testing, it is desired to record
the "first impression," not a reasoned, intellectual rating. The hedonic scale
is a simple system which testers readily understand, but it is liable to bias and
suffers from any limitations of the test subjects and limited test conditions. It
is necessary that the proper statistical design and method of evaluation be
employed. Limitations are caused by interactions such as those between
persons and odor types. Another objection is the fact that strong odor types
often predominate over weak odor types.
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 261
If subjective test values are to be useful, they must account for possible
fractionation. In water work, it could mean that a given sample location, say
on a stream, could yield odor values which are not representative of any
other locations, even those nearby, because the odor components weather or
decompose. The hedonic index will require modification, or some new scale
will have to be developed to meet the needs of water investigators. Complex
odors are best studied by profile methods. It has been noted that, as a
complex odor sample is diluted with reagent water, different odors are
detected than the one associated with the original sample. Instrumental
methods supporting the odor test are the best means of studying the nature
of the components of the odor mixture.
Odor-profile evaluation promises to be an acceptable means of evaluating
odor changes along a waterstream containing multiple municipal and
industrial effluents.
A number of methods for conducting and evaluating subjective testing
have been developed. The proper choice depends on the complexity of the
tests, the discriminatory power desired, and economics. It should be
emphasized that the proper statistical design of experiments must be made
before tests are begun. It is usually too late to rectify a poorly planned
experiment after the data are obtained. There is an ever present need to
balance practical or applied efficiency against statistical efficiency. Little
purpose is served if complex statistical forms are used when the problem
does not merit such sophistication.
Probably two testing procedures are best known and most used: the
triangular and the paired comparison tests. The triangular test is made by
presenting three coded samples to the tester. One differs from the other two
and the tester must distinguish the different flask. The testing procedure is
one of the best available if subtle differences exist between samples. Such
differences are involved at threshold dilutions of odorous waters. The
ranking tests described elsewhere are preferred when large differences exist.
In paired testing, the unknown sample is presented to the tester who matches
the unknown with one of a series of randomized dulutions of a known
substance or mixture. An estimation of the unknown is derived from the
over-all results.
Other techniques are available for specific purposes. These include paired
comparisons and duo-trio methods. The duo-trio is a paired test with the
standard also presented to the tester but in a manner differing from the
triangle test. First a paired sample is identified and given to the tester and
later two unknowns in random order. The tester must pick the different
sample. Although the samples are tested against the standard, the prob-
ability is 0.5 rather than 0.33 as in the triangle test.
Series tests are often used in water treating plants. A series of dilutions is
prepared and testers select one or more odorous samples from the array. If
odor thresholds are to be measured, care must be exercised to avoid having
panelists first exposed to suprathreshold concentrations.
In its simplest form, the Weber-Fichner law defining response to sensory
262 MANUAL ON WATER
Organic Chemicals
Organic substances are the chief source of taste and odor. They are
contributed to waters by industrial and municipal wastes, agricultural
activities, decay of vegetation, algae-actinomycete reproduction, and other
natural man-made processes. Floods loosen decaying vegetation and cause
sudden increases in lignin and tannin concentrations. These substances
impart color; a few operators have been able to correlate color and quality.
The organic materials rarely occur as single components. Usually a number
are present simultaneously and their combined sensory effect may be quite
unlike that of any of the original materials. Research has generated many
synthetic organic chemicals that are not readily biodegradable. If these
persistent or refractory substances also cause taste and odor, then special
treatment procedures are dictated. Often the sensory effect attributed to
specific organics is caused by other substances.
There have been many reports of the sensory effect of common detergents.
Investigation showed no sensory effect at levels of detergent considerably
greater than those found in most waters (maximum 10 mg/litre). Taste
thresholds of 50 mg/litre were found, but even higher levels were necessary
for detection of odor. Usually perfumes in packaged detergent products are
detected rather than the detergent itself. The presence of detergent, especially
in potable supplies from wells, is considered an indicator of pollution. Often
it is detected through foaming before infiltration of other products is noted.
Hard detergents are essentially not biodegradable, and activated carbon
treatment for sensory quality control is not usually effective except at very
high carbon dosages. Adsorption on carbon is enhanced below pH 9.
Chlorination may lead to odorous chloroproducts. Introduction of soft or
biodegradable detergents has decreased the possibility of long-term persis-
tance of these substances. However, their presence is usually the first
indicator of contamination.
Regardless of the source of organic material, water treatment personnel
should monitor its presence on a regular basis. Analyses made during taste
and odor problems are not too informative unless a base line has been
established during trouble-free periods.
Organic chemicals can cause a bad taste in fish and other aquatic foods.
The chemicals become concentrated in the flesh.
Although there have been many attempts to correlate taste and odor with
specific chemical properties, no completely successful scheme has been
developed. As new analytical devices of greater sensitivity are evolved, each
in turn has hopefully been assigned to correlation of sensory properties with
chemical structure. Claims for instrumental-sensory correlation have never
been universal and are usually restricted to a minor group of substances.
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 263
Inorganic Chemicals
Inorganic chemicals are less often associated with taste and odor in water
than are organic substances. They impart tastes rather than odors. Sulfides
are one of the most troublesome inorganic chemicals. The major water
supply in Florida, the Ocala limestone formation, contains concentrations of
1.0 to 4.0 mg/litre of dissolved sulfides (measured as hydrogen sulfide). The
odor persists because the water pH ranges from 7.2 to 7.8. Adjustment of pH
to 9.0 or higher removes odor and improves taste. The hydrogen sulfide
remains in the water as long as dissolved sulfides are present. Aeration,
chlorination, and ion exchange are all used in treating these waters.
Inorganic chemicals play an indirect role in biologically produced taste
and odors in water. Nitrogen and phosphorus compounds from agricultural
runoff and packaged detergents, for example, provide important biological
264 MANUAL ON WATER
nutrients. These stimulate algal and biological growth and may not, only
make water unpalatable but limit its use in domestic and industrial
operations.
Dissolved salts are a factor in water quality. The saline water desalting
research program is the major hope for many nations without suitable water
supplies. Inland chloride problems may be caused by discharge of industrial
wastes or deep-well brines. These obvious pollutants are usually controlled
before they reach taste threshold concentrations. Fluorides in the con-
centration used in water treatment are not usually considered a factor in
sensory quality.
Biological
Microscopic flora and fauna flourish or perish as a function of their
aqueous environment. Environmental factors include temperature, pH,
chemical composition, sunlight incidence, and dissolved oxygen level,
among others. Food and elemental nutrient requirements depend on the
specific organism. These microorganisms frequently consume complex
organic matter and produce intermediate substances as a consequence of
their metabolic processes. The metabolic intermediates and final products
may cause taste and odor problems. Algae, actinomycetes, protozoa,
rotifers, copepods, sulfur and iron bacteria, and Crustacea are among the
most important microorganisms. Biological action, both anaerobic and
aerobic, destroys or modifies odorous compounds. But odorous by-products
may form from materials that have little or no odor and these can modify the
character and intensity of specific odorants.
Biological self-purification of streams is an important factor in neutral-
izing man-made wastes. This self-purification capacity is an economically
significant phenomenon. It should not be exceeded, however, and it should
be equitably apportioned among municipalities and industry.
Taste and odor components of biological origin are very likely to appear
with seasonal frequency. Flushouts after low-flow periods of high biological
activity are a common difficulty. Where rivers freeze, anaerobic bottom
deposits are swept downstream during spring thaws. Thermal shocks that
destroy the natural stream biota can also induce tastes and odors. Decay of
vegetation is the leading cause of taste and odor in Western and South-
western states where high solar intensity acts upon shallow supplies. As
carbonaceous matter is metabolized, the concentration of by-product carbon
dioxide is increased; this in turn stimulates biological growth.
Algae are the most troublesome microorganisms, as far as tastes and
odors are concerned. If they do not cause the problem directly, they provide
food for other organisms which produce odorous metabolic products.
Decomposing algae release nonvolatile essential oils that are taste and odor
factors [7, 8]. Organic sulfur compounds have been identified as products of
bacterial decomposition of algae. Water use contributes fertilizing materials
for these organisms. Phosphate particularly promotes proliferation of algae.
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 265
Frequently, taste and odor problems occur long after algae blooms have
passed their peak; actinomycetes feeding on the algae are reported to be the
cause. This is confirmed by the observation that various waters containing
unlike algae populations will have similar odors after a period of heavy
growth. Pure algae cultures have been developed which yield earthy, grassy,
and fruity odors [P-77].
To minimize algae- and protozoa-created taste and odors, new reservoirs
should have the topsoil stripped and surrounding vegetation cut back.
Furthermore, domestic and industrial wastes which contribute nutrients
should be kept out of reservoirs. Since algae blooms occur at predictable
intervals, preventive measures are possible, for example, by treating in-
cipient blooms with an algicide.
Actinomycetes are organisms closely related to both bacteria and fungi.
They are colonial in behavior and are usually associated with soils, although
an aquatic group is a significant source of taste and odor in water. They
impart an earthy, musty, or woody odor to water and to fish flesh. An
earthy-smelling compound, geosmin [12-14], and related chemical com-
pounds have been isolated from actinomycetes. Mucidone, a chemically
different compound that produces a musty odor, has been isolated from
natural waters [75].
Quite often, tastes and odors have been attributed to algae when the real
cause was actinomycetes [76], These organisms grow in mud or silt,
especially if organic matter and nutrients are plentiful. They are quite
temperature-sensitive; 15°C represents a minimum for spore germination
and vegetative growth. Rising temperature increases growth, with no
apparent inhibition up to 38° C. They will grow in the dark in the laboratory,
but shallow waters up to depths of 28 cm (11 in.) enhance growth. Deep
bodies of water tend to discourage growth. Complex organic substances
(such as proteins) in water provide nutrients. Shallow-water reservoirs with
luxurious growths of grasses and rushes will harbor high concentrations of
actinomycetes in warm weather. Algae (planktonic and attached) serve the
same nutrient purpose. The degree of alkalinity affects growth; the greater
the alkalinity, the more favorable the environment. Growth is poor under
acidic conditions.
The metabolic by-products of actinomycetes, such as aromatic amines,
ketones, aldehydes, saturated fatty acids, and unsaturated aromatics have
been found to cause taste and odor in water. Minimum concentration in raw
water appears to be about 0.2 mg/litre actinomycetes. Isoamyl and isobutyl
amines, fatty acids, and unsaturated aromatics have been identified as
significant odorous metabolic by-products.
Streptomyces spores are very small and pass through common bacterial
filters. Sand filters in water-treating plants are therefore not effective in
removing them. Spores passing the filters can become attached to mineral
deposits in water distribution mains. There they can grow and impart taste
and odor not found in the water leaving the treatment plant.
Time or duration of odor production depends on temperature and source
266 MANUAL ON WATER
of nutrition. The first odor is usually fishy and runs two to ten days. The
next phase depends on the nutrient supply. If the primary stages of the
actinomycete growth have exhausted the nutrient, small sex cells are formed
as a zygote or seed. This ends the odor conditions. When sufficient nutrient
remains, the primary stage forms a motile zygote which develops into a large
secondary filament. These rapidly growing secondary filaments contribute a
grassy taste and odor to raw water which lasts two to ten days and then
changes to a pungent marshy odor. This odor may also last two to ten days,
and, if enough nutrient is available, will alter to a potato-bin or slightly
musty odor. If the nutrient is exhausted at any time, the odors soon cease.
This sequential development provides a clue to the occurence of recognizable
types of odor. It should serve as a guide to the waterworks operator to assure
action in the early stages of actinomycete activity.
Copper sulfate treatment of water for algae control is a preventive
measure widely used. Use of copper sulfate or copper citrate and other
chemicals for weed or algae control may upset the natural biological
balance. Cumulative build up of these compounds in fish caught for human
consumption poses questions about toxicological or palatability factors. If
copper sulfate levels are high, fish are eventually killed, thus creating further
biological imbalance which may result in increased growth and incidence of
algae.
Control of actinomycetes in reservoirs has not been successful. Various
chemicals have been tried with incomplete control and unfavorable eco-
nomics. It remains necessary to treat actinomycetes at the water plant,
because inflow of sewage and vegetal matter induces prolific growth in
reservoirs. The resulting odors have been a major problem in certain areas,
such as the Southwestern part of the United States, during the period April
to November, when temperature and light are conducive to actinomycete
propagation.
The taste and odor remaining in water is a function of the treatment
employed. Where actinomycetes are present, addition of as much as 10
mg/litre of chlorine may be necessary to reach the breakpoint. Threshold
odors rise with additions of chlorine until a free available chlorine residual is
present. The chloro-derivatives are especially odorous and not amenable to
complete oxidation even when a residual chlorine content is present. Large
additions of activated carbon will minimize odor but may not remove all of
it. The point of addition of the activated carbon is important. If chlorine or
chlorine dioxide are used, they will be preferentially absorbed by the
activated carbon. The carbon should therefore be added after these agents
have had enough time to become effective.
Taste
"Taste and odor" are used jointly in the vernacular of water technology.
Most of the reported studies concerning the taste and odor problem actually
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 267
emphasize or deal exclusively with odor. This arises from the inability to
separate the two sensations because taste is usually masked by olfactory
sensations. In some cases, taste tests are more sensitive than odor tests, but
very little has been published on taste alone. Four basic tastes are recog-
nized: salty, sweet, sour, and bitter. Variations of these are caused by
olfactory influences. Taste results from the presence of a substance in an
aqueous layer on the tongue, causing excitation of the receptor cells. As in
olfaction, different cells respond to different basic tastes. Taste is an overall
summation of these individual responses. Adaptation to taste, as in the case
of odor, occurs because the frequency of nerve impulses decreases under the
action of a steady stimulus. Taste sensitivity changes with age, as does the
spatial arrangement of the taste buds.
The same basic testing considerations important in odor testing apply to
taste testing. Background odors, temperature, and humidity should be
regulated; color bias should be recognized and controlled if necessary; and
the equipment used in the test should be free of foreign tastes. The taste test is
made by having the panelist(s) rinse the mouth with taste- and odor-free
water, expectorate the rinse, and repeat the procedure with the substance
being tested. The rinse water should not only be free of background taste but
be at sample temperature. Sample sizes should be reasonable, neither too
large nor too small. The sample size is controlled in some degree by the basic
taste. Sweet tastes usually require somewhat larger samples than bitter
tastes, because the latter cause sensation somewhat more rapidly. Usually,
taste testers make several tests per session without loss of precision, although
this has to be established in each situation. Threshold measurements are
based on the premise that concentrations in excess of these values are
unacceptable. This is true for odor but does not apply to mineral-induced
taste. Consumers prefer slightly mineralized water to distilled water. Con-
sequently, psychological scaling methods have been suggested as alternatives
to taste threshold measurements for establishing limiting standards for
mineralization.
An important consideration in taste testing is the possible hazard from
toxic substances. These may be the sensory factors in the water or the
reagents used in preparing the sample. Samples of water having residual
chlorine require dechlorination if the presence of organic tastes is to be
discerned. The dechlorination reagent of choice is sodium thiosulfate.
Sodium arsenite is often used in odor testing but should not be used in taste
testing because of the toxicological hazard.
Odor Terminology
The two most common descriptions of an odor are its intensity and its
characterization. Intensity is a measure of relative strength. Characterization
is the description of how it smells. For example, sweet and pungent are two
common characteristics. The threshold odor is the concentration of an odor
268 MANUAL ON WATER
TON = 2°"
There is another significance to the OH values. It has been shown [7] that
one OH value represents the order of reproducibility of the threshold odor
determination.
Odor Parameters
Any study of odor in water requires a reproducible method of test.
Extensive research [7] led to the development of a standard procedure,
ASTM Test for Odor in Industrial Water and Industrial Waste Water (D
1292) [77]. This procedure uses a three-flask array in panel testing. Two
flasks contain odor-free blanks and the third may be either a sample dilution
or a third blank. The test samples are prepared so that concentrations are
gradually increased from subthreshold level. Exposure to suprathreshold
concentrations usually interferes with subsequent threshold odor measure-
ment.
Reproducibility with several odorants has been found to be of the order of
approximately one-fold dilution or one OH unit. This means that dividing a
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 269
given odor sample in half by odor-free water in each step of the dilution
sequence is approximately equal to the accuracy of the panelists. Dilutions
of less than 50 percent are often used, but this is unjustified. The natural
variability for any person from day to day or even within a day may well
exceed this implied accuracy even under ideal environmental conditions.
Very important effects for person-chemical interaction have been demon-
strated. In other words, the kind of odorant and the choice of panelist are
highly interdependent with regard to the threshold odor result. This should
not be surprising. People vary in their ability to detect a given odor and they
also vary in their relative sensitivity to various odors. This contributes to the
range of personal preferences for many products from perfume to water. In
these studies, a variety of odor testing procedures was evaluated. It was
found that the environmental conditions were more important than the test
method if similar precautions were used.
The literature contains references to threshold odor tests made at a variety
of temperatures. Many plants use 60° C because this corresponds to hot-
water service in domestic applications. Others use lower temperatures,
particularly 40° C, which approximates body temperature. Statistical evalua-
tion of odor tests at 21°C, 40° C, and 60° C showed that (1) odor response
varied by 4 Oil values (16-fold change of concentration) between the least
and most sensitive person, and (2) between 21° and 60° C there was an
increase in overall sensitivity by the panel, corresponding to a decrease in
odorant concentration equivalent to 1.4 OH units. Although higher tempera-
tures do improve odorant volatility, there are other considerations. Panelists
preferred 40° C. They complained of losing initial odor sensations on second
inhalation and of steaming at 60° C. At 21°C, room temperature, they
regarded the odor sensation as being dead. The 40° C temperature has been
incorporated as a standard condition by ASTM. These tests also demon-
strated that person-chemical interaction and the overall variability of the test
procedure were approximately one Oil value.
Background odor may interfere with olfactory response. There has been
little published evidence to support this somewhat obvious generalization.
Food and beverage laboratories recognize this fact and do provide odor-free
atmospheres in their sensory testing laboratories. Few water laboratories
have such facilities. As part of the foregoing investigation, the background
odor effect was established for the standard odorants w-butanal and m-
cresol. Measurement of the threshold odor of each was made with the same
odor and with the differing odor in the atmosphere. The results showed that
there is a marked effect. The olfactory system is confused. If m-cresol was
the background odor, then detection of n-butanol in the threshold test was
enhanced but detection of m-cresol was hindered. Similarly, a background
of n-butanol suppressed detection of n-butanol and enhanced detection of
m-cresol in the threshold test. The only possible recommendation is that
background odor must be eliminated during odor testing.
270 MANUAL ON WATER
Odor Mixtures
Reports describing odors in water are often conflicting. This may be
because the complex effects of mixtures of odors are not usually recognized
in the water pollution field. Rarely are odors in natural or industrial waste
water the result of only one substance; more often they are a composite of a
number of odorants. When individual odorants mix, the result may be one
of additivity, synergism, or antagonism. If the substances combine to give an
odor intensity equivalent to the contribution of the individual odors, this is
additivity. For example, a mixture Of one part A and one part B of equal
odor intensity combine to produce an intensity equal to either 2A or 2B.
Synergism takes place when the combined odor intensity of the mixture is
greater than would be expected by simple addition of these separate
intensities. This occurs if A plus B produce an odor greater than 2A or 2B.
Similarly, antagonism is the suppression of combined odor effects so that A
plus B produces less odor than simple addition.
As if the odor mixture effect were not complicated enough, it is necessary
to consider that measurement involves persons of varying olfactory ability.
The previously cited examination of procedures and environmental factors
showed that there are significant person-to-person differences and person-
to-chemical interactions. The interaction refers to the varying sensitivity of a
given person to different kinds of odors. The effect of mixtures of odorants
in aqueous solution was studied. To do this, statistically-designed experi-
ments were devised so that the effects of person-to-person differences and of
person-to-chemical interactions could be isolated from the effect of odor
mixtures. Theoretical models were developed which were based on the
concepts of additivity, synergism, and antagonism [18]. These mathematical
models were developed for binary and for complex higher-ordered mixtures.
Several methods of data analysis were employed to eliminate any bias
possible from the choice of experimental procedure. Eight odorants of
differing sensory, physical, and chemical properties were selected: m-cresol
(phenolic); «-butyl mercaptan (sulfide); pyridine (amine); acrylonitrile (un-
satrated); n-amyl acetate (ester); n-butanol (alcohol); 2-4 dichlorophenol
(chlorinated phenol); and acetophenone (ketone). These were studied as
binary mixtures and as a blend of all eight. For the binary mixture study,
solutions were prepared of two components where one was 0, 25, 50, 75, or
100 percent of the total. Threshold odor measurements were made by
panelists using the ASTM Method D 1292 at 40° C. Synergism or antag-
onism of olfaction was the rule rather than the exception. It was also an
excellent demonstration of the importance of precise dilution preparation in
sensory testing. Often, very minor changes in relative concentration of one
component may change the resulting sensory response greatly.
An olfactory test of a complex mixture of eight odorants showed that
most of the 14 panelists either detected odor in the basic mix (containing !/g
threshold concentration of each of the eight odorants) or required further
CHAPTER 12. ON SENSORY EXAMINATION OF WATER 271
Threshold Odors
It is very difficult to find information on the threshold odor concentration
of chemicals in aqueous solution. Available data are questionable because of
the lack of environmental and procedural control. A summary of threshold
odor values obtained by ASTM Method D 1292 at 40° C for various
chemicals is given in Table 1.
The wide range of odor threshold concentrations has practical signifi-
cance. This range, particularly at the lower end, is of more importance than
the average value. This is the segment of population most apt to recognize
impaired water quality and register complaints. For example, the average
phenol threshold is at 6 mg/ litre, but the most sensitive testers could
distinguish 17 /ug/litre. The lease sensitive testers required 17 mg/litre, a
thousand-fold difference! These are interesting values because the U. S.
Public Health Service Drinking Water Standards [5] specify a limit of 1
/zg/litre phenol. This limit, which is below the 17 /ug/ litre lower limit found
in these tests, is based on taste and odor induced by chlorination. Chlorina-
tion of phenolics may greatly alter and intensify the odor of the parent
substance.
Chlorination
Chlorination destroys bacteria and organisms such as algae, and directly
or indirectly destroys tastes and odors. There are situations, however, when
chloro derivatives are more obnoxious as taste compounds than the original
chemical. Chloro derivatives are handled by a variety of methods. For
example, addition of ammonia prior to chlorination often prevents forma-
tion of chlorine-reaction products. Ammonia-chlorine treatment prevents
creation of odors by chlorination but in itself does not remove odors.
The chlorine requirement of waters varies as a function of the complexity
272 MANUAL ON WATER
Activated Carbon
The use of activated carbon for adsorption of taste and odors from
organic chemical contaminants is common. The dosage required is not
predictable from simple measurement of odor intensity or characterization
274 MANUAL ON WATER
Instrumental-Sensory Correlation
Recent developments in analytical instrumentation have expanded the
potential for instrumental-sensory correlation. Despite these advances, the
human nose is still a more sensitive detector of many organic materials than
the best man-made detectors. Particularly promising are the ionizatitm
detectors used with gas-liquid chromatography. The flame-ionization and
electron-capture detectors have been used to detect nanogram and picogram
concentrations of organic elements of complex tastes and odors. The
chromatographic and various infrared and other spectrograph techniques
may provide a key to greater understanding of sensory properties. Of
immediate practical use is the possibility of monitoring selected waste waters
or raw waters for specific organics known to be associated with taste and
odor in water problems. The early-warning feature of such a monitoring
program would be helpful to many industrial waste water and domestic
water treatment plant operators.
Correlations of instrumental and sensory responses have been made, but
the results are meager [22]. Typical are the characterizations of specific gas-
liquid chromatographic peaks separated from actinomycete cultures as
CHAPTER 12 ON SENSORY EXAMINATION OF WATER 275
References
[7] Baker, R. A., Journal, Water Pollution Control Federation, JWPCA, Vol. 34, 1962, pp.
582-591.
[2] Baker, R. A., Water Pollution Control Federation, JWPFA, Vol. 35, No. 11, 1963, pp.
1396-1402.
[3] Anderson, R. L. and Bancroft, T. A., Statistical Theory in Research, McGraw-Hill, New
York, 1952.
[4] Peryam, D. R. and Pilgrim, F. J., Food Technology, Vol. 11, 1957, pp. 9-14.
[5] U. S. Public Health Service, Drinking Water Standards, PHS Publication No. 956, U. S.
Government Printing Office, Washington, D. C., 1962.
[6] Kinney, J. E., Journal, American Water Works Association, JAWWA, Vol. 52,1960, pp.
505-514.
[7] Silvey, J. K. G., Proceedings, 44th Texas Water Works and Sewage Short School,
PTWOA, Vol. 44, 1961, p. 126.
[8] Henley, D. E., Glaze, W. H., and Silvey, J. K. G., Environmental Science and Tech-
nology Vol. 3, 1969, pp. 268-271.
[9] Jenkins, D., Medskar, L. L., and Thomas, J. F., Environmental Science and Technology
Vol. 1, 1967, pp. 731-735.
[10] Silvey, J. K. G., and Roach, A. W., Journal, American Water Works Association,
JAWWA, Vol. 51, 1959, pp. 20-32.
[77] Roach, A. W. and Silvey J. K. G.; American Microscopical Society, Vol. 77, No. 1,1958,
pp. 36-47.
[72] Medskar, L. L., Jenkins, D., and Thomas, J. F., Environmental Science and Technology,
Vol. 2, 1968, pp. 461-464.
[13] Gerber, N. N., Biotechnology and Bioengineering, Vol. 9, 1967, pp. 321-327.
[14] Rosen, A. A., Safferman, R. S., Mashni, C. I., and Romano, A. H., Applied Micro-
biology, Vol. 16, 1968, pp. 178-179.
[75] Dougherty, J. D. and Morris, R. L., Journal, American Water Works Association,
JAWWA, Vol. 59, 1967, pp. 1320-1326.
[16] Silvey, J. K. G., "Actinomycetes in Water Distribution Systems," University of Illinois
Engineering Experimental Station, Circular 81, 1963.
[77] Annual Book of ASTM Standards, Part 23, 1968.
[18] Baker, R. A., Journal, Water Pollution Control Federation, JWPFA, Vol. 35, 1963, pp.
728-741.
[79] Rosen, A. A., Peter, J. B., and Middleton, F. M., Journal, Water Pollution Control
Federation, JWPFA, Vol. 34, 1962, pp. 7-14.
[20] Rosen, A. A., Skeel, R. T., and Ettinger, M. E.,-Journal, Water Pollution Control
Federation, JWPFA, Vol. 35, 1963, pp. 777-782.
[27] Baker, R. A., Journal, American Water Works Association, JAWWA, Vol. 56, pp. 92-98.
[22] Reviews of Correlations of Objective-Subjective Methods in the Study of Odors and
Taste, ASTM STP 451, American Society for Testing and Materials, 1969.
[23] Silvey, J. K. G., Glaze, W. R., Hendricks, A., Henley, D.. and Matlock, J., Journal,
American Water Works Association, JAWWA, Vol. 60, 1 '68, pp. 440-450.
[24] Baker, R. A. and Jennings, R., "A Case Study of Microorganic Contaminants in River
Water," Industrial Water Engineering, Vol. 7, 1970.
STP442A-EB/Jul. 1978
276
Copyright© 1978 by ASTM International www.astm.org
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 277
Classification of Deposits
Since most of the crystalline water-formed deposits have the same
composition and structure as hydrothermal minerals, it is both helpful and
logical to use the mineral scheme for classification. For diagnostic purposes,
one of the most important types of information is the identification of the
compounds in a deposit according to the mineral species present.
Basic Compounds
Some relatively soluble metallic salts form, with the hydroxide of that
metal, very insoluble basic double salts. These are most often found on
metallic surfaces as corrosion products where water carries a considerable
amount of oxygen. An alkaline condition is not required and the com-
pounds may be formed at pH values below 7.0. Copper can form basic
carbonates, chlorides, and sulfates. Atacamite (aCuQ2-3Cu(OH)2) is
frequently found as a hard, very adherent corrosion deposit in condenser
tubes. Zinc forms a basic carbonate, as 2ZnCO3; 3Zn(OH)2 and a basic
magnesium chloride, MgCl2-5Mg(OH)2-8H2O, may be formed in seawater.
278 MANUAL ON WATER
Carbonates
Carbonates of most of the alkaline earth and heavy metal elements are
insoluble. The respective bicarbonates are much more soluble. However,
heat and an increase of pH value shift the bicarbonate to the normal
carbonate form to produce the respective insoluble compounds. Aragonite
(TCaCOs) and calcite (/SCaCOs) are found in heat exchangers and softener
and boiler sludges. Of the two, calcite is the more stable and is the high-
temperature form. Dolomite (CaCOs. MgCOs) may also be found where the
calcium-magnesium ratio is favorable to its formation. Occasionally, modi-
fied forms of calcium carbonate such as ankerite (CaCO3.(F.e, Mg, Mn)
COs) and gaylussite (CaCO3.Na2CO3.5H2O) precipitate in low-pressure
boilers.
Siderite (FeCOs) may precipitate from waters containing ferrous bi-
carbonate or may form as a corrosion product in condensate containing
carbon dioxide. Normal carbonates of other heavy metals are rarely formed
in industrial water.
Hydrated Oxides
The class of hydrated oxides contains principally the trivalent corrosion
and precipitation products of iron and aluminum. The term "hydrated
oxide" is more one of custom than exactitude. The formula M2Os.H2O is
correct for composition, but MO(OH) is more correct for structure.
The "hydrated oxides" of iron and aluminum are interrelated in that
temperature and time cause the more highly hydrated forms to lose water
and undergo alterations of crystal structure. This relationship is shown in the
following diagram:
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 279
Hydroxides
Simple hydroxides precipitate from solutions of high pH values, or under
special conditions hydrolyze in corrosion reactions. Brucite (Mg(OH)2) is
found in boiler and softener sludges but it can also form in environments of
relatively low pH values such as those found in lower stages of seawater
evaporators. Calcium hydroxide (Ca(OH)2) may scale out in lines carrying
lime slurries or in superheaters and steam lines by thermal hydrolysis of a
previously deposited calcium carbonate.
Ferrous hydroxide (Fe(OH)2) has been identified in corrosion pits, and
nickel hydroxide (Ni(OH)2> in exfoliated flakes from cupro-nickel stage
heaters.
Metals
Free metals in a deposit are usually the end product of a reducing
condition acting on a solution or an oxide of the metal. Dendritic copper is
present in many high-pressure boiler sludges and sedimentary deposits.
Copper lends weight to the mass of sludges, and part of its undesirability is
caused by the settling tendency it provides in areas of low water velocity.
Metallic iron may be found in some corrosion products either as an
inversion product of ferrous oxide at high temperatures or as a result of
isolation by the corrosion of surrounding grains. In the former case, FeaO4 is
also formed as follows:
4FeO — Fe + Fe3O4
Metal Oxides
Metal oxides are invariably the products of corrosion reactions, the
dehydration of hydrated oxides, or the decomposition of carbonates. The
oxides may be loose and porous or compact and adherent according to
conditions of formation. Oxygen for the formation of the oxide can be
provided by dissolved oxygen in the water or by bound oxygen from
molecular H2O. In the latter instance, hydrogen is produced.
Magnetite (FesCh) is formed under the greatest variety of conditions. FeO,
Fe3O4, and FeaOa can all be found in aqueous corrosion products of iron
280 MANUAL ON WATER
according to the amount of oxygen present. Fe3O4 and occasionally FeO are
the products in steam.
The two copper oxides, cuprite (CuzO) and tenorite (CuO), may both be
components of boiler sludge or corrosion films on copper, brass, or bronze.
High oxygen concentration and high pH values are favorable conditions for
theibrmation of tenorite, whereas cuprite is more likely the solid phase of a
lower pH and lower dissolved oxygen concentrations.
Corundum (aAhOa) has been found in high-pressure boilers and turbines
as an alteration of precipitated alumina. Zincite (ZnO) is a hot-water
corrosion product on metallic zinc.
Organic Salts
The mono- and di-hydrates of calcium oxalate (CaCzO^^O and CaCzCV
IH'zb) are practically the only organic salts of sufficient insolubility to be
found in industrial deposits. Certain food liquors containing oxalic acid and
calcium cause severe oxalate scaling in evaporators.
Phosphates
The insoluble phosphates in industrial waters are formed by the reaction
of soluble calcium, magnesium, or iron with a soluble phosphate added as a
form of treatment. Most boilers today are treated to precipitate the calcium
purposely as hydroxyapatite (Caie(OH)2(PO4)6) sludge. Although it is usu-
ally fluid and soft, it can form a compact scale. It may also undergo an
alteration in areas of high heat-exchange rates and highly concentrated
boiler water to form a hard scale, wilkeite (Cai0O[(Si, P, S)O4]6). Sodium
calcium phosphate (NaCaPO*) forms under similar conditions.
Other calcium phosphates, whitlockite (/JCaaPzOs) and dicalcium phos-
phate (CaHPO4), have crystallized out in chemical lines feeding boiler
drums.
Magnesium hydroxyphosphate (MgsPO4 • Mg(OH>2) is a sludge com-
ponent of boiler water having a high phosphate and a low silica concentra-
tion.
A low-temperature ferric phosphate, vivianite, Fe3(PO4)2'8H2O, is
occasionally found in cooling systems. It frequently is mixed with iron
oxides in deposits having a glassy appearance.
Silica
Uncombined silica as quartz or cristobalite forms by the hydrothermal
alteration of solid silicates or by direct crystallization from dissolved silica.
Quartz (SiO2> is one of the hardest of the minerals, but crystal size is small in
water-formed deposits so that the extreme hardness of the natural mineral is
not imparted to the deposit. A unique property of solubility in high-
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 281
Simple Silicates
The silicates of single cationic elements are classified as simple silicates.
The calcium and magnesium silicates have incongruent solubilities and
contain water of hydration when formed hydrothermally. The composition
of the solids is dependent upon temperature and pressure as well as on the
relative concentrations of the dissolved reacting ions.
The hydrous magnesium silicates, serpentine (3MgO-2SiO2'2H2O), talc
(3MgO-4SiO2-H2O), and sepiolite (2MgO • 3SiO2 • 2H2O), are soft, rather
poorly crystallized compounds. Detection by instrumental means is not
always successful. They are more frequently components of soft sludges
rather than hard scales. The formation results from the alteration and
crystallization of an absorption complex of dissolved silica on magnesium
hydroxide. Serpentine forms under the most varied conditions and for this
reason is the most common of the tfiree forms.
The hydrous calcium silicates, gyrolite (2CaO3SiO2-H2O), xonotlite
(5CaO-5SiO2-H2O), and foshagite (5CaO3SiO2-3H2O), like the hydrous
magnesium silicates, crystallize poorly but unlike them may be hard, tough,
and highly insulating. The common form is xonotlite, with gyrolite and
foshagite being somewhat rare.
The anhydrous simple silicates, fayalite (2FeO • SiO2), mullite (3AbOr
2SiO2), olivine (2(Mg, Fe)O-SiO2), and forsterite (2MgO-SiO2), are
commonly high-temperature dehydration products of related hydrous forms.
Willemite (2ZnO • SiO2) is one of the few anhydrous simple silicates formed
hydrothermally.
The sodium silicates, Na2SiO3 and j3Na2Si2O5, are somewhat soluble in
high-temperature steam and therefore are components of turbine blade
deposits. Their water solubility is appreciable, so that they may be removed
by washing the turbine internally with wet steam.
Complex Silicates
Silicate compounds of more than one cationic element are classified as
complex silicates. These hydrothermally formed compounds are often
crystallized from environments of very high heat input and are usually
282 MANUAL ON WATER
Sulfates
Of all the scale formers, calcium sulfate is most readily recognizable
because of the large crystals which are formed. Anhydrite (CaSO4) crystal-
lizes on heat-exchange surfaces in the form of large needle-like crystals
which grow perpendicular to the heat-exchange surface. The individual
crystals can be seen by the naked eye. Hemi-hydrate (CaSCV VSIfcO) and
gypsum (CaSO-rlHhO) are lower-temperature forms of calcium sulfate, the
former more likely to be found on steam generating surfaces and the latter in
nonsteaming exchangers.
Celestite (SrSCX) and barite (BaSO4) are highly insoluble but rather rare
because of the infrequency of strontium and barium in industrial water.
All sulfate scales are difficult to remove as they do not respond to acid
cleaning.
Sodium sulfate occurs in superheater and turbine blade deposits as
thenardite (Na2SO4-V), metathenardite (Na2SO4-I), Na2SO4 III, and burk-
eite (2Na2SO4-Na2CO3).
Sulfldes
Sulfides of metals are quite insoluble but generally do not protect metals
on which they are formed. Sulfides are usually associated with corrosion in
the presence of hydrogen sulfide or with a reducing reaction on a sulfate.
Cuprous heat-exchanger tubing may contain chalcocite (Cu2S) or covellite
(CuS).
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 283
Sampling of Deposits
Deposits are sampled at least twice before being submitted to chemical or
physical tests. The field man first collects the gross sample from its point of
formation, and the technician then prepares this sample for final examina-
tion. Deposits are not homogeneous but may differ in composition from one
part of a system to another. It is therefore important that the field samples be
taken from the point of occurrence without physical or chemical alteration.
Thin Films
Some deposits, particularly on rough or irregular surfaces, may be so thin
that scraping does not remove much of the material. If the deposit is not too
hard, a stiff bristle brush may be much more effective than scraping. If the
deposit is tightly adherent, and the surface is smooth, thermal or mechanical
shock will sometimes loosen it. Thermal shock may produce some alteration
or decomposition of the deposit; note should be made in the information
accompanying the sample when this method has been used.
Biological Slimes
It is frequently impossible to identify a biological slime definitely if it is
allowed to become dry before examination. If at all possible, therefore, the
deposit should be kept in its environmental water. In some cases, where gas
formation is active, as with sulfate-reducing bacteria, it may be necessary to
refrigerate the sample during shipment, or to add a bactericide. The latter
procedure of course kills the bacteria; it would make preparation of cultures
impossible. The discretion of the sampler must be relied upon in such
instances.
Selection of Samples
The selection of a sample or samples is usually somewhat limited, but
there are instances where a wide choice is possible. In cases where it is
possible to select the samples of a deposit, such selection is best guided by a
thorough consideration of the problem involved. Very often, the removal of
a number of samples will result in more informative analytical data than
would be obtained from one composite representing the entire mass of
deposit. A typical example is the sampling of deposits from a steam turbine.
Samples from each stage are more desirable than a composite sample from
all stages. Conversely, in the case of a tube failure in a steam generator, if
inspection shows other sections of the boiler to be in satisfactory condition, a
single sample from the affected area should suffice.
Deposits sometimes are encountered in layers. Usually it is possible in
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 285
such cases to select several samples so that the individual layers may be
examined in the laboratory, if desired.
Sample Quantity
The most desirable amount of deposit to be submitted as a sample is not
specific. The quantity of deposit that can be removed is often limited. In such
instances it is better to submit a single mixed sample of half a gram or less
than to collect no sample.
A deposit of 5 g is desirable for an extensive X-ray diffraction study,
although informative data may be obtained with as little as 0.1 g. A routine
chemical analysis usually is possible with a sample of 10 g, but an elaborate
laboratory investigation might require as much as 100 g.
Although there is a difference of opinion about the desired amount of
deposit to be submitted as a sample, it is definitely best to provide
considerably more sample than laboratory examination might require.
Laboratory Sampling
The final sampling is made by selecting a small representative portion
from the gross sample for examination by special instruments. If the sample
is received in contact with its original confining surface, the same pre-
cautions must be taken as described earlier in removing it from that surface.
If it is possible to make a separation of heterogeneous layers, it may be
advisable to do so, and to make separate examinations of these smaller select
'The italic numbers in brackets refer to the list of references appended to this chapter.
286 MANUAL ON WATER
Methods of Identification
The examination of any deposit begins with visual observation and the
recording of the description in terms of size, shape, contour, color, odor,
hardness, and magnetism. The choice of subsequent methods for identifica-
tion is frequently suggested by the visual appearance. In the case of inorganic
deposits, the proper step, after visual examination, is to study them under
magnification. This often reveals characteristics not visible to the unaided
eye. The texture of various layers is more pronounced, and recognition of
individual crystals may be possible.
After crushing or grinding, but before other tests are run, it is desirable to
heat a small amount of the sample gently in a crucible and to note its
behavior. A pronounced darkening of the sample is frequently indicative of
organic matter. The odor as the sample is heated can be used to identify
many types of organic material, such as carbohydrate, protein, amines, oil,
coal, sulfur compounds other than sulfate, and a number of others. The
suspicion of a given type of organic compound from the odor on heating
may be verified by extracting the sample with a suitable solvent, and using
the microscope, X-ray diffraction, or absorption spectroscopy to help
confirm the initial suspicion. Table 1 indicates the various techniques
applicable to the detection and identification of the types of material listed,
and is intended as a reference to the instrumental descriptions that follow.
The identification of water-formed deposits is not a matter of using the
proper single method, but of coordinating a number of methods to make
each supplement the others [2,3]. No single method tells all there is to be
known about a sample. Each has a special field of application with its
inherent advantages and disadvantages. The applications and limitations of
commonly used methods of identification are discussed in the following so
that the proper instrument or combination of instruments may be applied to
the investigation of these deposits.
Biological Microscope
The term "biological microscope" does not refer to a particular type of
microscope but rather to the use to which the microscope is put, namely the
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 287
located at the base of the instrument. The reflected beam is directed upward
through a condenser and through the sample, which has been mounted on a
glass slide and covered with a thin cover glass. The image of the micro-
organisms is magnified as the light continues upward through the lenses
of the objective and the eyepiece. The magnified image is either observed
directly at the eyepiece or photographed with a camera.
The living matter in biological deposits may consist of either single cell or
multicell species performing the functions of growth, reproduction, and
metabolism. Wide variations exist, however, in the conditions under which
these functions are performed. Indeed the environmental conditions are often
quite limited in this respect for any one kind of organism. For maintenance of
life some organisms require iron, some sulfur, some carbon, all with or
without oxygen, and they may be deprived of these essentials by changes in
industrial operations. Thus, in addition to the living organisms, the sample
may contain metabolic by-products and skeletons of dead organisms.
Observations of the material are made by enclosing a small drop of the
sample-bearing liquid between a glass slide and a cover glass. The outlines of
the objects under examination are observed under transmitted light. The
various shapes may be described as similar to rods, filaments, chains, stalks,
and capsules. Figure 3 shows some typical examples of magnified biological
material.
Identification of the specific species is made by recognition of charac-
teristic shapes and colors or by characteristic reaction to reagents. Some
organisms will adsorb specific dyes and be recognizable by this property.
Inorganic oxide sheaths may be dissolved from an organism by acids,
thereby exposing features not recognizable with the sheath in place. If the
sheath is iron oxide, the dissolved iron will color the liquid between the cover
glass and the slide, suggesting an iron bacterium.
Recognition by shape is sometimes difficult and, for confirmatory in-
formation, the organisms may be inoculated into a culture medium. After a
suitable incubation period the medium is tested for specific metabolic by-
products of the organism. For example, the formation of hydrogen sulfide in
a sulfate culture medium is confirmatory evidence of the presence of sulfate-
reducing bacteria.
Not all samples as received in the laboratory are suitable for biological
examination. When the number of organisms is so small that a single drop of
liquid might not contain any observable individuals of a suspected species,
the sample may be centrifuged to concentrate the organisms and the
observation made on the concentrate. On the other hand, samples may
contain so much clay or other suspended matter as to greatly interfere with
the examination. Such samples may be diluted to reduce the concentration
of impurities, or separation of biological from inorganic material must be
made before mounting the sample under the microscope.
The report of a microscopic examination usually indicates only those
recognized microorganisms for which definite proof of presence was estab-
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 289
(a) (No. 10) Cyclops large organism. Also _(<e) Gram positive bacillus,
shows (A) Synedra, (B) Ceratium, and (Q CO Gram positive cocci.
Nastoe. (g) Asterionella.
(b) Crenothrix with ferric oxide sheath in (h) Stephanodiscus.
place. (0 Crenothrix with iron removed and stained
(c) Spirogyra. with methylene blue.
(d) Anabena. (/) Ceratium.
lished. Quantitative values are assigned only when specific cultures can be
made.
A microscope with three objectives ( X 10, X43, and oil-immersion X 97),
two eyepieces ( X5 and X10), and an Abbe condenser can be purchased for
about $400. A more adequate assembly, including an illuminator and a
mechanical stage, can be bought for about $700.
The ASTM Test for Iron Bacteria in Industrial Water and Water-Formed
Deposits (Method D 932) [7]; ASTM Tests for Sulfate-Reducing Bacteria in
Industrial Water and Water-Formed Deposits (Method D 993) [7]; and
ASTM Identification of Types of Microorganisms and Microscopic Matter
in Industrial Water and Industrial Waste Water (Method D 1128) [7] provide
for identification of some bacteria and other microorganisms of industrial
importance. There are other sources \4-6\ of detailed information on the use
of the biological microscope.
(a) Striated calcium sulfate scale. (d) Calcium sulfate lienic hydrate deposits.
(b) Ferric oxide scale. (e) Magnetite scale.
(c) Magnesium phosphate scale.
FIG. 4—Typical water-formed deposits.
Many of the epoxy resins, especially those of low viscosity, are also excellent
impregnating materials. Many crystal phases can be recognized by their
shape and brightness under reflected light, even though direct observation of
optical properties cannot be made.
In some cases, it is possible to make thin sections of a scale, so that the
structure may be examined by transmitted light under the microscope.
Observation of birefringence and crystal orientation may suggest the
compounds present in such a scale. Most boiler scales and sludges are not
sufficiently coherent, however, nor do they consist of sufficiently large
crystals for such techniques to be fruitful.
A crushed sample, preferably 100-mesh or finer, is suitable for two types
of microscopic examination. Many crystals and compounds in deposits from
water can be identified and their amounts estimated by examination of the
powder under a chemical microscope equipped with polarized light, or with
a petrographic microscope. Identification is accomplished by immersion of
the powder in oils of various refractive indexes; determination of the indexes
of the crystalline compounds is made by observing their relief against the oil
of known refractive index.
Refractive indexes are determined by crushing the sample to a size which
will free from the agglomerate as many single crystals as possible without at
the same time producing particles too small for clear resolution under the
microscope. Sludge particles are often too small to provide optical data.
Large-size particles are no deterrent because these can be crushed to
sufficiently small size for measurements.
Amorphous material and glasses, as well as crystallized compounds, have
optical characteristics that can be measured and may form a basis for
identification. For examination of this type of material, optical microscopy
is superior to X-ray diffraction.
Chemical microscopy is simply the technique of performing normal
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 293
X-Ray Diffraction
X-ray diffraction produces a pattern of lines on photographic film or
peaks on a recorder chart. The position of the lines on the film or the peaks
on the chart for any given type of X-radiation is determined by the distances
between layers of atoms in the crystalline components of the sample. These
interatomic distances can be calculated from the measured positions of the
lines or peaks, and used to identify the crystalline compounds of a sample.
The essential functioning of the X-ray diffraction unit is illustrated in Fig.
6. X-rays pass through a collimator tube which restricts the beam to a very
thin pencil of parallel rays. The collimating tube may be an integral part of
the camera. The pencil of X-rays is intercepted by the sample located on the
central axis of the camera. A large percentage of the beam penetrates the
sample and is caught and dissipated in the beam trap. A small fraction of the
primary beam is diffracted to the outer circumference of the camera and
strikes the photographic film at definite positions depending upon the angles
of diffraction. The magnitude of these angles of diffraction is determined by
the atomic arrangement within the crystal compound producing the diffrac-
tion. After sufficient exposure, the photographic film is developed and
patterns are produced, those shown in Fig. 7 being typical. These are
compared with patterns or data produced by standard compounds. When
the position and intensity of lines from the pattern of an unknown
compound match those from the pattern of the standard, the unknown
material is identical with that of the standard. Identification therefore
requires a series of standards or a set of authenticated diffraction data. The
best single source of crystal data is the "Card Index File of X-ray Diffraction
Data for Chemical Analysis," available from ASTM. Details of procedure,
with additional literature references, are given in ASTM Identification of
Crystalline Compounds in Water-Formed Deposits by X-Ray Diffraction
(Method D 934) [/].
The X-ray diffraction method of analysis is essentially one of identifica-
tion of crystalline compounds present in a deposit. It is sometimes referred
to as the "powder diffraction method," a name that indicates the most useful
form in which samples are prepared for analysis. Most crystalline, water-
formed deposits do not occur as powders but must be finely ground for
proper mounting and for crystal distribution. Sludges usually are very finely
divided but may cement or harden on drying and may also contain flakes or
larger particles which are truly part of the sample. The only limitations on
the type of sample that can be used for powder diffraction are that it be
crystalline, that it be susceptible to grinding, and that a sufficient amount be
available for manipulation.
Although the X-ray diffraction method is not usually considered to be a
micro-method, with special care an analysis can be made with less than 10
mg of sample. Exposure of a sample to X-rays may require from 1 to 4 h,
and samples subject to change in the atmosphere in that length of time may
be protected by enclosure in an airtight capsule during exposure.
In recent years, direct measurement techniques of X-ray diffraction have
been introduced, employing counter tubes for detection of X-ray intensity.
These instruments have distinct advantages. Ordinarily, they employ a
somewhat larger sample, so that better integration of the overall com-
position of a sample is possible. Further, although only one sample may be
run at a time, the method is considerably faster than photographic methods,
because under most circumstances sufficient of the pattern can be run in a
matter of 30 min to 1 h. For detection of the presence or absence of a certain
phase, it is necessary to scan only over an area where a line unique to the
FIG. 7— Typical X-ray-diffraction patterns.
296 MANUAL ON WATER
slight solid solution. Also, in a camera that will allow reasonable exposure,
the lines on the film are relatively small, and it is not possible to detect very
slight variation in line width.
By scanning over the area of interest at slow speed with the diffractometer,
peaks of sharp lines can be located within 0.01 deg, thus permitting detection
of extremely slight solid solution. Further, by employing narrow slits and
fast time constants in the instrument, it is possible to achieve extremely high
resolution, of an order that would be almost physically impossible on a
photographic film. This allows at least partial separation of diffraction lines
of well-crystallized substances which are so slightly separated that they
might appear as a single line on a film. Of course, if the lines are exactly
superimposed, they cannot be separated even by high-resolution techniques.
There are, however, several distinct advantages to the photographic
method. First, a pattern of high quality can be obtained on a very small
amount of sample, such as 2 or 3 mg. Second, in a sample that gives a very
complex pattern, such as one containing a large number of crystal phases,
certain compounds found in deposits from water are prone to give somewhat
spotty lines if they are not ground sufficiently fine. These spotty lines stand
out quite well on the film, and permit separation of the pattern into two
distinct types of lines, which frequently aids identification. Quartz, calcium
sulfate, calcium carbonate, and analcite are compounds that often develop
rather large crystals and are particularly likely to give spotty lines. The third
advantage for film lies in the ease with which a number of X-ray patterns
may be compared by placing the films edge to edge on a viewing box. This is
done much more easily with films than with charts.
Because of its ability to give useful patterns with samples consisting of
very small crystals or of crystals that are opaque to light, the X-ray method is
generally more widely applicable to deposits than the petrographic micro-
scope. The microscope, however, can give useful information about the state
of aggregation, can detect amorphous materials which contribute little or
nothing to the X-ray pattern, and permits identification of a single crystal on
a whole slide of material, thus providing a sensitivity much greater than that
of the X-ray method, provided the crystal is of sufficient size. Where both
instruments are available, it is generally advisable to run the X-ray diffrac-
tion pattern first, thus giving a good average composition of the sample, and
to use the petrographic microscope to detect glasses and amorphous
materials—those substances present in too small amounts for X-ray de-
tection—and information about the state of agglomeration of the sample.
The report of an X-ray diffraction analysis should give the name and
formula for the crystalline species identified, together with an estimate of the
relative amounts of the identified phases present, and any remarks regarding
crystal size, solid solution, or other pertinent information that may have
been obtained.
The equipment used in the photographic method consists essentially of a
298 MANUAL ON WATER
X-Ray Spectroscopy
Secondary X-rays are generated when X-rays of sufficiently short wave-
length are absorbed by matter. These secondary rays are characteristic of the
elements present in the irradiated material. The X-ray spectrograph is an
instrument for separating the X-radiations from the various elements of the
absorbing material, and for detecting and recording their wavelengths and
relative intensities. The apparatus used for such detection is not greatly
different from the X-ray diffractometer, and most of the components of one
instrument are used for the other.
The chief difference lies in the fact that the sample is the source of the X-
radiation in X-ray spectroscopy, rather than the X-ray tube, as in dif-
fraction. A single crystal, cut parallel to one of the principal planes, takes the
place of the powdered sample in the diffractometer technique, and diffracts
the various wavelengths of X-rays at different angles, thus allowing each
wavelength to be separately detected by the counter tube.
X-ray spectra are very simple, consisting at the most of about 15 lines, not
all of which are of significant intensity. These lines as a group vary in
wavelength in a regular manner with the atomic number of the element.
Complete X-ray spectra are therefore known for all elements. The wave-
lengths have been precisely calculated, and most of them have been very
carefully checked experimentally.
The smaller the atomic number of the element, the longer the wavelength
of the corresponding lines of the X-ray spectra. "L" series spectra are used in
analysis for the heavy elements, that is to say, those heavier than barium,
and the "R" series for the lighter elements. Elements of atomic number
smaller than titanium give rise to radiation of sufficiently long wavelengths
that their absorption in air is too great for good sensitivity. A helium
atmosphere is therefore maintained from the sample, past the analyzing
crystal, to the window of the counter tube. This has allowed detection of
elements as light as sulfur. Softer radiation than this is absorbed strongly in
the window of sealed counter tubes, and counting losses are consequently
high. This has been solved recently by the use of a flow counter tube
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 299
Optical Spectroscopy
Emission spectroscopy is a method of analysis for elements that depends
on the fact that when atoms are excited by either thermal or electrical means,
light is given off as discrate wavelengths as the atoms return to their normal
state. If this light is defined by a slit, separated into its various wavelengths
by a prism or diffraction grating, brought to a focus by a lens system and
viewed with an eyepiece, recorded on film, or measured by photoelectric
means, the elements that have given rise to the spectral lines can be identified
by locating the characteristic wavelengths in published tables of spectra.
The common sources of excitation for spectrographic analysis are flame,
d-c arc, a-c arc, and high-voltage spark. Each has special uses, and the
advantage and limitations of each one will be discussed briefly.
The flame of a Bunsen or Meker burner is at a sufficiently high
temperature to excite the atoms of only the alkali and alkaline earth metals
and a few others, if the concentration is sufficiently high. Propane-air,
propane-oxygen, acetylene-air, oxygen-acetylene, and oxygenhydrogen
flames produce successively higher temperatures. The atoms of about 43
elements can be excited with acetylene-oxygen or hydrogen-oxygen flames.
The sensitivity for many of these elements is not very high. The flame is a
highly reproducible source, however, if fuel and' air or oxygen pressures are
carefully controlled; it is quite satisfactory for the analysis of solutions which
represent ideally homogeneous samples. The flame spectrophotometer is
actually a small direct-reading spectrograph.
The d-c arc, which is operated at a voltage from 50 to about 250, is an
extremely sensitive source because it is capable of producing very high
temperatures. The detection of a number of elements in parts-per-million
concentrations in a solid sample is quite possible with this energy source.
The reproducibility of this source is somewhat limited because of the
tendency of the arc to wander. It is therefore considered highly satisfactory
2
These are registered trademarks of E. I. du Pont de Nemours & Co., Inc., and Shawinigan
Products Corp., respectively.
300 MANUAL ON WATER
for qualitative analysis because of its sensitivity, but it is probably not the
best one for quantitative analysis.
The high-voltage a-c are, using a voltage of 1000 or more, is a steadier and
more reproducible source than the d-c arc and, except for extreme cases, has
adequate sensitivity for most of the elements. The chief drawback to this
source is the dangerously high voltage, which requires safety interlocks and
careful shielding for protection of the operator.
The high-voltage spark is a very reproducible source, using 10 000 to
50 000 V across the two electrodes, and a synchronous interrupterto extinguish
the spark and prevent it from becoming an arc. The discharge is predom-
inantly electrical in nature, rather than thermal, and in many cases it is cool
enough that one can handle the electrodes immediately after exposure. A
condenser and inductor are usually added to this circuit to produce some
heating effect. Although the reproducibility of the discharge is quite high,
because of the low temperature comparatively little material is consumed,
and sampling problems are sometimes major. The spark source, however, is
readily adapted to the analysis of solutions, where a completely homogeneous
sample is possible.
The simplest type of dispersing instrument is the visual spectroscope,
commonly called the Bunsen spectroscope. It consists of a focusing lens, a
slit, a prism, and a telescope on a movable arm for viewing the spectra
produced. In addition, a wavelength scale is usually sent through the prism
from a side tube, and brought to focus in the telescope just above the spectrum
of the sample to be studied. The spectroscope is limited to the elements
that have lines in the visible part of spectrum, and is generally considered
to be a qualitative instrument, although some estimate of amounts can
usually be made. The instrument is simple and it has many potential uses,
but it has the drawback of poor dispersion, which makes it difficult to resolve
some lines that are normally close together. In addition, simultaneous ob-
servation of all parts of the spectrum is not possible.
The spectrograph employs either a prism or a diffraction grating as the
dispersing device and, for general use, photographic film as the recording
medium. For routine production control, where the same elements are
normally being determined, it is entirely practical to replace the photo-
graphic film with a photoelectric device for recording the relative light
intensities of the various elements to be analyzed. Generally, however,
problem in industrial water treatment are sufficiently varied that the direct-
reading spectrograph would be of limited use.
Metals, which conduct electricity, can be used as their own electrodes, but
most of the materials encountered in industrial water treatment are non-
conductors. Therefore, the sample is usually placed in a small core in a
carbon or graphite electrode, which is generally made the lower electrode.
The upper electrode is usually a plain carbon or graphite rod, ground to a
blunt point. The cavity in the lower electrode may be formed with a center
post, to decrease wandering of the arc, and may also be undercut, the
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 301
narrow neck tending to increase the arc temperature by decreasing the con-
duction of heat down the electrode. Metal electrodes are occasionally used
for special cases, but graphite is quite satisfactory for general work.
Very satisfactory electrodes can be made for the a-c arc and high-voltage
spark by thoroughly mixing the powdered sample with graphite, often with
a buffer also, and pressing into a pellet under high pressure. The pellet is
placed in a metal holder, the other electrode being a tipped carbon rod.
This technique is not wholly satisfactory for use with the d-c arc, because
of the high temperature.
Fineness of the powdered sample is important. Since the sample usually
melts in the d-c arc, a 200-mesh sample is adequately fine. For the a-c arc
and high-voltage spark, however, where relatively little material is con-
sumed, the sample should be at least 325-mesh, or should be fused with a
flux to ensure uniformity. Alkali metal borates are satisfactory fluxes for
most samples. Solutions are atomized into the flame or spark. In the latter
case, a rotating graphite disk which dips into a container of the solution
can be used; the spark is generated at the side of the disk opposite the
solution container. One great advantage for the solution method is the
ease with which synthetic standards are prepared, and the simplicity of the
addition of an internal standard to the unknown sample to serve as a
reference. This procedure increases accuracy by allowing the determination
of concentration ratios rather than absolute values of concentration.
ASTM Committee E-2 on Emission Spectroscopy publishes a number of
methods in a single volume for determination of impurities in various
materials. Most of these, however, are not applicable to deposits from water
because of the lack of a uniform matrix. Possible methods have been pub-
lished elsewhere, and are currently being submitted to Committee E-2 for
inclusion in future publications. These so-called "Universal Methods" are
generally of somewhat lower accuracy than those for determining impurities
in rather pure materials, but are of much wider applicability. It seems
probable that many of these will be adaptable for use in deposits from water.
A complete spectroscope, with an adequate d-c arc source and various
accessory materials, can be purchased for slightly under a thousand dollars.
Spectrographic units, which include microphotometers for measuring the
photographic film or plate, start in the neighborhood of $13 500, and may
run as high as $45 000 (with computer interface and cathode ray tube
display, up to $160 000), depending upon the complexity of the equipment
desired.
The microphotometer is actually a dual instrument. It normally consists
of equipment for projecting a reference film, on which the location of the
sensitive lines of the various elements are indicated, beside that of the
unknown spectrum for qualitative analysis. In addition, a densitometer
portion permits determination of the photographic blackness, expressed as
percent transmittance, for any given line. A comparison of photographic
blackness with known samples is used to plot working curves for the
302 MANUAL ON WATER
Electron Microscope
Many particles of sludge, as well as certain corrosion products, are too
finely divided to be studied with an optical microscope. These small par-
ticles can often be profitably studied by electron microscopy. The electron
microscope is similar to the optical microscope in many ways, but the entire
optical path is in high vacuum. Electrons are generated by a hot filament,
and are driven from the filament by a focusing cap at high negative
potential, located immediately behind the filament. The electron beam is
further focused by a series of electrostatic or electromagnetic lenses, corre-
ponding to the condenser in an optical microscope. The crystals, or other
matter making up the sample, absorb electrons according to their thickness
and the absorbing power of the atoms, and the shadow thus formed is
viewed on a fluorescent screen, or photographed. The resolving power of
the electron beam is very high, and magnification of the photographic plate
may be used to bring out more detail.
The sample for examination should be dispersed as much as possible, as
agglomerates of a large number of particles cannot be studied except at
the edges. A thin film of a resin such as Formvar or collodion is perpared
by placing a drop of solution of the resin on water and allowing the solvent
to evaporate. The film is then picked up on a platinum screen, and the
sample deposited on the film and allowed to dry.
A second technique that may be applicable is the replica technique,
normally used to study metal surfaces. In this method, the resin is applied
to the surface to be studied, allowed to dry and then stripped off, usually by
immersion in water. The film retains the contours of the surface to which
it was applied; thus it is thinner where there were elevations and thicker
where there were depressions. The film is removed from the surface of the
water on the platinum screen, as in the foregoing, and viewed with the
microscope. The replica may be shadowed with chromium metal evaporated
on the surface to improve contrast.
Much can be learned about the crystal shapes and the sizes of sludge
particles, the type of material which acts to bind them together, and ten-
dencies to twin, or branch, by study of electron micrographs. Most of these
phenomena occur in crystals that are under 1 Aim in size, and this makes
study with the optical microscope nearly impossible. Because certain unique
properties of a crystalline substance, such as refractive index, cannot be
measured with the electron microscope, this instrument should not be
considered a means of identifying a completely unknown substance. Rather,
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 303
Summary
The primary object of all sampling procedures is to bring the original
specimen to the place of observation or analysis without alteration of
CHAPTER 13 ON SAMPLING AND IDENTIFICATION OF DEPOSITS 305
TABLE 2—Typical report form for results by different methods of identification for two
different samples.
Sample A Sample B
CHEMICAL ANALYSIS
SiO2 19.7 SiO2 17.9
Fe203 26.6 Fe203 2.6
CaO 10.8 CaO 30.8
MgO 16.2 MgO 17.9
S03 0.1 SO3 0.1
P205 12.3 C02 24.2
Cu 5.4 Loss on ignition 30.5
Loss on ignition 8.5
MICROSCOPICAL ANALYSIS
Considerable amount of iron oxide present in Large amount of highly birefringent calcite
colored bands. Some hydroxyapatite and present. Magnesium silicate also present,
considerable amount of poorly crystalized Iron oxides present as a minor constituent,
compound, probably magnesium silicate.
Small quantities of dendrites of metallic
copper.
SPECTROSCOPIC ANALYSIS
Constituents over 5 percent: Constituents over 5 percent:
Si, Fe, Ca, and Mg Si, Ca, and Mg
Constituents 0.5 to 5 percent: Constituents 0.5 to 5 percent:
Cu Fe
Constituents 0.05 to 0.5 percent: Constituents 0.05 to 0.5 percent:
Mn and Cr Zn, Al, and Mn
SPECTROGRAPHIC ANALYSIS
Mn 0.13 Zn 0.43
Cr 0.07 Al 0.17
Ni 0.01 Mn 0.08
Cu 5.29 Pb 0.02
306 MANUAL ON WATER
References
[/] Annual Book of ASTM Standards, Part 31.
[2] Symposium on the Identification of Water-Formed Deposits, Scales, and Corrosion
Deposits by Physico-Chemical Methods. Proceedings, ASTM,'Vol. 43, 1943, pp. 1269-
1310.
[3] Symposium on Identification of Water-Formed Deposits, ASTM STP 256, American
Society for Testing and Materials, 1959.
[4] Bergey, D. H., Manual of Determinative Bacteriology, Williams and Wilkins Co., Balti-
more, Md., 1938.
[5] Manual of Methods for Pure Culture Study of Bacteria, Biotech Publications, Geneva,
N. Y., 1946.
[6] Tanner, F. W., The Microbiology of Foods, 2nd ed., Garrard Press, Champaign, 111.,
1944.
[7] Berry, T. F., Allen, W. C., and Snow, R. B., Journal, American Ceramic Society,
JACSA, Vol. 33, 1950, p. 121.
[8] Chamot, E. M. and Mason, C. W., Handbook of Chemical Microscopy, 3rd ed., Wiley,
New York, 1958.
[9] Larsen, E. S., and Berman H., "The Microscopic Determination of the Non-Opaque
Minerals," Bulletin 848, U. S. Geological Survey, 1934.
[70] Winchell, A. N., The Microscopic Character of Artificial Inorganic Substances of Arti-
ficial Minerals, Wiley, New York, 1943.
[11] Walstrom, E. E., Optical Crystallography, John Wiley, New York, 1943.
[12] Winchell, A. N., Elements of Optical Mineralogy, Wiley, New York, 1929, 1933, 1937.
STP442A-EB/Jul. 1978
Many of the difficulties that arise during the industrial use of water are
closely related to water-formed sludges, scales, and corrosion products.
These water-formed deposits are the accumulations of insoluble material
derived from the water, or are formed by the reaction of water with surfaces
in contact with it. The composition of such deposits can be used to diagnose
the reason(s) for deposition, to determine preventive treatment of either the
water or its environment, and to effect their removal. A thorough and
accurate analysis is an important beginning in this process.
The analysis of water-formed deposits must be versatile and compre-
hensive in order to handle the most complex sample. It must also be flexible
enough to handle the simplest samples easily and efficiently. The usual
quantitative analysis will yield the elemental composition of the major
constituents of such deposits. When single elements or simple compounds
predominate, such an analysis is probably sufficient. For more complex
deposits, however, other tools must be used to determine accurately the
combinations of these elements. These include emission spectroscopy, X-ray
diffraction, X-ray fluorescence, electron probe microanalysis, flame photo-
metry, atomic absorption, petrographic microscope, and the electron micro-
scope. A method for atomic absorption and spectrographic analysis_is
outlined in ASTM Testing Water-Formed Deposits (Method D 2331) [7]1; a
procedure for identification by X-ray diffraction is dealt with in ASTM Test
for Identification of Crystalline Compounds in Water-Formed Deposits by
X-Ray Diffraction (Method D 934) [7]; X-ray fluorescence is covered in
ASTM Analysis of Water-Formed Deposits by X-Ray Fluorescence (Method
D 2332) [/]; flame photometry in ASTM Test for Sodium and Potassium Ions
in Industrial Water and Water-Formed Deposits by Flame Photometry
(Methods D 1428) [7]; and microscopy in ASTM Examination of Water-
Formed Deposits by Chemical Microscopy (Method D 1245) [7]; These and
other instrumental techniques are also discussed in Chapter 13.
It is often possible to determine the source or cause of water-formed
deposits from the results of chemical and physical analyses. The treatment
'The italic numbers in brackets refer to the list of references appended to this chapter.
307
Copyright© 1978 by ASTM International www.astm.org
308 MANUAL ON WATER
Analysis of Deposits
Any analytical scheme can be only a guide, and the analyst must use his
skill and ingenuity in carrying out or modifying such a scheme. It is
impossible to draw a blueprint that will fit rigidly all water-formed deposits
that may confront the analyst. The amount of sample available may dictate
that only a few tests be made. Preliminary examination may show that only
a few tests are needed for determination of the important constituents.
Frequently, direct determinations for single constituents can be made
without going through a sequential analysis. Copper can be selectively
extracted with ammoniacal persulfate and the amount of copper determined
photometrically from the color of the extract. Silica can be dissolved from
the sample by molten sodium hydroxide and the extracted silica determined
colorimetrically with the molybdate-blue procedure. These and other rela-
tively rapid determinations of one or more constituents are given in ASTM
Method D 2331.
The analysis scheme shown graphically in Fig. 1, and the separate steps
are discussed in the following paragraphs.
310 MANUAL ON WATER
I
Exploratory tests (aliquots of redried (105 C) extract residue
Organic extract
(for analysis see text)
H2S by evolution 1
*j£rt Water soluble CO? by evolution Ha and K ($« \ea and
(for onolysi, 1 ASTM Method D 513 ASTM Method
m Clnp D1428)
Ignition loss
Dissolve-HN03, HCland HC >4 (to fumes) - dilute and filter
Si02 and inclusim
HF treatment
Fuse residue with NajCOs
1 and add to main filtrate _
Treatment of Extracts
Mother liquor separated from a field sample frequently will include solids
that led to formation of the deposit. Soluble constituents such as chloride,
sulfate, nitrate, and metal ions can be detected by standard analytical
procedures such as the ASTM methods Ref /.
CHAPTER 14 ON CHEMICAL ANALYSIS OF DEPOSITS 311
Water-Soluble Matter
This test should be made immediately ahead of the ignition-loss test, and
on the same sample, to remove hydrates and certain other components that
might confuse the ignition-loss value. If appreciable water-soluble matter is
present, it should be examined for the usual water-soluble ions: chlorides,
bromides, fluorides, sulfides, sulfates, phosphates, nitrates, silicates, and
metal ions. If any are found in significant amounts, they should be
determined quantitatively. Normally the water-soluble content of a water-
side deposit will be low, but certain deposits, like calcium hydroxide, can
cause difficulty even thpugh they are reasonably soluble.
Ignition Loss
Ignition loss will include such items as organic matter, carbon, sulfur
(sulfite and sulfide), carbon dioxide from carbonates, and, on rare occasions,
nitrogen oxides or ammonia. Certain hydrates not removed by the water
solubility test also may be decomposed. The results of the ignition-loss test
are difficult to interpret, for while some constituents are being driven away,
others are being oxidized to higher weight values. For example, reduced
forms of iron oxide and copper can increase in weight on ignition.
The principal merit of ignition is in helping to confirm the presence of
constituents indicated by other tests. If a large amount of free copper is
found in preliminary inspection, a proportionate increase in weight on
ignition will be expected. On the other hand, if a large amount of organic
copper is observed in the extraction test, then a large loss of weight on
ignition would be expected.
Often, heating to a lower temperature than the usual 900 to 1000°C will
provide useful information. Carbonaceous samples, for example, should be
heated to a maximum temperature of 500° C. The report of analysis should
give the ignition temperature and length of ignition time.
Sulfate
Sulfate is determined by precipitation as barium sulfate as given in ASTM
Test for Sulfate in Industrial Water and Industrial Waste Water (Method D
516) [/]. If the iron content is high, preliminary precipitation and filtration
to remove excess iron will reduce to a minimum the contamination of the
barium sulfate precipitate.
Manganese
Since the primary solution is a perchloric acid medium, manganese can be
determined colorimetrically by the standard potassium periodate method
described in various texts.
314 MANUAL ON WATER
Titanium
The standard method of oxidation with peroxide and determining tita-
nium by comparison with color standards is satisfactory for most boiler
deposit work. Vanadium produces a similar color and will yield essentially a
quantitative error. If the vanadium content is know, it can be subtracted.
Again, the absence of vanadium from most water-formed deposits makes
this error relatively unimportant.
Expressing Results
The results of analysis are generally reported in terms of basic oxides and
acid anhydrides, as shown in ASTM Reporting Results of Examination and
Analysis of Water-Formed Deposits (Method D 933) [/]. This procedure
does not provide for reporting definite molecular combinations. The ex-
pression of analytical results in terms of basic oxides should not be taken as
implying that any of the oxides are present in the sample as such. This
method of reporting results is only an arbitrary procedure of long usage.
2
"ZINCON" is a trade name of The La Motte Chemical Products Company for their 2-
carboxy-2'-hydroxy-5'-sulfoformazylbenzene.
316 MANUAL ON WATER
Conclusions
The preceding information on analysis of deposits is not intended to be
exhaustive. The discussion and tables of compounds likely to be found in
water-formed deposits (Table 1 and Chapter 13) should be used as a guide by
the analyst in determining his course of procedure. There may be occasions
when preliminary qualitative tests indicate the presence of elements not
included in the scheme discussed herein. In such cases, the analyst will
perforce have to use his ingenuity and modify the procedures to effect the
necessary separations and choose methods which will adequately determine
the elements so indicated. Many of the methods discussed in Chapter 11 for
the analysis of industrail waters may be applicable to the determination of
certain constituents of water-formed deposits, and the analyst is advised to
study that chapter carefully.
TABLE I—Continued.
/3 Chalcocite )8Cu 2 S
Chalcopyrite CuFeS2
Copper Cu
Copper aluminate CuAlO2
Corundum a Al2O,
Covellite CuS
Cristoballite SiO2
Cuprite Cu2O
Delafossite Cu2O-Fe2O3
Dolomite CaCOrMgCO,
Fayalite 2FeO-Si02
Ferrous bicarbonate Fe(HC03)2
Ferrous sulfate monohydrate FeSO4-H2O
Ferrous sulfate quadrahydrate FeSO4-4H2O
5 Ferric Oxide 6 Fe2O3
/? Ferric oxide monohydrate 0 Fe2OvH20
Fluorite CaF2
Foshagite 5CaO-3SiO2-3H2O
Forsterite 2MgO-SiO2
Gaylussite CaOVNa2COr5H2O
Gehlenite 3CaO-Al2Or2SiO2
Gibbsite 7 A1203-3H2O
Glauconite K2(MgFe)2AU(Si40,0)3(OH)12
Goethite a Fe2O3-H2O
Gypsum CaSO4-2H2O
Gyrolite 2CaO-3SiO2-H2O
Halite NaCl
Hematite Fe203
Hemihydrate CaSO4-^H 2 0
Hemimorphite Zru(OH)2SiO7-H2O
Hydromagnesite 4MgO-3CO2-4H2O
Hydrotalcite MgCo3-5Mg(OH)2-2Al(OH)3-4H2O
Hydroxyapatite Caio(OH)2(PO4)6
Hydroczincite 2ZnC03-3Zn(OH)2
Iron Fe '
Lazurite 3Na2O-3Al2O3-6SiO2-2Na2S
Lead Pb
Lepidocrocite y Fe2O3-H2O
Libethenite 4CuO-P2O5-H2O
Maghemite 7 Fe2O3
Magnesia MgO
Magnesium chloride hydrate (basic) MgCl2-5Mg(OH)2-8H2O
Magnesium hydroxyphosphate Mg3(P04)2-Mg(OH)2
Magnesite MgC03
Magnetite Fe2O3
Malachite CuC03-Cu(OH)2
Meta halloysite Al2O3-2SiO2-xH2O
Meta thenardite Na2SO4I
Montmorillonite Al2O3-4SiO2-H2O-nH20
Mullite 3Al203-2SiO2
Muscovite KAl2(Si3Al)0,o(OH2F)2
Natrolite Na2O-Al2O3-3SiO2-2H2O
Nontronite H4(A1, Fe)2Si2O9
Noselite 4Na20-3Al2O3-6SiO2-S03
Oldhamite CaS
Olivine 2(Mg, Fe)O-SiO2
Para sepiolite 2MgO-3SiO2-2H20
(Continued)
318 MANUAL ON WATER
TABLE 1— Continued.
Paratacamite 7 CuCl: 3Cu(OH):
Pectolite Na:O-4CaO-6SiOrH:O
Periclase MgO
Portlandite Ca(OH):
Pyrrhotite FeS
Quartz SiO:
Sepiolite 2MgO3Si02-2H2O
Serpentine 3MgO2SiO2-2H2O
Siderite FeCO,
Smithsonite ZnCO,
Sodium disilicate p Na2Si2O5
Sodium metasilicate Na2SiO.
Sphalerite 0ZnS
Syngenite K2SO4-CaSO4-H2O
Talc 3MgO-4Si02-H2O
Tenorite CuO
Teschemacherite NH4HCO,
Thenardite Na2SO4(V)
Thermonatrite Na2CO,H2O
Troilite FeS
Trona 3Na20-4C02-5H20
Vermiculite (Mg, Fc)3(Al, Si)4O,o(OH)2-4H2O
Vivianite Fe3(PO4)2-8H2O
Wedellite CaC2O4-2H20
Wilkeite Ca,00[(Si, P, S)04]6
Willemite Zn2SiC>4
Witherite BaCd
Whitlockite 0 Ca3P2O8
Wollastonite /3 CaSiOi
Wustite FeO
Xonotlite 5CaO-5SiO2-H20
Zinc A ZnOxH 2 O
B ZnO-yH2O
E ZnO-zH2O
Zincite ZnO
Zincosite ZnSCX
References
[/] Annual Book of ASTM Standards, Part 23.
[2] Feigl, Fritz, Spot Tests in Inorganic^^Analysis, 5th ed., Elsevier, New York, 1958.
[3] Furman, N. H., Ed., Standard Methods of Chemical Analysis, 6th ed., Van Nostrand,
New York, Vol. 1, 1962, p. 1031.
[4] Furman, N. H., Ed., Standard Methods of Chemical Analysis, 6th ed., Van Nostranu,
New York, Vol. 1, 1962, p. 282.
STP442A-EB/Jul. 1978
All streams and other water bodies contain sediment in variable quantity
and character. Methods for measurement of these sediments are affected by
the sediment mode (suspended or deposited), by the characteristics of the
water body, and by the spacial and temporal variations of the sediments.
The purpose of this chapter is to indicate some of the needs for sediment
measurements, describe some of the more common sediment environments
in which it may be necessary to make measurements, and provide general
references to the commonly used methods for making these measurements.
Many activities in the conservation, development, and utilization of land,
mineral, and water resources affect sediment movement and thereby may
create sediment-related problems. For example, a change in the runoff
regime from a drainage basin may concentrate or disperse sediment in the
stream channel and,, in turn, affect the flow capacity of the stream. Because
of the complex interrelationships that affect sedimentation phenomena, a
knowledge of climate, the physical attributes of drainage basins, the
hydraulic and hydrologic characteristics of streamflow, and the quantitative
and qualitative aspects of sediment is required to solve sediment problems.
One might think that the solution to most sediment problems would be to
stop landscape and channel erosion. This is not only impossible, but would
severely upset the natural balance so that a host of new problems would
emerge. Experience has shown that erosion should be carefully controlled to
fit the situation. Intensive sediment movement (perhaps 100 t/ha) from a
small construction site may be tolerated for a few weeks, especially if the
sediment is deposited before it reaches a stream; but a relatively small
amount of top soil (perhaps 1 t/ha/year) from a cropland with adsorbed
herbicides may be intolerable if it reaches a stream.
Experience gained over the years has led to a greater understanding and
appreciation of sediment problems; however, recent lawsuits attest to the
fact that man's activity has caused, and will continue to cause, detrimental
environmental changes resulting from the transport of fluvial sediment. Life
scientists have become increasingly aware of the effect of sediment on the
flora and fauna of streams and other water bodies. As an example, bottom
sediments contaminated by industrial or municipal wastes may be dispersed
319
Copyright© 1978 by ASTM International www.astm.org
320 MANUAL ON WATER
by dredging operations, and thereby made available to enter the food chain
through fish and other aquatic life. Numerous references can be found
showing that bottom sediments in rivers are capable of adsorbing pesticides,
trace metals, and other toxic chemical constituents.
Glymph [7]1 indicates that we have recently begun to appreciate the water-
quality implications of sediment as a pollutant in the same context as
industrial wastes, effluents from sewage treatment plants, and other kinds of
pollutants. Rutherford [2] has asked the pertinent question: How much
longer can the strained soil colloids near commercial, industrial, and other
waste-producing areas continue to extract and store pollutants through ionic
exchange before they become totally clogged, and how fast are these soils
becoming unwanted sediments in nearby water bodies? These aspects of
sedimentation require new levels of sophistication for determining sediment
yields and sediment properties in small basins to form the basis for cost-
effective sediment and pollution management programs.
The scope of water-related sediment problems varies widely in intensity
and in time and space. The most prevalent problems, however, range from
the hour-by-hour impacts on small streams of sediments that are eroded
from cropland or construction sites during rainstorms to continuous impacts
on large streams of sedimentation phenomena that affect aesthetics, stream-
channel andpreservoir capacity, and the disposition of sorbed pollutants.
Although visual inspections may be helpful, a solution to a sediment
problem usually requires scientific measurements that serve to define the
quantitative and qualitative character of sediments suspended in, trans-
ported by, and deposited from natural and man-made streams and water
bodies.
Modeling experts have made some progress, though sometimes with
conflicting results, in outlining predictive equations in sedimentation. How-
ever, it seems that there is only a remote possibility for development of a
complete set of such equations. Therefore, numerical simulation techniques
using current and pertinent basic data offer the most practical basis for
predicting specific fluvial sediment phenomena.
Because of the impact of an ever-changing environment on sediment
movement, it is expected that there will be an increasing need for sediment
measurements to obtain information on its quantity and characteristics
which can be correlated with these environmental changes. Sediment data
are also needed to help verify the effectiveness of sediment-control measures.
Most sediment measurements are made to satisfy one of three general
program objectives:
1. To obtain general information from a network of sediment-measuring
stations which provide unbiased comprehensive information about sediment
concentration and movement.
2. To obtain special information relative to specific problems so water
managers can better choose among alternative actions.
'The italic numbers in brackets refer to the list of references appended to this chapter.
CHAPTER 15 ON SEDIMENT IN STREAMS AND OTHER WATER BODIES 321
Streams
Although the land-surface environments are the basic sources of supply
for stream sediment, the stream channel itself may be a sediment source. As
noted, the processes of erosion and deposition on the landscape cause a
highly variable quantity of sediment to be available for movement by
streams. In discussing sediment available to streams, it is useful to classify
sediment as either fine or coarse.
Fine Sediment—Fine sediment (< 0.062 mm) is easily suspended by
natural stream turbulence, and hence travels through a stream system with
about the same velocity as the water. The quantity of fine sediment moving
at a given stream cross section depends on the amount of erosion in the basin
and the routing of the particles by the flow to this section. The quantity
moving is only indirectly dependent on the flow rate of the stream. The exact
concentration of fine sediment in transport during stormflow is unpre-
dictable with respect to time, and frequently increases by a factor of 100 to
1000 times that of "normal flow." Thus, sediment measurement techniques
require a program to obtain a sufficient number of observations to define the
large temporal variations in concentrations.
Coarse Sediment—Coarse sediment (> 0.062 mm) usually is found in
appreciable quantities in the bed of a stream and may be transported both as
suspended load and as bedload. The mode and rates of transport depend on
the properties of the fluid, the sediment, the hydraulics of flow, and the
characteristics of the channel geometry. Thus; it follows that coarse-
sediment discharge often can be roughly related to water discharge at a given
stream transect (cross section).
The movement of coarse particles consists of a series of steps interrupted
by periods of no motion, when the particle is a part of the bed material. A
particle moves and becomes a part of either the suspended load or the
bedload whenever lift and drag forces or impact from another moving
particle, or both, overcome the resisting forces and dislodge it from its
resting place. The magnitudes of the forces vary according to the fluid
properties, the velocity and turbulence of the flow, the physical character of
the particle, and the degree of exposure of the particle. The degree of
exposure depends largely on the size and shape of the particle relative to
other particles in the bed mixture, and to the position of the particle relative
CHAPTER 15 ON SEDIMENT IN STREAMS AND OTHER WATER BODIES 323
where
Qs = "instantaneous" suspended-sediment discharge through a section
of area A,
U = velocity of sediment particles through an elemental area dA, and
C - suspended-sediment concentration in the elemental spatial volume
Ut'dA, in which t' is one unit of time used to express U.
In the practical application of Eq 1, U is considered to be equal to the flow
velocity and C is considered to be constant during any given sampling period
associated with its determination. Integrating the Eq 1 over time yields the
quantity of suspended-sediment discharge during any specified duration, T.
That is
s=$TQsdt=ST$cudAdt
A (2)
Estuaries
Significant differences in the sediment environment are found in different
„ types of estuaries. In estuaries where the tidal volume of sea water flowing
into and out of the estuary is very large relative to the volume of river flow,
sufficient mixing usually occurs so that the vertical distribution of salinity is
uniform with depth and only a longitudinal salinity gradient exists. Under
these circumstances, the flow is not vastly different from rapidly varying
unsteady flow in rivers, and sedimentation processes are roughly similar to
those that occur under like flows in a river.
In the so-called partially mixed estuary, which is the most prevalent type
of major estuary along the Atlantic and Pacific coasts of North America, the
volume of freshwater inflow is sufficiently large relative to the volume of
seawater flow that a complex pattern of salinity (and therefore density)
gradients develops. This produces a net vertical circulation in which seaward
from a point on the channel bottom—termed the null point or the point of
zero net flow—there is a predominance of landward flow of relatively dense
saline water along the bottom, and a predominance of seaward flow of less
dense relatively freshwater near the surface, even though the body of the
flow alternates direction periodically in accordance with the tide. This
CHAPTER 15 ON SEDIMENT IN STREAMS AND OTHER WATER BODIES 325
Methods of Measurement
A wide number of samplers and procedures have been developed and are
commonly used for sampling sediment in streams and other water bodies. In
326 MANUAL ON WATER
general, the requisites for sampling sediment that is in motion are sub-
stantially different from those for sampling stationary deposited sediment.
Prior to documentation of specific instructions by ASTM, specifications of
samplers and sampling procedures are given in Chapter 3 of a National
Handbook of Recommended Methods for Water-Data Acquisition pre-
pared by a working group of representatives from Federal agencies in-
terested in aspects of sediment measurement. The chapter also includes
instructions for sample handling and preservation, laboratory analysis,
methods for making reservoir surveys, methods for documenting stream
channel changes, and quality control for the sediment measurement pro-
gram.
References
[/] Rutherford, G. K., "Anthropogenic Sources of Heavy Metals for Sediment Transport,"
Proceedings, Conference on Fluvial Transport of Sediment-Associated Nutrients and
Contaminants, Kitchener, Ontario, 1976 (in process).
[2] Glymph, L. M., 1975, "Evolving Emphasis in Sediment-Yield Predictions," Present and
Prospective Technology for Predicting Sediment Yields and Sources, U. S. Department
of Agriculture, ARS-S-40, Washington, D. C, pp. 1-4.
STP442A-EB/Jul. 1978
Before the summer of 1945, it could be fairly stated that the problem of
radioactive contamination of water did not exist. True, some radioactive
springs were known, but these aroused little interest, except for possible use
of the supposed healing properties of the water. The successful testing of an
atomic bomb in the New Mexico desert on July 16, 1945, changed this
situation. Fogging of some packages of photographic film was traced to
radioactive debris from this bomb. The radionuclides had got into the
process water and then into the wrapping paper. This is the first known
damage to a commercial product from radioactively contaminated water.
Radioactivity may be defined as the spontaneous emission of penetrating
energetic radiation from certain atomic nuclei. The early workers in the field
soon classified the radiation into three types, called alpha (a), beta (0), and
gamma (7) rays, on the basis of their ability to penetrate matter. They were
also able to establish their nature, finding that alpha and beta rays were
high-speed particles, while gamma rays were electromagnetic waves similar
to X-rays. The results of these early studies can be tabulated as shown in
Table 1.
The emission of these radiations is associated with a nuclear disinte^
gration, which is the rearrangement of the constituents of the nucleus into a
more stable configuration with an associated release of energy. The rate of
emission is characteristic of the radioactive material (also called radio-
nuclide), and is described by the time required for half of the unstable nuclei
to complete their rearrangements and emissions: the half-life. After the lapse
of one half-life, since the number of unstable nuclei has been reduced to one-
half the original number, the emission rate (or activity) is also reduced to one
half of its initial value. The quantity of radioactive material is measured by
the rate of disintegration; that amount of a nuclide in which 3.7 X.1010 atoms
disintegrate per second is defined as a curie. Ordinarily, subdivisions of this
unit, milli-, micro-, or even micromicrocuries, are used. These are 10-*, 10~6,
and 10~12 curies respectively. The term picocurie, is currently used as a
synonym for micromicrocurie.
The energy released in a nuclear disintegration is large, usually of the
order of a million times as much as is involved in ordinary chemical changes.
When alpha particles or gamma rays are emitted, these carry off sub-
stantially all the energy release. In beta emission, however, the available
energy is divided between the beta particle and a neutrino, which is not
ordinarily observable. The division of the energy varies in individual
disintegrations, so that a particular beta particle may have an energy from
zero up to the maximum available, the average being about one third of the
total energy released. Consequently, beta radiation has a continuous energy
spectrum, while alpha and gamma radiations are characterized by line
spectra.
The unit of energy most used in radioactivity is the electron volt, the
energy gained by an electron in passing through a potential difference of 1 V.
It is equal to 1.6 x TO"12 ergs. Alpha particles have energies of a few million'
electron volts (MeV); beta and gamma radiations may have energies from
zero up to a few MeV.
The three types of radiations interact with matter in somewhat different
ways. Both of the charged particles (alpha and beta) react primarily by
electrostatic interaction with the electrons of the material, transferring
energy to each electron that they approach sufficiently closely. Quantita-
tively, the actions differ considerably, with the heavier, slower-moving alpha
particle interacting with many more electrons per unit path length. The
interaction of gamma radiation with matter is essentially statistical in nature,
with each individual gamma photon transferring no energy until it interacts,
usually with an electron, whereupon it transfers all or a large part of its
energy. The gamma radiation has no definite range, but is statistically
reduced in quantity as it passes through matter. This gamma interaction has
been compared to the process of firing machine gun bullets at random into a
forest, in which each bullet is unaffected until it strikes a tree, when it loses
all or part (if it ricochets) of its energy. The extent of the interaction of the
three types of radiation with matter is illustrated in Table 2.
The primary effect of the interaction of any one of the three types of
radiation with matter is the transfer of energy to electrons, resulting in the
production of ions or of excited molecules. Secondary changes in matter
include such phenomena as the darkening of photographic film, the
initiation of chemical changes, and biological effects. The extent of such
CHAPTER 16 ON RADIOACTIVE NUCLIDES IN WATER 329
Cosmic-Ray-Produced Nuclides
A few radioactive materials of short half-life exist in nature from
continuous production by cosmic-ray bombardment of the atmosphere.
These nuclides are also listed in Table 4. The most important of these are
carbon-14 and hydrogen 3 (tritium). Carbon-14 is formed by the action of
cosmic-ray neutrons on atmospheric nitrogen, while tritium is formed
directly in the splitting of atoms struck by the high-energy cosmic ray
particles. Both of these are oxidized, to carbon dioxide and water, and enter
the biosphere and hydrosphere. None of the other radioactive nuclides
332 MANUAL ON WATER
Ores
The primary natural materials useful in nuclear energy are uranium and
thorium. Uranium-235 is the only natural fissionable material; uranium-238
and thorium-232 are the raw materials for manufacture of artificial fis-
sionable materials. The first steps in nuclear technology are thus the mining
and refining of these materials. Uranium and thorium are each the pro-
genitor of long series of radioactive elements, any or all of which may be
present in the ores.
Of all the daughter elements, those of relatively long half-life include
thorium-230 (ionium), radium-226, and lead-210 (radium D) in the uranium-
radium series, and radium-228 (mesothorium 1) and thorium-228 (radio-
thorium) in the thorium series. The long-lived protactinium-231 and
CHAPTER 16 ON RADIOACTIVE NUCLIDES IN WATER 333
actinium-227 occur in uranium, but since they are derived from relatively
scarce uranium-235 (0.71 percent), they are less important. In removing the
desired uranium or thorium from ore, the other radioactive elements present
will be left behind. Depending upon the process, these elements may occur in
various chemical forms with different solubilities. Those of long half-life will
persist much longer than any conceivable control measures and their
treatment must be absolutely foolproof. The more soluble materials, of
course, may eventually reach and contaminate waters. Of all the nuclides
listed in the preceding paragraph, radium-226 is the most harmful in a water
environment by reason of its biochemical properties, its long half-life, and
the energetic radiations of it and its immediate daughter products. The
present maximum permissible concentration of this material in uncontrolled
waters is only 4 X 10~9 /iCi/ml (about 9 disintegrations/min/litre), or 4X
10~12g/litre. Obviously, extreme precautions are necessary to limit losses to
this small amount.
Natural Water
Water itself, when exposed to a neutron flux, does not yield any important
radioactivities. There is a rather intense radiation from nitrogen-16, a
product of the interaction of neutrons with oxygen-16, but this material has
such a short half-life (7) that any system suitable for containing the reactor
will be adequate to protect against it. But many materials present in natural
waters will yield radionuclides of relatively long half-life under neutron
irradiation. The potential hazard from these materials must be considered in
plant operations, and, if discharged, their concentrations must be kept below
values at which they might be detrimental to the environment.
The largest American installation using natural water as coolant is the
reactor complex at Hanford, Wash. The effect of the reactor operations on
the Columbia River has been studied extensively, including the radionuclide
content of the water, and of fish and other biological forms in the river.
Although a large number of radionuclides are formed in the water during its
passage through the reactors, most of these have such short half-lives that
they very soon become insignificant. Radioactive forms of manganese,
arsenic, copper, sodium, phosphorus, zinc, chromium, and iron are prom-
inent in the reactor cooling water, and many others are formed in lesser
amounts.
In addition to the radionuclides formed by neutron irradiation of stable
elements in the water, there is always the possibility of fission product
leakage from the fuel elements into the cooling water. While careful design
and painstaking workmanship confine such leakage to trivial amounts, some
fission products can be identified in the water. The most important of these
are iodine, strontium, barium, and the rare earths. Generally speaking,
fission products are of greater biological significance than the induced
activities, and very elaborate instrumentation is provided to detect leakage
before it becomes a problem.
A rather special case of potential formation of radionuclides in a natural
water is the operation of nuclear-powered vessels. Here, although the
coolant moderator is usually very carefully purified water in a closed system,
the designer must consider the possibility of reactor neutrons passing
through the hull to activate sodium and other elements in the water in which
the ship floats. Sufficient neutron shielding to prevent this is therefore
included in the reactor plant.
Treated Waters
In most water-moderated or water-cooled reactors, extremely pure de-
mineralized water is used. This may be ordinary (light) water or deuterium
oxide (heavy water). In many systems the water is continuously purified by
ion-exchange demineralizers.
There are several reasons for using such rigorously purified water in
336 MANUAL ON WATER
Canal Coolants
In addition to reactor coolant and moderator, water is used in the "canals"
in which fuel elements are stored prior to processing. These fuel elements,
containing an enormous quantity of radioisotopes, require considerable
cooling to dissipate the residual heat of the radioactive decay. The gamma
radiation from these elements is very intense, so that they must be heavily
shielded to permit plant personnel to work in the vicinity. Water about 7.6 m
(25 ft) deep serves both of these purposes satisfactorily. The fuel elements,
after a sufficient cooling period, are removed by remote-control tools.
CHAPTER 16 ON RADIOACTIVE NUCLIOES IN WATER 337
Fission Products
The most widespread type of radioactive contamination at present is fall-
out from nuclear weapons testings These tests have produced a considerable
atmospheric content of fission products of intermediate and long half-lives,
which gradually settle to the earth. In addition to settling under their own
weight and as a result of atmospheric currents, large quantities of these
materials are brought down by rain and snow.
In the United States during October 1958, it was unusual to find a rain or
a surface water that contained no detectable fission-product activity.
Levels of activity in rain may range from a few to thousands of picocuries
per litre, while in surface waters they will generally be of the order of tens
of picocuries per litre. In the period during and shortly after a weapons test
series, rain activity may reach the order of hundreds of thousands and
surface water activities hundreds of picocuries per litre. These increases are
primarily due to fission products of short half-life, which do jiot persist in
the atmosphere. Levels in groundwaters are ordinarily much lower than
these, depending largely on the speed with which the groundwater is
replenished by rain and surface water.
When rain containing fission product activity falls on the ground, much
of the activity is transferred to the soil, mostly by adsorption on soil par-
ticles or on atmospheric particulates washed down with the rain. As a
result, the fraction of radioactive material reaching streams or other bodies
of water is relatively small, except where large water areas are exposed to
direct rainout. Although water contamination is less than it would be if
these mechanisms were not operative, this cannot be counted as a clear
gain since much of the radioactivity remaining in the soil becomes available
to plants, and so enters the food chain with the possibility of eventual
ingestion by humans. Where rainfall is collected in cisterns for drinking
water, much of the radioactivity is removed by adsorption on the collection
surfaces, and by settling out and adsorption on the walls of the cistern.
The fission products cover a wide range of chemical elements. Conse-
quently, their behavior in water is characterized by large variations. Some,
such as zirconium, being very insoluble in most aquatic environments,
settle out more or less rapidly with paniculate material, thus becoming
concentrated in silts and sludges. Others remain in solution for a much
338 MANUAL ON WATER
longer time and hence can be carried much farther in streams. Still others
enter into the biological cycle and become distributed in a manner de-
pending upon the biota present in each stream.
As a result of the processes described in the preceding paragraph, com-
bined with normal radioactive decay, the total activity of a body of water
may decrease rapidly after contamination. This decrease, however, does
not necessarily imply a proportionate decrease in the biological hazard of
this water, which depends strongly upon the radionuclide composition of
the contamination. Removal of even large amounts of a relatively non-
hazardous component does not have much effect on the potential biological
damage.
Induced Activities
In addition to the fission products which are formed in fairly definite
proportions in the actual nuclear explosion, radioactive materials are
formed by irradiation with the neutrons produced in the explosion. The
nature and quantity of these induced radioactive nuclides depend on the
exact circumstances of the explosion, which determine the exposure to
neutron fluxes. Thus, in a high-altitude burst, only those materials present
in the bomb and in the air could be irradiated, while in a burst close to the
ground, all the elements present in the soil would be potential sources of
induced activity. In a subsurface explosion at sea, such materials as the
sodium in the water would become radiocative under the resultant neutron
bombardment.
The amount of fission product radioactivity formed during an explosion
is so large that normally the induced activity would not be noticeable in
the early stages; however, as the fission products of short half-life disappear,
those induced activities of longer half-life would become relatively more
prominent. A number of these induced radionuclides are concentrated by
biological systems and in many cases they have detected in fish or other
specimens taken from the water.
Table 6 lists some of the more important fission products and induced
radioisotopes that have been found in fallout.
Kadiotracers in Water
Induced activities
Carbon-14 Cobalt-57
Calcium-45 Cobalt-58
Manganese-54 Cobalt-60
Iron-55 Zinc-65
Iron-59
in tracing stream flow, oranges are reasonably satisfactory (at least so far as
surface flow is concerned), and fluorescein dye in solution is usually suitable.
The same principles apply with radiotracers. In flow studies, presumably the
best radiotracer for water would be tritiated water; reasonably good results
could be expected with tracers which react w^ith the stream environment to a
very small degree, while tracers that tend to precipitate out, enter into the
biology of the stream, or be removed by ion-exchange properties of the silts,
would give poorer, less conclusive results.
After it has been established that one (or several) tracers are suitable, a
number of other characteristics of the radioactive material become im-
portant. These characteristics include ease of detection and measurement,
suitable half-life (long enough for the experiment but not so long as to
interfere with subsequent experiments or use of the water), low radiological
hazard, availability, and low (or at least reasonable) cost.
Hydraulic Tracing
A fairly large number of radionuclides have been used in tracing flow.
Tritium would be ideal except for the difficulty of measuring its extremely
soft beta radiation. Excellent results have been obtained with bromine-82,
but there is the objection that the material has a half-life of only 36 h. It is
therefore most useful in studying small artificial systems, such as settling
basins and the like. Another halogen that has been used successfully in such
applications is iodine-131.
In longer studies, a nuclide of greater half-life usually is needed. lodine-
131 is sufficiently long-lived for many experiments, but the maximum
permissible concentration of this material in public waters is so low that its
340 MANUAL ON WATER
use is thereby restricted. One of the best nuclides for flow tracing in nature is
rubidium-86, which has a half-life of 19 days, emits readily detectable beta
and gamma radiation, and is relatively insensitive to precipitation or other
sedimentation. Scandium-46 has also been used under conditions such that it
would remain in solution or at least form fine, essentially nonsettling
particles. In following the movement of silts, scandium-46 and gold-198 have
proved suitable.
Biological Tracing
The discussion here will be confined to studies of the movement of
radioisotopes in the biota of a stream. This is particularly important in
understanding the fate of radionuclides introduced into a stream. The
outstanding opportunity for this type of study has been in the Columbia
River, where use of the river water as reactor coolant has resulted in the
presence of a wide spectrum of irradiated radioelements in the stream. Many
of these materials are concentrated strongly by algae and other plankton;
much of this concentration appears to be a surface or adsorption phenom-
enon. As one examines other forms higher in the food chain, the number of
elements concentrated (and often the degree of concentration) becomes less,
partly because of rejection of these elements in the diet or in digestion, partly
by disappearance of nuclides of short half-life. Thus, in the Columbia River,
the nuclides most generally present in fish are phosphorus-32 and strontium-
89, in contrast to the reactor effluent activities, which consist largely of
arsenic, manganese, and copper.
Some laboratory experiments have been performed on the uptake of
certain nuclides by fish and other aquatic forms. Most of the work has been
concentrated on fission products, particularly strontium and cesium. The
results of these studies, oversimplified, may be summarized by saying that
many elements are taken up by the more primitive feeders, such as algae and
mollusks. Forms feeding upon these primitive forms generally take up less of
the insoluble elements, except in the contents of the digestive tract. A
number of nonfission-product nuclides, particularly zinc, cobalt, and iron
isotopes, are taken up by mollusks, and surprisingly large quantities of zinc
have been found in fish.
High-Activity Wastes
High-activity wastes may be defined as those containing radionuclides at a
concentration of the order of curies per gallon. Most of these wastes
originate in the chemical processing of irradiated reactor fuels. Their
treatment is made difficult by their chemical properties (acidity, salt content,
and so on) as well as by their radioactivity. Generally speaking, these wastes
cannot be discharged. They must be stored, and treatment and disposal is
only a way of making the storage as inexpensive as possible. The wastes may
be stored in tanks, or disposal may be concealed as in discharge to the ocean
or into geological formations, or they may be converted into a solid,
nonleachable form. In all these cases, however, there is reliance on the
material staying where it is put, and not being allowed to leak into the
environment.
The only reliable, tested method for large quantities of high-level wastes is
permanent tank storage. The waste is usually concentrated by evaporation to
the greatest extent possible, the condensate being discharged as a low-level
waste. The concentrated bottoms are then transferred to special tanks. These
tanks must be corrosion-resistant and must provide for removal of the heat
produced by radioactive disintegration. Although storage is stated to be
"permanent," this cannot yet be considered definitely established, because
the nuclear industry is less than thirty years old and retention for centuries is
required. It is definitely established, however, that this treatment is ex-
pensive.
A treatment successfully used on small quantities of highly radioactive
wastes is conversion into a solid such as concrete. One way of doing this is to
add enough cement to the waste that it will set. The cement is usually
allowed to set in drums, which are then buried either in the ground or in the
deep sea. A modification of this method which offers much promise, and
which has been tested on a small scale, is conversion of the waste into a
glassy or ceramic material. The waste is calcined to alumina or zirconia and
leached. The leached radionuclides may be taken up on clay be adsorption or
ion exchange, and the clay is then fired to change its crystal structure in such
a way that the radionuclides cannot be desorbed or leached. The ceramic
pellets could presumably be stored much more cheaply than tank storage,
because of the two factors of reduced volume and noncorrosive nature.
Another form of treatment that has been proved in the laboratory involves
separation of the long-lived nuclides strontium-90 and cesium-137 on
barium sulfate and potassium alum, respectively. These two nuclides may
then be stored rather cheaply because the volume has been markedly
reduced. An aqueous phase suitable for discharge is obtained by solvent
CHAPTER 16 ON RADIOACTIVE NUCLIDES IN WATER 343
extraction of the residual fission products from the waste water. These
fission products present a much simpler storage problem because of their
shorter half-lives.
Ultimate Disposal
The term "disposal at sea" really has two meanings. In one, it is
contemplated that the material remain sealed indefinitely out of contact with
the seawater; in the other, the material is introduced into the deep sea but is
not sealed from it, and reliance is placed on the slowness of mixing in the sea
to limit the spread of radioactivity into the human environment. Unfor-
tunately, our present knowledge of the sea is not adequate to permit full
confidence in slow mixing. Rates of transport, and especially of biological
transport, are still very uncertain. Therefore, all present disposal at sea is
actually sealed storage. Sealed containers, usually concrete-filled steel
drums, designed to withstand the pressures and corrosion of the sea, are
discharged into depths of 1000 fathoms or more. Presumably the drum and
eventually the concrete will be corroded away, but it is hoped that this
process will be slow enough that even the longer-lived dangerous nuclides
will have decayed to insignificant levels.
Because of the cost of tank storage and of transportation for burial at sea,
there is much interest in underground disposal. This is different from
discharge into the soil as utilized for low-level wastes. The concept with high-
activity wastes is utilization of sealed geological formations as permanent
storage. A number of types of geological formations have been considered;
at present the most promising appear to be salt domes.
Sampling
In sampling water for determination of its radioactivity, whether this be
for gross or for radionuclide assay, the normal principles of sampling apply.
Since no analysis is better than the sample, it is necessary to make certain
that the sample drawn is actually representative of what is needed, both in
space and time. The possibility that the analyst may require a continuously
composited sample, even one composited proportionally to flow rate, should .
not be disregarded. Where adequate mixing is not assured, a number of
samples from different points and various depths may be taken, either for
individual analysis or for compositing. The principles involved in this aspect
of sampling will not be mentioned further, because they have been covered in
detail in Chapter 9.
Sampling for radioactivity determinations, however, does have one
requirement not commonly found in other sampling. This is the need to
prevent loss of the radioactive material to the sampler or container. When,
344 MANUAL ON WATER
as is often the case, the amount of nuclide is only of the order of 10~12 g, or
even less, normal adsorptive losses on container walls may amount to an
important percentage of the activity. Glass or plastic materials appear to give
somewhat less difficulty of this kind than do metals. Where necessary,
addition of carrier materials or chelating agents or acidification may be
employed to minimize adsorptive losses.
Often, no adsorptive losses are found in sampling streams or other natural
waters. It appears that in such waters the easily adsorbable materials are
already on the surfaces of whatever suspended solids may be present.
Therefore, treatment to prevent adsorption may result in undesired transfer
of radionuclides from the suspended to the dissolved phase.
Measurement
Only the mos*t general survey of the problems of measurement of
radioactivity in water is in order here. Specific details are the subject of
numerous papers and books. As it is often necessary to measure extremely
small amounts of radioactive material in water, the problem of sensitivity or
detectability becomes paramount.
Detectability is limited by the random nature of the radioactive disinte-
gration process. The result is a statistical uncertainty in the number of counts
observed, setting an inherent lower limit to the precision of the deter-
mination. At low enough levels, there is a question of whether there actually
were any counts in a given period beyond what might be due to the
background, that is, the counts caused by cosmic rays and by naturally
occurring radionuclides in and around the instrument. Three techniques are
available to get enough counts to permit a definite answer to this question:
start with a large sample, detect as many of the radiations as possible, and
suppress the background. It is not often convenient to collect or process
samples larger than a litre or so, and sample size is often further restricted by
solids content. This will be further considered in the discussion of methods
of sample preparation.
High efficiency of detection is chiefly a function of the instrument type,
although it is also affected by sample preparation. As far as the instrument is
concerned, three factors are paramount. First is geometry, or fraction of
radiation emitted toward the detector. This is primarily determined by
sample and detector size, and by the distance between them. Next comes
absorption, which refers to failure of part of the radiation to penetrate the
sample solids, the air or other material between the sample and detector, or
the wall of the detector itself. Third is the actual detector efficiency, or the
fraction of radiations entering the detector which causes a response. Highest
overall efficiency occurs when a sample is placed inside a detector able to
respond to each disintegration. Such 100 percent efficiency is customarily
attained only with gaseous samples, although it can be approached with
solid samples in special 4-pi counters.
CHAPTER 16 ON RADIOACTIVE NUCLIDES IN WATER 346
Instrumentation Types
Three principles of detection are used in measurement: gas ionization,
scintillation, and photographic darkening. The last is omitted as not strictly
an instrumental technique, although it is very widely used in such applica-
tions as personnel monitoring by film badges and in autoradiography. Each
of the other two techniques may be used to provide an average, pointer-type
indication, or to count individual events.
A second classification of instruments is by the type of radiation they are
designed to measure. Since alpha particles are characterized by small
penetrating power and high energy dissipation, alpha detectors must be
made with extremely thin windows for the entrance of the radiation, or
(more usual) with provision for the sample to be introduced into the
detector. Only moderate amplification is provided to take advantage of the
high energy dissipation, permitting low response for other types of radiation,
including cosmic rays. In scintillation alpha detectors, discrimination against
other radiations is provided by using a very thin zinc sulfide scintillating
screen which gives only very small light pulses with beta and gamma
radiation.
In the detection of beta particles, window requirements are less stringent
than for alpha particles. The ordinary Geiger-Miiller tubes may have glass or
metal walls with a thickness of 30 mg/cm2, or mica windows from 1 to 4
mg/cm2 thick. For the highest efficiency, the sample may be introduced into
the detector, as for alpha particles. In fact, the same instrument may be used
to detect alpha particles or beta (plus alpha) particles merely by changing the
voltage so as to provide higher or lower amplification. Scintillation beta
detectors commonly have an organic scintillator, such as an anthracene
crystal. The scintillator molecules may be dispersed in plastic to make
detectors of varying sizes and shapes.
Gamma rays are characterized by large penetration through matter;
therefore the detectors should have as much mass as possible. High atomic
number increases the response. Ionization chambers may contain gas under
high pressure, while gamma Geiger tubes usually have cathodes of silver,
bismuth, or other heavy metal. Windows may be made heavy (300 mg/cm2
or more) to reduce response to beta particles. The detection of gamma
346 MANUAL ON WATER
Sample Preparation
Sample preparation techniques are intimately connected with the type of
radiation and with the instrumentation available. Alpha particles travel only
a few micrometres in water and beta particles only a few millimetres; thus
any detector measuring these in unprocessed water will be observing only a
very thin film immediately surrounding it. Such an instrument will therefore
respond only to relatively high radionuclide contents. Gamma rays, on the
other hand, have a much larger range in water, and large unprocessed
samples can be used. Even in this case, the material at large distances from
the detector will have poorer geometrical efficiency.
For alpha and beta measurements, and for many gamma measurements,
separation of the radioactive material from the water is required. The most
common technique for this is evaporation of the water and transfer of the
residual solids to a dish or planchet suitable for the counter being used.
Removal of the water does not completely eliminate self-absorption loss.
Even with a sample as thin as 5 mg/cm2, an appreciable part of the beta
radiation and as much as 50 percent of the alpha radiation are lost.
Chemical separation is required where a specific radionuclide must be
determined in a mixture. This technique must also be used if the solids
content of the water is so high that simple evaporation is inapplicable.
Hazards
Sources of Information
Because of the novelty of the subject of radioactivity to many of the readers of this Manual,
information on the literature of this field may be useful. It is not possible to make an exhaustive
compilation of sources; accordingly, the following materials have been listed in the belief that
they form a useful survey. Very possibly, equally good materials have been omitted through lack
of acquaintance with them.
Books
For the novice in the field, books undoubtedly give the best introduction to a subject. The
first three books listed are excellent surveys of radioactivity and atomic energy, at a level
comprehensible to the nonspecialist:
Friedlander, G., Kennedy, J. W., and Miller, J. M., Nuclear and Radiochemistry, 2nd ed.,
Wiley, New York, 1964.
Lapp, R. E. and Andrews, H. L., Nuclear Radiation Physics, 3rd ed., Prentice-Hall, New
York, 1963.
Glasstone, S., Sourcebook on Atomic Energy, 3rd ed., Van Nostrand, Princeton, N. J., 1967.
The next book can be recommended as a classic in the field, although somewhat old. It is
particularly strong with respect to naturally occurring radionuclides:
Rutherford, E. R., Chadwick, J., and Ellis, C. E., Radiations from Radioactive Substances,
Cambridge University Press, 1951.
The next group includes somewhat less general texts, each good in its field, which is generally
indicated by the title:
Murray, R. L., Introduction to Nuclear Engineering, 2nd ed., Prentice-Hall, New York, 1961.
Glasstone, S., Principles of Nuclear Reactor Engineering, Van Nostrand, Princeton, N. J., 1955.
McCullough, C. R., Safety Aspects of Nuclear Reactors, Van Nostrand, Princeton, N. J., 1957.
Sharpe, J., Nuclear Radiation Detectors, Methuen, London, England, and Wiley, New York,
1955.
Taylor, D., The Measurement of Radioisotopes, Methuen, London, England, and Wiley, New
York, 1951.
Smyth, H. D., "A General Account of the Development of Methods of Using Atomic Energy
for Military Purpose Under the Auspices of the United States government" (1940-1945), U. S.
Government Printing Office, Washington, D. C., 1945 (better known as the "Smyth Report").
Glasstone, S., Ed., The Effects of Nuclear Weapons, U. S. Government Printing Office,
Washington, D. C., 1957 (much information on fallout).
Coryell, C. D., and Sugarman, N., Eds., Radiochemical Studies: The Fission Products,
McGraw-Hill, New York, 1951.
Wahl, A. C., and Bonner, N. A., Radioactivity Applied to Chemistry, Wiley, New York, 1951.
Compendia
Intermediate between books and the periodical literature are reports of conferences, groups
of papers, and similar compendia. A few of these may be listed:
National Nuclear Energy Series—a record and summary of Manhattan District and early
Atomic Energy Commission research. McGraw-Hill, New York.
Proceedings, International Conference on the Peaseful Uses of Atomic Energy, the record of the
1955 Geneva Conference^6 volumes, United Nations, New York, 1956.
Proceedings, Second International Conference on the TeacefuJJUses of Atomic Energy, the
record of the 1958 Geneva Conference, 34 volumes, United Nations, "New York, 1959. (An
edited series of 12 volumes is available from Pergamon Press, New York.)
Progress in Nuclear Energy, nine series each covering a specific area. Probably will appear
annually. Pergamon Press, New York.
350 MANUAL ON WATER
Periodical Literature
The periodical literature in nuclear energy is so voluminous that only a brief glimpse into the
field can be given. In addition to the usual journal publications, a vast number of government
reports (including U. S. Atomic Energy Commission, U. K. Atomic Energy Authority, and
similar groups) are available. For this reason, the abstract literature in this field is especially
important. Fortunately, the first journal listed below does an outstanding job of covering the
report literature, in addition to providing adequate coverage of the journals. The other abstract
coverage listed is generally somewhat more specialized than Nuclear Science Abstracts.
Abstracts, Reviews, and Bibliographies
Nuclear Science Abstracts, NSAB-A
Public Health Engineering Abstracts
CHAPTER 16 ON RADIOACTIVE NUCLIDES IN WATER 351
General Journals
Water Journals:
Miscellaneous
essential difference between the PWR and BWR is that the latter uses a
direct cycle, that is, no heat exchanger.
Typical operating conditions for the BWR are given in Table 1.
Reactor Components
A power reactor is composed of a core or group of fuel elements, control
rods, coolant, and moderator (Fig. 3). Heat energy is generated in the
reactor core, which contains an array of fuel assemblies. Various typical
PWR cores are rated from approximately 1500 to 3500 MWt (megawatt
thermal) with corresponding electrical outputs of 500 to 1200 MWe. An 800-
MWe core, for example, is approximately a right circular cylinder with an
equivalent diameter of 345 cm (136 in.), an active height of 348 cm (137 in.),
and is made up of 217 fuel assemblies. About 80 metric tons of uranium
oxide (UCh) are used in the reactor core. The core is completely open,
shrouded only at the outer periphery.
Each fuel assembly is made up of 176 fuel rods supported within a rigid
frame consisting of stainless steel upper and lower end fittings, Zircaloy fuel
rod spacer grids, and five Zircaloy axial guide tubes which will accept a
control element assembly (control rods). The overall length is about 394 cm
(155 in.), and the cross section is approximately 8 in. (20 cm) square. Each
assembly weighs about 585 kg (1300 Ib) (Fig. 3).
Each fuel rod contains sintered uranium oxide pellets of approximately
10 mm (0.4-in.) diameter and approximately 15 mm (0.6-in.) long. The
Zircaloy-4 cladding tube is approximately 0.66 mm (0.026 in.) thick. This
material has good corrosion behavior in the reactor environment and has
low neutron absorption cross sections. The tube length accommodates the fuel
pellet column and a fuel and gas expansion space. A diametral gap between
the pellets and the cladding provides for differential expansion between the
cladding and fuel to limit clad strain.
Control rods are located in selected fuel assemblies and contain materials
356 MANUAL ON WATER
Materials of Construction
The materials of construction listed in Table 2 are typical of modern water
reactors and consists of 300-series stainless steel primary system surfaces,
Zircaloy-clad fuel elements, and, in PWR's, Inconel-600 steam generator
tubing. With the possible exception of core materials, conventional con-
struction materials are used throughout the reactor coolant and steam-
condensate cycle.
These materials are common to both systems. For BWR's and those
PWR's that produce superheated steam, no copper alloys can be used for
condenser or feed water heater material; stainless steel only is employed.
This is to prevent thermally insulating copper deposits from forming on
fuel element surfaces (BWR) or steam generator (superheat section) tubing
(PWR).
Water Quality
High-purity water is needed in nuclear applications principally to pre-
clude fouling of heat-transfer surfaces, prevent corrosion, and preclude the
creation of radioactive materials through nuclear activation processes.
Corrosion can impair material integrity or increase corrosion product
concentrations, which result in activated residues on the primary system
surfaces, filters, and in waste systems.
Water has many uses in a nuclear plant, and the end use dictates the
quality requirements. The water used is largely recycled, but normal valve
or gland leakage may contain radioactivity and must be collected and
processed prior to reuse or discharge. Radioactive liquid waste processing
employs a wide variety of water purification techniques. Water is also used
for shielding in fuel storage pools, as a cooling fluid in reactor and auxiliary
cooling circuits, and as the working fluid.
As in any power cycle, long-term reliability is a necessary goal. To
achieve this goal, water quality control is established to opitimize the
environment in which the system materials will operate. The main objectives
of this control are:
1. To reduce the general corrosion of system materials.
2. To maintain material integrity of components and piping.
3. To assist in reactivity control of the reactor in PWR's.
The first two objectives are applicable to any power plant water treatment
program regardless of whether conventional or nuclear fuel is used. The
nuclear water technologist deals largely with the same problems as the
conventional power plant chemist.
There are many similarities in water quality requirements between PWR
and BWR power plants. In the primary system of a PWR or BWR, the
presence of the reactor neutron flux results in unique chemical conditions
not found in fossil-fueled plants. This flux has two major effects on water
chemistry control:
1. Impurities can be made radioactive.
2. Radiation can induce or cause normally nonoccurring chemical reac-
tions to take place.
mg/1
Chloride <0.15
Dissolved oxygen [temperature 66° C (1506F)] <0.10
In a PWR, hydrazine is employed during startup operations to ensure
that oxygen is not present to induce the stress corrosion reaction.
Oxygen reacts with hydrazine as follows:
The control rods are adjusted according to the need to compensate for
short-term changes, thus maintaining the power level. The movement of
the rods is usually initiated by an automatic controller. Power maneuvering
is accomplished by control rod movement also. A certain number of the
control rods are always kept in the "full out" position to provide the means
for fast reactor shutdown if needed.
Burnable poisons are employed as fixed poison rods in the fuel assemblies.
They accomplish two purposes: (1) they compensate for fuel burnup, and
(2) they help shape the power distribution within the core. Early in core
life, when the new fuel contains more fissile material, the burnable poi-
sons absorb neutrons, thus holding the reactivity and power down. By the
end of cycle, when a large portion of the fissile material is gone due to fuel
burnup, the burnable poisions are not present. Through reactions induced
by neutron absorption, they are converted into neutral materials with small
neutron absorption cross sections. Also in the beginning of the cycle, vhen
new fuel is introduced into the core, the local variations in power density are
relatively high. Judicious placement of the burnable poison rods makes more
360 MANUAL ON WATER
FIG. 5—Effect of temperature on the decomposition of fl2^4 for a reaction time of 0.8 min
with initial ^2^4 of 0.5 ppm in carbon steel and stainless steel tubing.
The kinetics of these reactions are quite rapid during reactor operation, and
many intermediate products are postulated before formation of the end
products. Since these reactions are dependent on the reactor flux, they are
first order with respect to the reactor power level and the concentrations of
reactants.
It is apparent from Reactions 3 through 6 that the presence of free hydro-
gen can shift the equilibrium of these reactions to preclude the excess
decomposition of water or formation of nitric acid. For this reason, PWR's
operate with an excess of hydrogen (added as hydrogen gas).
362 MANUAL ON WATER
FIG. 6—pH of various solutions (with and without boric acid) versus temperature.
CHAPTER 17 ON NUCLEAR WATER TECHNOLOGY 363
(approximately 0.9 to <0.01 ppm), which had been used to maintain a high
pH condition in the coolant. No boron was present during this test. Coolant
average temperature began to decrease coincidentally with lithium removal
(pH decrease). After the pH stabilized at approximately 5.75 (low pH), T
average continued to decrease for 24 h. Following this operation, lithium
hydroxide was added, and coolant T average began to rise and returned to
the predicted burnup rate after 24 h.
Figure It) shows the correlation of experimental data from field studies at
Yankee. The data points represent operation over a wide variety of boric
acid concentrations and include essentially zero boron.
Early speculations on the reason for pH-induced reactivity swings were
that neutron poisons from either defective silver-indium-cadmium control
rods or soluble boric acid were removed from core surfaces as a result of
alkali additions to the coolant. Later observations indicated that (1) the
magnitude of the effect was independent of boric acid concentration; (2)
there was no evidence of the appearance or disappearance of neutron
poisons during the reactivity change; (3) there was no effect at zero power;
and (4) it was independent of the choice of alkali but related by magnitude
and direction of pH change.
Tests now indicate that a more satisfactory hypothesis would involve the
effect of coolant chemistry on the structure or distribution, or both, of
corrosion product films on clad fuel surfaces. Changes in the properties of
these deposits affect (1) heat-transfer characteristics, which in turn affect fuel
temperature and, hence, reactivity due to the fuel Doppler effect; (2) the
extent and nature of local boiling, thereby changing the local and core
average voids, which would affect the void coefficient of reactivity; and (3)
366 MANUAL ON WATER
system hydraulic properties with associated changes in flow, that is, core AP,
and temperature.
Radioactivity
Nuclear steam supply systems employing pressurized water reactors are
indirect-cycle systems. The primary coolant, which picks up radioactivity
FIG. 11—Chemical and volume control system flow diagram.
370 MANUAL ON WATER
Fission Products
Fission products from two basic sources may be present in the reactor
coolant. The first is uranium contamination on the surface or in the metal
matrix of fuel cladding and core structural materials. This is essentially the
background or base activity and has been present in all reactors. A second
source of fission products arises when the cladding, which encapsulates the
fuel, is penetrated or has minor leakage. This condition has been observed in
reactors and does not impede safe continued operation of the plant.
The system design provides for operation of the core with a significant
fraction of the fuel elements being defective. Routine monitoring of fission
products provides the operator with trends in coolant activity and a history
of the relationship between various activity species. The information on
activity and ratios of activity of specific nuclides is useful for assessing
changes in the source of fission products.
One method widely used for routine monitoring of fission products is the
radiochemical analysis of 1-131 and 1-133. The relationship between these
isotopes is a function of the release mechanism; that is, recoil from surface or
a cladding interstitial uranium atom produces a different ratio than diffusion
from a defective fuel rod. Both mechanisms may be operating and releasing
fission products to the coolant simultaneously. However, the ratio between
the two iodine isotopes would reveal which release mechanism was pre-
dominant.
If fuel cladding failure is suspected, confirmation can be obtained by
observing the behavior of short half-life fission products during start-up
power transients. This effect, called "water-logging," is the result of water
entering the defective fuel rod during shutdown, and ejection of that water
and its contained activity upon resumption of power operation.
CHAPTER 17 ON NUCLEAR WATER TECHNOLOGY 371
Activation of Water
The isotopes N-13, N-16, N-17, and F-18 result from neutron activation of
oxygen isotopes occurring naturally in the light-water moderator. The
activity levels are a function of the reactor flux and system volume:
FIG. 12—Connecticut Yankee reactor coolant 1-131 concentrator versus power level, MWe.
372 MANUAL ON WATER
TABLE 6—Shippingport Atomic Power Station nonvolatile gamma activity. Core I Seed 3.
Percent of Total
Activity at Sampling Time. Gamma Radiation
Nuclide Half-Life dpm/ml" juc/ml /> At 1 h
N" 9.99 min 1.82X 104 8.19X 10"' 0.3
W"7 24 h 2.22 X 10' 9.00 X 10 4 2.9
Na :4
15 h I.92X 10" 8.64 X 10~4 1.8
p,s
109.8 h 2.8 X 104 I.26X 10": 21.3
Cs"s 32 min 1.03X 104 4.68 X 10~- 3.1
Mn 56 2.58 h 5.65 X 10' 2.54 X 10~- 4.5
Mn M 313davs 3.43 X I0: 1.09X 10"4 0.2
CuM 12.8 h ' 6.4 X 104 2.88 X 10": 39.2
I1JI 8 days 4.2 X 10' I.89X 10~5
I1" 21 h 1.03X 10' 4.67 X 10"4 14.8
I"4 52 min l.OOX 104 4.5 X 10"'
,,,5
6.7 h 1.92X 10: 8.64 X 10
Activation of Impurities
The concentration of impurities in reactor coolant is generally kept
extremely low by the strict control of makeup water quality, and by internal
purification. However, the small quantities of impurities present do become
activated and these can add to the system activities. The two most common
isotopes are:
Nuclide Half-Life Nuclear Reaction Target Source
Na24 15 h Na23 (n, y)Na24 impurity in water
Ar41 1.83 h Ar40 (n, y)Ar** air in water
Those plants which employ lithium hydroxide use lithium with the Li7
isotope only to avoid the generation of tritium from the Li6 isotope:
Fe Iron 10
Chromium 30
Nickel 60
These corrosion and wear products are released from the surface of the plant
piping and components and transported by the circulating coolant. A small
CHAPTER 17 ON NUCLEAR WATER TECHNOLOGY 375
percentage of these oxides is removed from the circulating coolant by the ion
exchanger in the CVCS. The metal oxides we are concerned with are those
which are deposited on the core where they become activated by core
radiation, the degree of activation depending upon the residence time on the
core. Initially, on a clean core surface, some of the corrosion products which
strike the surface adhere to the zirconium oxide surface. As more oxide
particles strike the surface, the deposit begins to build up. This continues
unless the shear forces on the oxide particles, due to the coolant flowing past
the particles, equal or exceed the forces causing the corrosion products to
adhere to the surface. Therefore, the erodable or loose layer will be limited
by the localized increase in coolant velocity through the core, the amount of
corrosion products released to the coolant being a function of the change in
velocity.
These activated metal oxides are then transported by the circulating
coolant. Again, a small percentage will be removed by the CVCS ion
exchanger, but some will redeposit on the plant surfaces as well as on the
core. When they deposit on the plant surfaces, a radiation level increase on
these surfaces will result and will be reflected in the radiation levels of the
primary system. Subsequent operation will result in release of deposits back
to the coolant which can again redeposit on the core to become further
activitated. The nuclides which have the greatest contribution to these
radiation levels are as follows:
Nuclide Half-Life Nuclear Reaction Target Source
51 50 51
Cr 27.8 days Cr («, 7) Cr steel and Inconel
Mn54 313 days Fe54 (n, p) Mn54 steel and Inconel
Fe59 45 days Fe58 (n, y) Fe59 steel and Inconel
Co58 71 days Ni58 (n, p) Co58 steel and Inconel
Co60 5.26 years Co59 (n, 7) Co60 stellite, steel
Cu64 12.8 h Cu63 (n, y) Cu64 17-4 PH steel
Zr95 65 days Zr94 (n, y) Zr95 Zircaloy
W181 130 days W180 (n, 7) W181 steel
W187 24 h W1M> (n, 7) W187 steel
FIG. 14—5/eom generatorfor an 800-M We PWR nuclear steam supply system (two required)
(1 ft- 30.48 cm; 1 in. = 2.54 'cm).
Water conditions for the two types of units reflect necessary differences in
water conditioning and auxiliary water treatment systems and equipment to
ensure efficient long-term operation.
One of the unique conditions of PWR operation is that reactor coolant at
a higher pressure than the secondary water may leak into the boiler if tubing
integrity is breached. This can cause the introduction of primary system fluid
containing boric acid and radioactive materials into the steam-condensate
cycle. The special considerations concerning this situation are discussed
later.
The unit pressure vessel is carbon steel and the boiler tubing is 19-mm (3/4
in.) diameter iron-chromium-nickel (alloy 600) having 40 to 50 mil wall
thickness. Chemistry adjustment to the boiler and feedwater is done (1) to
minimize corrosion of materials of construction, and (2) to ensure long-term
tubing integrity. The selection of additives and control limits recognizes that
the normal running, transient, and upset conditions may occur during plant
operation and that may result in potentially deleterious conditions to the
system.
Water conditions typically maintained with the steam generator are listed
in Table 7. These conditions recognize that occasional deviations from
normal may occur due to incursions of raw (cooling) water from surface
condenser tube leakage.
The steam generator is protected from corrosion or fouling of heat-
transfer surfaces, and steam purity is ensured by the control of chemical
additives and blowdown. Specific corrective measures largely depend on the
quality of raw water (whether brackish or freshwater, etc.) and the size or
rate of the leak.
An operational philosophy with respect to in-leakage is outlined in Table
8 and is based on the objectives stated in the preceding paragraph.
When "solids" chemical treatment is employed, there is no need for
condensate polishing equipment, since feedwater contaminants will con-
centrate in the generator or react with phosphates to form precipitates which
can be removed by blowdown.
Feedwater
The steam generator acts as a concentrating device during operation.
Soluble feedwater impurities which enter the steam generator become
concentrated in the water since the steam leaving the drum does not carry off
any appreciable amount. The recommended feedwater quality values given
in Table 9 cover a number of dissolved and suspended constituents and are
based on external or corrosion sources. For example, any contribution to
Total dissolved solids LIMITED TDS<1000 ppm immediately start chemical injection pumps to
0.5 - 2.0 ppm schedule inspection and pH 9.8 to 10.5 maintain required phosphate and pH conditions.
(abnormal) repair of condenser as PO4 15 to 40 ppm Increase blowdown rate to limit total dissolved
soon as system load re- Cl 250 ppm max solids concentration.
quirements permit.
Total dissolved solids EMERGENCY TDSOOOO ppm immediately start chemical injection pumps to main-
<2.0 ppm (excessive) (a) immediately reduce load pH 9.8 to 10.5 tain required phosphate and pH conditions. Do
as necessary to permit isola- PO4 15 to 40 ppm not continue to operate system if pH cannot be
tion of damaged conden- Cl 250 ppm max maintained above 8.0, or total dissolved solids
ser section. below 1000 ppm.
(6) prepare for orderly shut- if system goes into an orderly shutdown operation,
down of the system if feed- prepare to establish chemical conditions for wet
water TDS concentration layup of steam generator and auxiliary equipment
cannot be quickly reduced during condenser repair.
below 2.0 ppm.
CHAPTER 17 ON NUCLEAR WATER TECHNOLOGY 379
feedwater impurity concentration due to steam generator carry-over is
allowed in addition to the contribution from an external source. Thus, if 0.2
percent moisture carry-over occurs with 500 ppm dissolved solids in the
steam generator, then 1 ppm solids would be present in the feedwater due to
carry-over, and the limit on total dissolved solids (TDS) for normal
operation would then be 1.5 ppm instead of 0.5 ppm.
The TDS limit is specified to minimize steam generator fouling. Since
TDS can, in general, be measured quickly by conductivity instrumentation,
this category of impurities serves as a primary indicator of cycle contamina-
tion. The normal chloride concentration limit assures that long-term opera-
tion will not result in chloride-induced corrosion problems within the
secondary cycle. The silica concentration limit assures that silica carry-over
to the turbine by the vapor or steam solubility phenomena does not occur to
any appreciable extent with respect to turbine fouling. The oxygen and pH
specifications should limit the pickup of iron and copper from the feedwater
cycle to those levels necessary for long-term steam generator cleanliness.
Secondary cycle operation is considered normal as long as feedwater TDS
due to external sources is less than 0.5 ppm. Coupled with this is the
requirement that pH value, oxygen level, and copper/ iron levels are within
the values given in Table 9.
Operation with feedwater TDS concentration between 0.5 and 2.0 ppm
should be limited, and condenser repairs should be scheduled as soon as
practical. Values of feedwater solids concentration due to external source
contribution above 2 ppm are considered emergency levels. The unit load
should be immediately reduced, the damaged condenser section isolated, and
necessary repair work scheduled. The steam generator-turbine cycle should
be shut down if feedwater concentration cannot be quickly reduced to values
below 2 ppm.
operates wet after the first stage, these compounds will pass through the
turbine and have no effect on performance of the system.
Tests showed that Na2SO4 had low solubility (5 ppb); therefore, if it is
present in concentrations higher than 5 ppm, it may form deposits. However,
tests showed that soluble salts are easily removed by rinsing with feedwater-
quality water.
Primary-To-Secondary Leakage
In a PWR or closed-cycle power plant, reactor water can leak into the
boiler water or working fluid if steam generator tube integrity is breached.
Should this occur, primary water containing boric acid and radioactivity will
enter the secondary system.
stages of low-pressure turbines has been observed, but these deposits have
not affected turbine capability.
The feedwater will become contaminated with boric acid because of the
volatility phenomenon. For instance, about 60 ppm of boric acid will be
expected to be feedwater with 800 ppm boric acid in the generator, if
condensate demineralization is not utilized. Feedwater impurity limits must,
therefore, be raised to accomodate the presence of boric acid. Because of the
lower amount of boric acid in this part of the cycle, a maximum level of 1.0
ppm ammonia should be utilized to maintain feedwater pH values above 8.0.
Additionally, since ammonia is volatile, all portions of the feedwater system,
including those sections that bypass the normal ammonia injection points,
will equilibriate to the same pH level.
The carry-over of the biologically significant radioactive iodine has been
shown to be influenced by boiler water chemistry. When coordinated
phosphate/sulfite treatment has been used, no vaporization beyond normal
entrainment in moisture has been observed.
The benefit derived is a significantly lower release of iodine from the
secondary system off-gas. This is because the only form of iodine that is
volatile is the elemental (I2) form. In the presence of reducing sulfites in the
steam generator, any iodine introduced via primary-to-secondary leakage
will react to form nonvolatile iodides:
These reactions prevent the escape of iodine activity from the steam
generator as volatile iodine vapors in the steam, and limit iodine activity
release to that associated with moisture carry-over.
The amount of boric acid that would be present in the secondary system
feedwater in a full-size unit depends mainly on the leak rate, the concentra-
tion of H3BO3 in the reactor coolant, and the HjBO3 removel efficiency of
the condensate demineralizers. We have made extensive calculations, as-
suming leak rates from 0.000003 to 0.003 m 3 /s (0.05 to 50.0 gal/min), reactor
coolant H3BO3 concentrations from 0.006 to 0.82 m 3 /s (100 to 13 000
gal/min, and 0, 50, and 100 percent removal of H3BO3 by the condensate
polishing demineralizers. Table 11 lists some of these data.
The feedwater reference pH at 25° C (77° F) decreases with increasing
boric acid in the secondary system. However, boric acid at the concentra-
tions studied has little effect on the pH at elevated temperatures. In most
cases, the pH [25° C (77° F)] does not decrease below 9.4 [25° C (77° F)] as
long as the demineralizer is removing at least 50 percent of the H3BO3
leaking into the secondary system. Also, in some cases, the addition of a
small amount of ammonia will compensate for a pH [25°C (77°F)] decrease
below 9.3.
Earlier research on the behavior of both high-flow-rate deep-bed and
Powdex condensate polishers was extended to study their behavior in the
event of a boric acid leak. Table 12 shows the ultimate capacities obtained in
laboratory tests using 1.0, 10.0, or 100.0 ppm H3BO3 and —1.5 ppm NH 3
[equivalent to a pH (room temperature) of 9.5 at normal conditions] in the
influent. The results show that both types of systems can remove low
concentrations of boric acid that would be present in the secondary system if
a tube leak occurred. The presence of boric acid does not significantly affect
the capability of deep-bed demineralizers for removing sodium and chloride.
The condensate polishing system will continue to protect the OTSG and
turbine from condenser leak contaminants during a simultaneous OTSG
tube leak.
Summary
In this brief review, we have attempted to present the salient features of
the water chemistry control required for reliable operation of water reactors.
The 20 years of development and more than 10 years of operational
experience with the control principles described in this paper have led to an
accumulation of the technology which supports reliable plant operations.
Bibliography
Allen, A. O., The Radiation Chemistry of Water and Aqueous Solutions, Van Nostrand, New
York, 1961.
Bartnoff, S., Weisman, J., and Layman, W. H., Transactions, American Nuclear Society,
Vol. 7, No. 2, Nov. 1964.
Bergmann, C. A., "Effect of Low Cobalt Impurity Stainless Steel on Coolant Activity of
PWR's," American Chemical Society, April 1964.
Byrnes, D. E., "Some Physicochemical .Studies of Boric Acid Solutions at High Tempera-
tures," WCAP-3713, Sept. 1962.
TABLE 11—Reactor coolant to secondary-system boric acid leak calculations?
Reactor
Leak Coolant pH@ pH@ pH@ pH@ pH@ pH@
Rate, H3B03, H3B03fc 25° C 140°C 188°C 237° C 278° C 304° C NH^
f
gal/min* ppm ppm (77°F)r (285° F)< (370° F) (160°F)< (532° F)< (579° F)< ppm
0.05 13000 0.08 9.5 7.1 6.61 6.26 6.09 6.06 0
0.05 100 0.0006 9.5 7.1 6.61 6.26 6.09 6.06 0
0.5 13000 0.8 9.43 7.1 6.62 6.26 6.09 6.06 0
0.5 100 0.006 9.5 7.1 6.62 6.26 6.09 6.06 0
5.0 13000 8.1 9.09 7.08 6.61 6.26 6.09 6.06 1.7
5.0 100 0.06 9.5 7.09 6.61 6.26 6.09 6.06 0
50.0 13000 81.4 8.1 7.00 6.61 6.29 6.14 6.14 24
50.0 100 0.63 9.46 7.12 6.64 6.29 6.15 6.14 0
7.0* 5.71 5.36 5.21 5.36 5.43
9.S> 7.1 6.61 6.26 6.09 6.06
"'Assuming 50 percent removal of HjBOj by condensate polishing demineralizers. Lithium is 2.0 ppm Li in reactor coolant at all times. Ammonia is 1.5
ppm NHU in condensate and feedwater. The calculated values are for equilibrium conditions using 100 percent condensate polishing and 50 percent steam
flow to the feedwater heaters.
''Boric acid concentration at the demineralizer influent, shell side of the feedwater heater, and in the steam generator.
'The pH with H3BO3 and 1.5 ppm NH 3 present.
<AThe amount of NHj necessary to increase the pH to 9.3 @25°C (77°F).
''The pH of pure water at various temperatures.
'The pH of 1.5 ppm NHj at various temperatures.
®l gal/ min = 0.00006 m3s.
CHAPTER 17 ON NUCLEAR WATER TECHNOLOGY 385
POWDEX TESTS*
Influent, ppm Ultimate Capacity
HiBOj Ib HjBOi/lb dry anion (OH)
1.0 0.03
10.0 0.14
100.0 0.24
-All tests used NH4R-ROH resin in a 2:1 ratio. Flowrate was 50 gal/min/ft 2 and temperature
25°C (75°F).
6
All tests used NH4R-ROH resin in a 1:1 ratio and dosage of 0.15 lb/ft 2 . Flowrate was 163
litres/min/m 2 (4 gal/min/ft 2 ) and temperature 25°C (75°F).
Cohen, P., Water Coolant Technology of Power Reactors, American Nuclear Society
Monograph, Gordon and Breach Science Publishers, New York, 1969.
Cohen, P. and Graves, H. W., Jr., Nucleonics, Vol. 22, No. 5, May 1964.
Connally, J., "Closed Cycle Reactor Plant Operating Experience at Yankee Rowe," National
Association of Corrosion Engineers, Houston, Tex. 1969.
Copson, H. R. and Berry, W. E., Corrosion, Vol. 16, 1960, pp. 79t-85t.
Copson, H. R. and Berry, W. E., Corrosion, Vol. 18, 1962, pp. 21t-26t.
Dickinson, N. L. et al, Proceedings, American Power Conference, Vol. 19, 1957, pp. 692-706.
Eichenberg, et al, "Effects of Irradiation and Bulk UO2," WAPD-183, Oct. 1957.
Graves, R. H., "Chemistry and Waste Management at the Conneticut Yankee Atomic Power
Plant," National Association of Corrosion Engineers, Houston^ Tex., 1969.
Hicks, J. H., et al, "Nuclear Steam Supply System Water Chemistry," B&W TPI-11,
Babcock & Wilcox.
Lechnick, W., Martucci, J. A., and Scherer, R. D., "Shippingport Operations," DLCS 36403,
Operational Chemistry, Part 5, Chapter 1, 1963.
Martucci, J. A. and Reckman, B. J., Jr., "Water Technology for PWR Nuclear Power
Plants," Nov. 1970.
Meek, M. E., "The Calculated pH of Aqueous Boric Acid Solutions as a Function of
Temperature and Added Base Content," WCAP-3269-51, March 1951.
Miller, D. A. and Bryant, P. E. C., "Corrosion and Coolant Chemistry Interactions in
Pressurized Water Reactors," National Association of Corrosion Engineers, March 1970.
Picone, L. F., "The In-Pile Test of Chemical Shim," WCAP-3729, June 1963.
Rodden, C. J., "Analysis of Essential Nuclear Reactor Materials," Division of Technical
Information, U. S. Atomic Energy Commission, 1964.
Sawochka and Pearl, "Corrosion Product Chemistry of a Boiling Water Reactor," NEDO
13129, Class I, Aug. 1970.
Stein, W., "Chemistry at the Indian Point Nuclear Power Station," National Association of
Corrosion Engineers, Houston, Tex., 1969.
Tash, J. A., Martucci, J. A., and Dunn, D. N., "Shippingport Operations," DLCS 36401,
Operational Chemistry, Part 4, Chapter 3.
Van Rooyen, D., Copson, H. R., and Berry, W. E., "Corrosion Behavior of Nickel-
386 MANUAL ON WATER
Summary
'The italic numbers in brackets refer to the list of references appended to this chapter.
387
Copyright© 1978 by ASTM International www.astm.org
388 MANUAL ON WATER
General
Experimental Design
In order to properly design valid experimental procedures, careful con-
sideration must be given to the following:
(a) The radionuclide to be determined.
(b) The relative activity levels of interferences.
(c) The type and energy of the radiation.
(d) The original sample matrix.
(e) The required accuracy.
Having considered the foregoing, it is now possible to make the following
decisions:
(a) In what chemical or physical form must the sample be for radioassay?
(b) What chemical purification steps are necessary?
(c) What type of detector is required?
(d) Is energy spectrometry required?
(e) How long must the sample be counted in order to obtain statistically
valid data?
(/) Must isotopic composition be determined?
(g) What size sample is required?
For example, gamma-ray measurements can usually be performed with
little or no sample preparation whereas both alpha and beta counting will
always require chemical processing. If low levels of radiation are to be
determined', very large sample and complex counting equipment may be
necessary.
More detailed discussions of the problems and interferences are included
in the sections for each particular type of radiation to be measured.
Apparatus
The apparatus required for the measurement of radioactivity consists, in
general, of the detector and associated electronic equipment. The latter
usually includes a stable power supply, preamplifiers, a device to store or
display, or both, the electrical pulses generated by the detector, and one or
more devices to record information.
Some detectors and high-gain amplifiers are temperature senstive; there-
fore, changes in pulse amplitude can occur as the ambient room temperature
varies. For this reason, it is necessary to provide temperature-controlled air
conditioning in the counting room.
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 389
Special Instrumentation
This section describes some radiation detection instruments and auxiliary
equipment that may be required for special application in the measurement
of radioactivity in water.
4-Tr Counter—The 4-?r counter is a detector designed for the measure-
ment of the absolute disintegration rate of a radioactive source by counting
the source under conditions that approach a geometry of 4-7r steradians. Its
most prevalent use is for the absolute measurement of beta emitters [3,4],
and for this purpose a gas-flow proportional counter similar to that in Fig. 1
is common. It consists of two hemispherical or cylindrical chambers whose
walls form the cathode, and with a looped-wire anode in each chamber. The
source is mounted on a thin supporting film between the two halves, and the
counts recorded in each half are summed. An argon (90 percent)-methane
(10 percent) gas mixture can be used; however, pure methane gives flatter
and longer plateaus and is preferred for the most accurate work. The
disadvantage is that considerably higher voltages, about 3000 V, rather than
the 2000 V suitable for argon-methane, are necessary. As with all gas-filled
proportional counters, very pure gas is necessary for very high detector
efficiency. The absence of electronegative gases that attach electrons is
particularly important since the negative pulse due to electrons is counted in
gamma-ray counting, the efficiency of the crystal for the gamma energy
being measured and the absorption in the crystal cover must be taken into
account.
The liquid scintillation counter is also essentially a 4-rr counter for beta
particles, since nearly all the radiations are emitted into and interact with the
detecting medium.
Low-Geometry Counters—This type of instrument is particularly useful
for the absolute counting of alpha particles. The alpha emitter, in the form of
a very thin solid source, is placed at a distance from the detector such that
only a small fraction ( < 1 percent) of the alpha particles are emitted in a
direction to enter the counter. This solid angle is obtained from the physical
measurements of the instrument. The space between the source and detector
is evacuated to eliminate the loss of alpha particles by absorption in air. The
detector can be any counter that is 100 percent efficient for all alpha particles
that enter the sensitive volume—a gas-flow proportional counter with a
window that is thin (about 1 mg/cm2) covering. The advantages of this
instrument for absolute alpha counting are (1) that the effect of absorption
of alpha particles in the source itself is kept to a minimum since only
particles that travel the minimum distance in the source enter the detector
(particles that have longer paths in the source are emitted at the wrong
angle), and (2) that back-scattered alpha particles (those emitted into the
source backing and reflected back up through the source) lose sufficient
energy so they cannot enter the detector. One such instrument is described in
Reference 12.
Internal Gas Counters—The internal gas counter, so named because the
radioactive material, in the gaseous state, is placed inside a counting
chamber and thus becomes part of the counting gas itself, is useful for high-
efficiency counting of weak beta and X-ray emitters. The radiations do not
have to penetrate a counter window or solid source before entering the
sensitive volume of a detector. The counter may be an ionization chamber,
or it may be operated in the Geiger or proportional mode. Most present-day
instruments are of the latter type, and they generally take the form of a metal
or metal-coated glass cylinder as cathode with a thin anode wire running
coaxially through it and insulated from the cylinder ends. A wire through the
wall makes electrical contact to the cathode. The counter has a tube opening
through which it may be connected to a gas-handling system for filling. The
purity of the gas is important for efficient and reproducible counting,
particularly in the proportional mode.
In a modification of the internal gas counter, scintillation counting has
been used in place of gas-ionization counting. The inner walls of the
chamber are coated with a scintillation material and the radioactive gas
introduced. An optical window is made a part of the chamber, and the
counting done by placing this window on a multiplier phototube to detect
the scintillations. This system is particularly useful for counting radon gas
with zinc sulfide as the scintillator. Additional details on internal gas
counting may be found in Reference [13].
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 393
when a high voltage is applied. Because of the high mobility of the small
lithium atom, the detector must be kept cold to prevent the diffusion of
lithium out of the crystal. In addition, in order to obtain high resolution, the
detector must be operated at low temperatures to reduce thermal noise. At
room temperature, sufficient free electrons will be present in the crystal to
obscure the measurement of gamma and X-rays (but not of alpha particles).
Consequently, the detectors are operated and kept at liquid nitrogen
temperatures by a cryostat consisting of a metallic cold-finger immersed in a
Dewar flask containing liquid nitrogen. If the detector is allowed to warm to
room temperature for a short time, its resolution will deteriorate and in an
hour or so it will lose sufficient lithium so it cannot function as a detector
without redrifting. The detector is kept hermetically sealed in a vacuum to
prevent impurities from condensing on the surface and lowering its resis-
tance, and to reduce beat transfer from the room to the crystal. Aluminum is
the usual covering, and a molecular sieve or vac-ion pump is incorporated
into the system to maintain the vacuum. The electronic components required
to obtain spectra are similar to that for sodium iodide crystals, except that
because smaller pulses must be measured, high-quality electronics are
needed. The complete system includes a high-voltage bias supply for the
detector (up to 5000 V for large depletion volumes), a preamplifier, amplifier
(usually charge-sensitive), biased amplifier (if needed), pulse height analyzer,
and recording device.
A gamma-ray entering either a Nal(Tl) crystal or a semiconductor
detector may lose all or part of its energy in the detector. In the former case,
through multiple Compton interactions or the photoelectric effect, a full
energy peak is obtained. Otherwise, only part of the energy will be observed
and a Compton continuum spectrum is seen. An alternative process for high-
energy gamma-rays (< 1.02 MeV) is pair production, in which an electron-
position pair is produced, and gamma-ray peaks are observed at 0.511 MeV
intervals below the full energy peak. The two most important operating
characteristics of gamma detectors are efficiency and resolution. The "peak-
to-Compton" or "peak-to-valley" ratio is frequently given in the literature
and is related to both efficiency and resolution. These parameters should be
specified by the manufacturer and the conditions under which they were
measured should be given.
The resolution of sodium iodide crystals is usually specified in terms of the
width of the full-energy gamma-ray peak at half its maximum, the "full
width at half maximum" (FWHM). This is shown graphically in the gamma-
ray spectrum in Fig. 2. The resolution improves with increasing energy and
the standard for comparison is usually the 0.662 MeV gamma ray emitted in
the decay of 137Cs. Good sodium iodide crystals have resolutions in the range
of 6.5 to 7 percent for 137Cs. Detection efficiency for the same geometry and
window thickness is a function of several parameters, and much published
information of efficiencies for various energies, detector sizes, source to
detector distances, and other variables is available [14], The efficiency for
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 395
silicon, and 3 mm-1 for germanium. However, germanium detectors are not
yet available in sizes approaching that of sodium iodide. The efficiency of a
germanium (lithium) detector is generally expressed by comparison with that
of a 76- by 76-mm cylindrical Na(Tl) detector. Comparison is made between
the full-energy peak efficiencies for the 1.33-MeV gamma ray of ^Co when
the source is 250 mm from the detector. A germanium detector with a
volume of 35 cm3 has an efficiency about 5 percent that of a 76- by 76-mm
Nal(Tl) crystal. Larger Ge(Li) detectors are available with relative ef-
ficiencies of 25 to 30 percent.
There are limitations in the efficiency of the light production and
collection processes in the sodium-iodide-photomultiplier system that make
its resolution inferior to that of semiconductor detectors. One important
factor is that about 500 eV are required to produce an electron at the
photocathode in a sodium iodide detector system, while the average energy
to produce the analogous electron-hole pair in silicon is only 3.5 eV and in
germanium 2.8 eV. The resolution of semiconductor detectors does not
change greatly with energy. Presently available germanium detectors have
resolutions of 1.5 to 2.8 keV at 1.33 MeV and are from 3 to 30 percent
efficient compared with a 76 by 76 mm Nal(Tl) detector. This greater
resolution makes this detector the one of choice for gamma-ray spectrometry
and cancels to some extent the higher efficiency available from sodium
iodide. Since the pulses from a single photopeak are spread over a much
smaller energy range in germanium than in sodium iodide, the background
under the peak is much less. This means that for small sources of moderately
energetic gamma rays, germanium is more sensitive than sodium iodide. This
is indicated in Table 1, where the efficiencies and backgrounds of a 76- by 76-
mm sodium iodide crystal and a 35-cm3 (5.5 percent efficiency) germanium
detector are compared.
Spectra of beta particles and conversion electrons can be obtained with
sodium iodide and semiconductor detectors sufficiently thick (a few centi-
metres) to absorb the particles completely. One disadvantage of sodium
iodide and cooled lithium-drifted semiconductors is their relatively thick
entrance windows. Other semiconductor detectors, particularly the silicon
surface barrier type, have thin entrance windows and can be used for beta
particles at room temperature or better at 0°C. The 5- to 10-keV resolution
for 600-keV electrons is better than the 12- to 30-keV resolution for 5-MeV
alpha particles.
Good spectra of low-energy beta particles, conversion electrons, and X-
rays can be obtained with a gas-flow proportional counter provided that a
linear preamplifer is used. The resolution is intermediate between sodium
iodide and germanium. To reduce back-scattering, the chamber should be
made of low-Z material. A counter constructed of a cylinder of graphite-
impregnated plastic, lucite ends, and a thin coaxial center wire gives good
spectra for such radiations [14]. A hole is cut into the outer wall and covered
with aluminized Mylar film to provide a thin entrance window. Argon (90
percent)-methane (10 percent) is a suitable counting gas.
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 397
0.66 MeV
Nal 20 14 9 4.1 6.3
Ge 0.11 1.3 0.68 3.6 6.8
1.33 MeV
Nal 8 5.8 3.8 6.2 9.5
Ge 0.055 0.75 0.38 4.5 8.9
NOTES—
Nal: 76 mm diameter by 76 mm high cylindrical detector.
Ge(Li): 35 cm3 active volume—5.5 percent efficiency.
A = small source placed on detector.
B = 57 by 57 by 57-mm-thick source place on detector.
Counting efficiency: percent of photons emitted from the source that give a full-energy peak.
Shielding: 152 mm of iron, 3.2 mm lead.
Counting time: One 30 000 s count for both source and background.
Detection limit: The number of photons emitted from the source whose net count equals
twice the counting error, or
where N is the total number of counts recorded when the source is measured, and NB is the
total number of counts recorded when the background is measured.
which minimizes evaporation by loss either through the walls or out of the
stopper.
If a planchet is prepared as a standard, it should be placed in a suitable
container for storage which will prevent the surface containing the activity
from being contacted. A recommended practice is the preparation of two
standards, using one and storing the second for periodic checks to see that
the working standard has not been altered.
Counter Control Charts—The daily standard counts made on any counter
must be evaluated on a statistical basis and the best way to do this is to
maintain a control chart on each counter. A control chart is a graph showing
the number of counts recorded in a fixed counting period against day of the
year. The initial entry, N is determined from the average of several
measurements over a period of days. Then the error bands of x and
± 2±3S
S x are entered (Sx- \/N) and lines are drawn on the chart which allow for
decay of the standard over the year. For a long-lived source, such as cesium-
137, which has a half life of 30 years, about 2.5 percent of the activity is lost
in one year. An example of a control chart is shown in Fig. 4.
The result of the standard count is entered in the control chart and the
following action is taken:
If the result is inside the ± 2SX band, the counter is considered to be in
control.
If the result lies outside the ± 2SX band but inside the ± 35V band, the
counter is considered to be in control, but this result should be flagged.
If the result lies outside the ± 35V band, the counter is considered out of
control. Corrective action is needed if repeated counts remain outside the
± 3SX band.
For alpha and gamma spectrometry it is also important to monitor for
system resolution.
404 MANUAL ON WATER
In addition to the control charts made on each counter, all pertinent in-
formation about the system should be kept in a log book or permanent file:
Counter Logs
a and j3 Counters 7 Spectrometers
Standard counts Standard counts
Background counts Standard resolution
System changes Background counts
Control charts Control charts
Counting Statistics
Each nuclear disintegration [5,20,27] is a completely random and inde-
pendent process. Established methods of statistical analysis are available to
describe the random phenomenon of nuclear disintegration. The total
number of particles counted in a time period can be shown to deviate from
the average according to the expression, N ±\fN~, where N is the number of
counts in the counting period t. Similar behavior is found in the background
count rate for any counter, and the recorded background will deviate from
the average according to the expression NB ±-\fNB, where NB is the number
of counts recorded in the counting period tB. The net count rate found
is then
where Sx is the standard deviation of the net count rate and is given by
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 405
or for the net count rate with its standard deviation we have
In practice, many counts will "be made which deviate from the average by
more or less than the standard deviation since 5V by definition would give
those limits X - Sx and X + Sv which would include about 68 percent of
all observed values. In terms of the population of observations between
limits, we can express the change of probability of a result being between the
limits X - K S{ and X + KS, as "confidence levels" where K is simply a
multiplier for Sv. In evaluating the effect of K, we can tabulate K and the
confidence level.
itself being counted and by all substances separating the sample from the
detector. This effect is usually small for gamma radiation, but beta and alpha
radiation are seriously affected. If sources of the same atomic number and
mass are compared on the same counter in the same geometry, absorption
will be constant under these conditions but should not be ignored. Since
the sample mass may vary significantly, calibration curves must be con-
structed to correct for changes in self-absorption.
Quenching: This is any process which reduces the photon output in a
scintillation system; this in turn reduces the measured count rate. Quenching
can be caused by such things as sample color and chemicals in the sample.
The need to correct for this phenomenon can be avoided if samples of the
same color and same chemical composition are compared. If this is not
possible, most instrument manufacturers and texts describe methods for
construction of calibration curves to correct for this phenomenon [22-24].
Overall Uncertainty in a Determination—Measurement results should be
reported with the estimated overall measurement uncertainties shown. There
are two approaches to this. One is a rigid propagation of uncertainties,
which is not sound in practice since the individual components are not well
characterized, and the second is a combination of known uncertainties. In
combining uncertainties, use the relationship
where
S = overall uncertainty of measurement (RSD),
S\ = random counting uncertainty (RSD),
5*2 = other random uncertainties (RSD),
where
Sy spec = overall error for the measurement (relative standard deviation
or RSD),
SV = calibration uncertainty (RSD), and
Sa = counting uncertainty (RSD).
where
Sx = overall uncertainty for measurement (RSD),
SM = intrinsic precision of method (RSD),
Sa = counting uncertainty (RSD), and
Sc = calibration uncertainty (RSD).
(NOTE: The use of ASTM Methods which have been round-robin tested will give you a method
where Sx is known.)
If the sample and background counting times are equal (/ = IB), we can use a
slightly different form
408 MANUAL ON WATER
counts
The total count form is simpler to use in estimation of MDA's, but care
must be taken in converting from total counts back to concentration in
the sample. An example of the calculation of MDA's follows for ASTM
Test for Radioactive Barium in Water (D 2038), which covers the deter-
mination of barium-140 in water:
By beta counting, assuming 80 percent chemical yield and counting at 40
percent efficiency with 1-cpm background. For 100-min count periods we
have
counts
MDA
MDA =
MDA= 107 counts
in dpm terms
MDA = = 21.9 dpm
MDA =
in dpm terms
MDA= = 11.5dpm
where
N = number of counts accumulated,
/ = sample counting period, min,
NB = number of background counts accumulated,
tB = background counting period, min,
C = net counts per minute per millilitre, cpm/ml
V = volume of sample, millilitres, and
Y = fractional recovery of species (unity in methods where complete
recovery is assumed).
where
D = disintegrations per minute per millilitre, dpm/ ml
410 MANUAL ON WATER
E= GP
where
G = fractional abundance of gamma ray concerned and
P = photopeak detection efficiency (fraction).
In beta counting
where
fj ~ detector efficiency factor for a source of given beta energy,
fa = absorber factor for total absorber thickness (detector window + air
space + absorber + cover) for a source of given beta energy,
fs= self-absorption and backscatter factor for a given precipitate thick-
ness and given beta energy, and
fm = number of charged particles per disintegration.
where
A = concentration in microcuries per millilitre (juCi/ml).
D = D° exp (-0.693 t/ 7)
where
D° = disintegration rate at time zero, that is, reference time
t = elapsed time between measurement and reference time, and
T = half-life of nuclide.
Alpha Counting
This section covers the measurement of the alpha particle radioactivity
of water. It is applicable to alpha emitters having energies above 3 MeV
at activity levels above 0.5 picocuries per sample.
Summary—Alpha particles are characterized by intense loss of energy
in passing through matter. This intense loss of energy is used in differ-
entiating alpha radioactivity from other types through the dense ionization
or intense scintillation it produces. This high rate of loss of energy in
passing through matter, however, also makes sample preparation conditions
for alpha counting more stringent than is necessary for other types of
radiation.
Alpha Detectors—Alpha radioactivity is normally measured by one of
several types of detectors in combination with suitable electronic com-
ponents. The detector devices most used are ionization chambers, pro-
portional counters, silicon semiconductor detectors, and scintillation
counters. The associated electronic components in all cases would include
high-voltage power supplies, preamplifiers, amplifiers, sealers, and re-
cording devices.
Detection Technique—In all of these systems, the initial event is con-
verted to an electrical pulse which is amplified to a voltage sufficient to
operate the sealer mechanism where provision is made for recording each
pulse. The number of pulses per unit of time is directly related to the disin-
tegration rate of the test sample. The efficiency of the system can be deter-
mined by counting standards prepared in the same manner as the samples.
An arbitrary efficiency factor can be defined in terms of a different radio-
nuclide such as natural uranium, polonium-210, plutonium-239, or ameri-
cium-241.
Measurement Variables—The measured alpha counting rate from a
sample will depend on a number of variables. The most important of these
variables are geometry, source diameter, self-absorption, absorption in
air and detector window, coincidence losses, and backscatter. These are
discussed in detail in the literature [4,5] and in many cases can be measured
or corrected for by holding conditions constant during the counting of
samples and standards. These effects may be described by the following
relationship
where
Apparatus
lonization Chambers—Alpha particles entering the sensitive region of an
ionization chamber produce dense ionization of the counting gas. The
electrons are collected at the anode, thus developing a voltage pulse. Gridded
ion chambers are used for alpha spectrometry, but have been replaced by
solid-state detectors. The major advantage of the ion chamber is its ability to
measure large area samples with essentially a 2?r geometry. The chambers
are operated at an overpressure with gas mixtures such as 10 percent
methane-90 percent argon or 2 percent ethylene-98 percent argon. The peak
resolution of such a detector is about 50-keV FWHM; refer to ASTM
Recommended Practice for Alpha Spectrometry (D 3084).
Proportional Counters—Alpha particles entering the sensitive region of a
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 413
proportional counter produce ionization of the counting gas. In this case, the
electrons are accelerated toward the anode, producing secondary ionization
and developing a large voltage pulse by gas amplification. Proportional
counters are usually operated in the "limited proportional" range, where the
total ionization is proportional to the primary ionization produced by the
alpha particle.
Proportional detectors are generally constructed of stainless steel or
aluminum; see Fig. 5. No additional shielding is required for alpha
proportional counting. The counter should be capable of accepting mounts
up to 51 mm in diameter. Proportional detectors are available in two types,
either with or without a window between the sample and the counting
chamber. The manufacturer's specifications for either type should include
performance estimates of background count rate, length and slope of the
voltage plateau, and efficiency of counting a specified electrodeposited
standard source along with the type of gas used in the tests. For a window
flow counter, the window thickness in milligrams per square centimetre
should also be specified. With windowless low counter, the sample and
sample mount should be made of an electrical conductor in order to avoid
erratic behavior, due to static charge buildup.
Alpha emitters are counted with proportional instruments in 2?r, or 50
percent, configuration. TWO-TT geometry is obtained by placing the sample
on a flat planchet inside the detector. Half the alpha particles are emitted
downward into the planchet, of which approximately 2 percent are back-
scattered in the upward direction. The other half are emitted upward into the
gas volume.
Typical parameters for the alpha windowless flow counter are: back-
ground count rate—10 counts per hour; length of voltage plateau— 300 V;
slope of voltage plateau—1 percent per 100 V for an electrodeposited source.
For a window flow counter, typical values are: window thickness—1
mg/cm2; background count rate—10 counts per hour; length of voltage
plateau—300 V; slope of voltage plateau—1 percent per 100 V for an
in distinguishing between the two. The problem is primarily due to the broad
continuum of beta energy distribution up to the maximum energy, and the
poor resolution of liquid scintillation spectrometers. This problem is aggra-
vated because the light yield per MeV of alpha particles in most liquid
scintillators is approximately tenfold lower than a beta particle of equivalent
energy, putting the pulses from alphas and high-energy betas in the same
region. Correction for beta activity may be made by certain mathematical or
graphical techniques. It is preferable to separate the alpha emitter from the
bulk of the beta activity by chemistry.
Semiconductor Detectors—The semiconductor detectors used for alpha
counting are essentially solid-state ionization chambers. The ionization of
the gas in an ionization chamber by alpha particles produces electron-ion
pairs while in a semiconductor detector, electron-hole pairs are produced.
The liberated charge is collected by an electric field and amplified by a
charge-sensitive amplifier. In general, silicon surface barrier detectors are
used for alpha counting. These detectors are /i-type base material upon
which gold is evaporated to make a contact. The semiconductor material
must have a high resistivity since the background is a function of the leakage
current. This leakage current is present in an electric field since the starting
material is a semiconductor, not an insulator. The reversed bias which is
applied reduces the leakage current, and a "depletion layer" of free-charge
carriers is created. This layer is very thin and the leakage current extremely
low; therefore, the interactions of photons with the detector will have a
neglible effect. Since the detector shows a linear response with energy, any
interactions of beta particles with the detector can be eliminated by
electronic discrimination. The semiconductor is of special interest in alpha
counting, where spectrometric measurements may be made, since the
average energy required to produce an electron-hole pair in silicon is 3.5
±0.1 eV, compared with the 25 to 30 eV to produce an ion pair in a gridded
ionization chamber. Consequently, silicon detectors provide much improved
resolution and also normally have lower background count rates.
The detector size is generally less than 25 mm (1 in.) in diameter, since the
resolution decreases and cost increases with detector size. For best results,
the sample should be electrodeposited to make an essentially massless
source. The detector is operated in a vacuum chamber. Typical backgrounds
range from 0.3 to 0.6 counts per hour. Additional specifications for detectors
may be found in ASTM Method D 3084.
Absorption—The range of alpha particles is a few centimetres in air and a
few thousandths of a centimetre in solids. Even fairly short path lengths in
air and passage through thin windows will result in the absorption of some
fraction of the alpha radiation.
Calibration of alpha counting equipment for specific nuclide measurement
should be carried out using a standard of similar alpha energy measured
under exactly the same conditions as the sample to be counted.
When the gross alpha activity of a sample is to be measured [ASTM Test
416 MANUAL ON WATER
Activity C =
where:
Disintegration rate
Concentration A =
where:
A = concentration in microcuries per millilitre (/uCi/ml).
where
EM = efficiency of counter for natural uranium (fraction).
To properly evaluate the result, the uncertainty associated with the con-
centration should be calculated according to the recommended procedure
given earlier.
Beta Counting
This section covers the measurement of the beta particle radioactivity of
water. It also covers the general techniques used to prepare and measure
the activity resulting from radiochemical separation of specific nuclides or
groups of nuclides in water samples. It is applicable to beta emitters with
activity levels above 10 picocuries per sample for most counting systems.
For samples of lower activity, see ASTM Recommended Practice for Low-
Level Activity Measurements (D 3085) [2]. The method is not applicable
to samples containing radionuclides that are volatile under conditions of the
analysis. General information on radioactivity and measurement of radia-
tion may be found in the literature [9,11}.
Summary—Beta radioactivity may be measured by one of several types
of instruments which provide a detector and a combined amplifier, power
supply, and sealer. The most widely used detectors are proportional or
Geiger-Muller counters, but scintillation systems offer certain advantages.
Among the gas ionization-type detectors, the proportional-type counter
is preferable because of the shorter resolving time and greater stability of the
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 419
instrument. For perparing solid sources from water samples for beta activity
measurement, the test sample is reduced to the minimum weight of solid
material having measurable beta activity by precipitation, ion exchange, or
evaporation techniques. For measuring solid sources resulting from in-
dividual radiochemical separation procedures, the precipitate is appro-
priately mounted for counting.
Beta particles entering the sensitive region of the detector produce
ionization or scintillation photons which are converted into an electrical
pulse suitable for counting. The number of pulses per unit time is directly
related to the disintegration rate of the sample by an overall efficiency factor.
This factor combines the effects of sample-to-detector geometry, sample self-
shielding, backscatter, absorption in air and in the detector window (if any),
and detector efficiency. Because most of these individual components in the
overall beta-particle detection efficiency factor vary with beta energy, the
situation can become complex when a mixture of beta emitters is present in
the sample. The overall detection efficiency factor may be empirically
determined with prepared standards of composition identical to that of the
sample specimen, or an arbitrary efficiency factor can be defined in terms of
a single standard such as cesium-137 or other nuclide. Gross counts can
provide only a very limited amount of information and therefore should be
used only for screening purposes or to indicate trends.
Liquid scintillation counting avoids many sources of error associated with
counting solid beta sources, such as (1) self-absorption, (2) backscattering,
(3) loss of activity during evaporation due to volatilization or spattering, and
(4) variable detection efficiency over a wide beta-energy range. In addition to
the greatly improved accuracy offered by liquid scintillation counting,
sample preparation time and counting times are significantly shorter.
Sample preparation involves only adding a sample aliquot to the scintillator
or gel phosphor. Because every radioactive atom is essentially surrounded by
detector molecules, the probability of detection is quite high even for low-
energy beta particles. Radionuclides having maximum beta energies of 200
keV or more are detected with essentially 100 percent efficiency. Liquid
scintillation can, at times, be disadvantageous due to chemiluminescence,
phosphorescence, quenching, or the typically higher backgrounds.
Organic scintillators, such as p-terphenyl plus a wave shifter, in a plastic
monomer are polymerized to form sheet material of any desired thickness.
The plastic phosphor counting system [10] has its widest use as a beta
particle detector for separated, solid samples rather than for beta spectro-
metry applications.
This plastic beta scintillator phosphor is mounted directly on the sample
and is discarded after counting. The phosphor-sample sandwich is placed in
direct contact with the photomultiplier tube yielding essentially a 2n
configuration. Since the output pulse of the detector system is energy
dependent, the counting efficiency for a given phosphor thickness of 0.0254
cm yields the highest counting efficiency with the lowest background.
Solid samples, precipitates from radiochemical separations containing 3
420 MANUAL ON WATER
where
cpm = recorded counts per minute, corrected for background, and
dpm = disintegrations per minute yielding beta particles.
Gp = source-to-detector geometry, which is the solid angle subtended
by the sensitive area of the detector. This is corrected for most
easily by maintaining constant counting configuration and geo-
metry for standards and sample measurements.
fhs = backscatter factor, or ratio of cpm with backing to cpm without
backing. This is the phenomenon in which particles originally
emitted away from the detector are scattered back toward it by
reflection off the source backing material. Its value ranged from 1
to almost 2, depending on the thickness and atomic number of the
backing material. The backscatter error may be minimized by
using identical backing material for counting standard and samples.
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 421
fm. = factor to correct for losses due to absorption in the air and window
of external counters. It is equal to the ratio of the actual counting
rate to that which would be obtained if there were no absorption
by the air and window between the source and sensitive volume of
the detector. It is related to the absorption coefficient and density
of the absorber by the approximate equation, af w= exp (-JLUC),
where /x — absorption coefficient, in square centimetres per milli-
gram, and x = absorber density in milligrams per square centi-
metre. In practice, it can be accounted for, together with the
geometric factor, by maintaining the geometry of the counting
configuration constant for standards and samples.
fh= factor to correct a disk source counting rate to the counting rate
of the same activity as a point source on the same axis of the
system. This can be corrected for by preparing and counting the
standard in the same configuration as the samples.
fssg = factor to correct for the absorption and scatter of beta particles
within the material accompanying the radioactive element.
f(. = factor to correct the counting rate for instrument resolving time
losses and defined by the simplified equation,/.= (l-nt), where
n = observed counts per minute and / = instrument resolving
time in minutes. Generally, the sample size or source-to-detector
distance is selected to preclude counting losses. Such losses are
negligible for count rates of less than 80 000 counts per minute if
proportional detectors are used. Information on the effect of
instrument resolving time on the sample count rate as well as
methods for determining the resolving time of the counting
systems may be found in the literature [77].
where
dpm = disintegrations per minute, yielding beta particles;
cpm = recorded counts per minute, corrected for background;
fe* = detection efficiency factor; observed cpm/dpm ratio for known
standard of some radionuclide counted under identical conditions
with no quenching; and
fq = quench correction factor, observed ratio of cpm-quenched/cpm-
unquenched for known standard of same radionuclide with equiv-
alent quenching.
Interferences
Solid Sources—Material interposed between the test sample and the
detector, as well as increasing mass in the radioactive sample itself, produces
significant losses in sample counting rates. Since the absorption of beta
particles in the sample solids increases with increasing mass and varies
inversely with the maximum beta energy, sample residue must remain
constant between related test samples and should duplicate the residue of the
evaporated standard.
Most beta-particle counters are somewhat sensitive to alpha, gamma, and
X-ray radiations, with the degree of efficiency dependent upon the type of
detector [77]. The effect of the interfering radiations on the beta counting
rate is more easily evaluated with external-type counters where appropriate
absorbers can be placed between the sample and detector to evaluate the
effects of interfering radiation.
(NOTE: The detection efficiency may be assumed to be unity for beta emitters having
maximum energies of 200 keV or greater.)
Liquid Scintillation—Liquid scintillation samples are subject to inter-
ference by substances which quench or enhance the scintillation process.
This includes any chemiluminescence which changes the photon yield.
Substances such as oxidants, organohalides, ketones, and aldeyhydes are to
be particularly avoided. A second type of quenching is color quenching, in
which a colored solution impairs the light collection efficiency for the
photons produced.
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 423
Apparatus
Beta Particle Counter—The end-window Geiger-Muller tube and the
internal or external proportional gas-flow chambers are the two most
prevalent types of detectors. Other types of detectors include scintillators
and solid-state detectors. The material used in the construction of the
detector and its surroundings should contain a minimal level of detectable
radioactivity. If the detector is of the window-type, the window thickness
may be used in calculating beta ray attenuation; however, direct calibration
of the entire counting system with standards is recommended. The manu-
facturer should provide all settings and data required for reliable and
accurate operation of the instrument. Detectors requiring external posi-
tioning of the test sample shall include a support of low-density material
(aluminum or plastic) which assures a reproducible geometry between the
sample and the detector. Because different sample-to-detector geometries are
convenient for differing sample activity levels, the sample support may
provide several fixed positions ranging from 0.5 to 10 cm from the detector.
Liquid Scintillation—Liquid scintillation counting systems use an organic
phosphor as the primary detector. This organic phosphor is combined with
the sample in an appropriate solvent which achieves a uniform dispersion. A
second organic phosphor often is included in the liquid scintillation "cock-
tail" as a wavelength shifter. The wavelength shifter efficiently absorbs the
photons of the primary phosphor and re-emits them at a longer wavelength
more compatible with the multiplier phototube. Liquid scintillation counting
systems use either a single multiplier phototube or two multiplier phototubes
in coincidence. The coincidence counting arrangement is less likely to accept
a spurious noise pulse which occurs in a single phototube, and thus provides
lower background. The requirement that both multiplier phototubes re-
spond to each has a slight effect on the overall detection efficiency of betas
with E-max >200 keV; however, system response to beta £-max <200 keV
will be significant. The need to minimize detectable radioactivity in the
detector and its surrounding is likewise important in liquid scintillation
counting. To achieve this scintillation grade, organic phosphors and solvents
are prepared from low carbon-14 materials such as petroleum. The counting
vials are of low-potassium glass or plastic to mimimize counts due to
potassium-40. Liquid scintillation provides a fixed geometry from a given-
size counting vial and liquid volume.
Detector Shield—The detector assembly should be surrounded by an
external radiation shield of massive metal equivalent to approximately 51
cm of lead and lined with 3.2-mm-thick aluminium. The material of
construction should be of minimal detectable radioactivity. The shield
should have a door or port for inserting or removing specimens. Detectors
having other than completely opaque windows are light-sensitive. The design
of the shield and its openings should eliminate direct light paths to the
detector window; beveling of door and opening generally is satisfactory.
Liquid scintillation counting systems must provide an interlock which
424 MANUAL ON WATER
protects the photocathode of the multiplier phototube from light when the
sample counting chamber is opened.
Associated Electronic Equipment—The high-voltage power supply ampli-
fier, sealer, and mechanical register normally are contained in a single
chassis. The power supply and amplifier sections are matched with the type
of detector to produce satisfactory operating characteristics and to provide
sufficient range in adjustments to maintain stable conditions. The sealer
should have capacity for storing and visually displaying at least 9 x 105
counts. The instrument should have an adjustable input sensitivity matched
to that of the detector, and variable high-voltage power supply. (An
adjustable power supply and meter are unnecessary for liquid scintillation
systems.) Counting chambers of Geiger-Muller and proportional counters
contain a suitable counting gas and an electrode. Counting rates which
exceed 10 000 cpm must be corrected for dead-time loss when using a Geiger-
Muller tube. As the applied voltage to the electrode is increased, the
counting chamber exhibits responses which are characteristic of a particular
voltage region. At low voltages of the order of 100 V, there is no
multiplication of the ionization caused by a charged particle. At voltages
approaching 1000 V, there is appreciable amplification of any ionization
within the counting chamber; however, the size of the output pulse is
proportional to the amount of initial ionization. When operated in this
voltage region, the device is known as a proportional counter. Usually there
is a region at least 100 V wide, known as a plateau, wherein the count rate of
a standard is relatively unaffected. The operating voltage for proportional
counters is selected to approximate the middle of this plateau in order to
maintain stable responses during small voltage shifts. The plateau region is
determined by counting a given source at voltage settings which differ by 25
or 50 V. The number of counts at each setting is recorded, and the resultant
counts versus voltage are plotted as shown in Fig. 6. Voltage plateau curves
are to be remeasured periodically to ensure continued instrument stability,
or whenever an instrument malfunction is indicated. If the voltage is
increased beyond the proportional region into the 1500 to 2000 V region, the
pulse size increases and the dependence on the initial ionization intensity
Beta particles are easily deflected in passing through matter. Some beta
particles emitted in a direction away from the detector can be deflected by
the source-backing material and scattered toward the detector. This phen-
omenon leads to an increased number of beta particles reaching the detector
over that expressed from geometric considerations alone. Backscatter
increases rapidly with increasing thickness and atomic number of the
backing material. Backscatter effects may be held constant by maintaining
sample size and mounts constant for relative measurements. If backscatter
corrections must be made, these corrections can be determined by counting a
sample first on thin film mount, and then recounting when backed by the
desired backing material. Backscatter does have the effect of increasing the
number of particles which reach the detector, thereby increasing the
counting efficiency.
components; this residual curve may be processed again in the same way to
reduce (in principle) any complex decay curve into its component parts. In
actual practice, uncertainties in the observed data place a practical limit to a
three-component system except in unusual cases, and often a two-component
system may not be satisfactorily resolved because of similar decay constants.
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 429
Since the residual curve in Fig. 7 (1 day half-life) does not deviate from the
straight line, and the original curve is concave except in the final portion, a
two-component system on independently-decaying activities is indicated. In
accumulating decay data, care must be taken to avoid disturbing the source
and to locate the sample in the same geometrical position for each
measurement. If the instrument is calibrated for the specific characteristics
of the source and for the energies of the radiations measured, the count rate
shown at the ordinate intercept of the extrapolated straight lines at t0 will be
equal to the disintegration rate at /0. However, this technique requires
specific beta-energy knowledge for each component of the sample, as well as
counting instrument standardization at these same energies under identical
conditions. In practice, gamma spectrometry is preferred; see ASTM Test
for Gamma Spectrometry of Water (D 2459) [7] for resolving mixtures of all
radionuclides except pure beta emitters. An additional complication in
decay curve interpretation is the growth of radioactive daughters. See
standard Refs 11 and 20 for a discussion of this.
absorber to be used. The source must not be moved after the first count rate,
which is obtained with no absorber between the source and the detector. The
activity of the source should be close to the maximum allowed by resolving
time of the instrument. Absorption coefficients given in the literature and
half-thickness data utilize the initial portions of the absorption curve and are
not as accurate as the total absorption determination. More accurate
methods for determination of beta particles range, from absorption curves,
are the comparison method of Feather [77] and Harley et al [33]
Many liquid scintillation counting systems provide an output suitable for
accumulation and storage of beta spectra of known maximum energy. To
obtain the most accurate beta maximum energy measurement, the pulse
height-energy relationship of the system must be calibrated [34]. With the
aid of this relationship, the pulse height distribution of the sample may
be converted to a Curie plot [35] and extrapolated to obtain maximum beta
energy. Excellent agreement with beta-energy spectrometry values has been
obtained with this technique [36]. A Curie plot is shown in Fig. 10.
Calculations—Results may be expressed in observed counts per minute
per millimetre for comparing relative activities of a group of samples as in
tracer experiments
432 MANUAL ON WATER
FIG. 10— Curie plot of the /3- spectrum of "4 In. Note especially that N means N(n), the
number of fi rays in a momentum interval A, of constant size. The horizontal coordinate is the
kinetic energy E, which corresponds to the midpoint of the momentum interval n + An. When
spectral data give a straight line, such as this one, the N(n) is in agreement with the Fermi
momentum distribution. The intercept of this straight line, on the energy axis, gives the
disintegration energy Emax (E*), if the rest mass of the neutrino is zero. (From Lawson and
Cork, Physical Review, Vol. 57, 1940/7. 982.
where
N = number of counts accumulated,
t = sample counting period, min,
NB — number of background counts accumulated,
tB = background counting period, min,
K = volume of initial sample, ml, and
C = net counts per minute per millilitre (cpm/ml).
where
C = net counts per minute per millilitre (cpm/ml), and
£i37Cs = efficiency for counting Cs-137 beta particles plus conversion
electrons (count rate + emission rate).
If it is known that only one nuclide is present, its disintegration rate may
be determined by use of the efficiency factor measured with a reference
standard of the same nuclide. The results may be calculated as follows
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 433
where
N = number of counts accumulated,
B = background in counts per minute (cpm),
D = disintegration rate per minute per millilitre (dpm/ml),
E = efficiency of counter for specific nuclide (counts + disintegrations),
V = millilitre of test specimen,
Y = recovery of species (unity in cases where complete recovery is
assumed), and
t = count period, min.
where
A = concentration, microcuries per millilitre,
D = disintegration rate per minute per millilitre (dpm/ml), and
2.22 X 106 = conversion factor, disintegration per minute per microcurie.
Gamma Counting
This section covers the measurement of gross gamma radioactivity of
water. Since gamma radiation is a penetrating form of radiation, it can be
used for samples of any form and geometry as long as standards of the same
form are available and are counted at the same geometry to calibrate the
detector. Because of this penetrating nature, small variations in sample
density or sample thickness are usually not significant and gamma counting
is the preferred method in general radiochemical work. When a standard
cannot be obtained in the matrix being counted, a correction for the
different absorption in the matrices must be made.
Since different nuclides emit distinct and constant spectra of gamma
radiation, the use of an energy-discriminating system provides identification
and measurement of all the components present in a mixture of radio-
activity, and this technique is covered in ASTM Recommended Practice for
Gamma-Ray Spectrometry (D 2459) [7]. Gamma counting and gamma
spectrometry are applicable to levels of about 10 picocuries or above.
General information on gamma ray detectors and gamma counting is
covered in the literature [11,16].
434 MANUAL ON WATER
Summary
Gamma counting is generally carried out using solid detectors since a gas-
filled detector will not provide adequate stopping power for energetic
gammas. In solids such as sodium iodide (thallium) or cesium iodine, the
gammas interact by excitation of atoms, and energy is transferred to orbital
electrons and then released as light photons when the orbits are refilled. The
scintillations are easily detected and amplified into useable electrical pulses
by a multiplier phototube. The Nal (Tl) detector is the recommended
detector for gross gamma counting.
In semiconductor detectors such as Si (Li) and Ge (Li) the gamma photons
produce electron-hole pairs and the electrons are collected by an applied
electrical field. A charge-sensitive preamplifier is used to detect the change
transferred and produce a useable electrical pulse. The semiconductor
detectors are widely used in gamma spectrometry (see ASTM Method D
2459-72) and are not reviewed in this practice.
The output pulses from the multiplier phototube or preamplifier are
directly proportional to the amount of energy deposited, which could either
be total and be included in the photopeak or fractional and be included in
the continuum or escape peaks, in the detector, by the incident photon. The
pulses may be counted using a sealer or analyzed by pulse height to produce
a gamma ray spectrum.
Gamma photons interact with the detector by three distinct processes. The
photoelectric effect results in complete absorption of the photon energy and
produces the full energy or photopeak shown in Fig. 11 results. The third
interaction is pair production, which occurs at energies above 1.02 MeV and
results in disappearance of the photon when an electron positron pair is
produced. The electron and positron give up their kinetic energy to the
detector and the resulting electron joins the electron population of the
detector; the positron, however, is annihilated in combining with an electron
and produces two gamma photons of 0.511 MeV each. One or both of the
0.511 MeV photons may escape from the detector without interacting and
the "single escape" and "double escape" peaks shown in Fig. 12 result. The
Comptons from a higher energy photon always present an interference
problem in the counting of gamma photons, and appropriate corrections
must be made for this effect. Pair production can also be considered as an
interference since the excape peaks may have an energy equal to the lower-
energy gamma of interest.
The change of absorption coefficient with gamma energy results in a wide
variation of detection efficiency. The detection efficiency falls rapidly as
gamma energy increases, for a fixed size of detector. Two other important
effects are seen as a result of variation of absorption coefficient; firstly, low-
energy photons may be absorbed in massive samples, such as large bottles of
water, and erroneous results obtained. A similar absorption effect is seen in
germanium (lithium) systems where the can around the detector acts as an
absorber for very-low-energy gammas and the efficiency passes through a
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 435
maximum usually around 100 keV. The second results is that for low-energy
gammas a thin detector may be as efficient as a much thicker one since the
low-energy gammas are easily stopped in the thin detector.
Because of this variation in efficiency and the possible interferences from
other activities, gross gamma counting is only reliable when used to compare
standards and samples of the same nuclide. The use of gross gamma
monitoring systems should be avoided when possible, and, in all cases,
proper allowance must be made for the lack of accuracy.
Interferences
The natural background persent at all locations is detected very efficiently
by gamma detectors and presents a significant interference which must be
reduced by the use of shielding. Low-radioactivity-level lead or steel should
be used and, for a 76- by 76-mm sodium iodide detector, about 102 mm of
436 MANUAL ON WATER
since for a given source strength the count rate is higher than for a detector
of lower efficiency. For moderate and high source strengths, the tradeoff is a
poor one and the well counter is best suited for low level work where its high
efficiency is an important advantage.
Cascade summing may occur when nuclides which decay by a gamma
cascade are counted. Cobalt-60 is an example; 1.17 MeV and 1.33 MeV from
the same decay may enter the detector and be absorbed, giving a 2.50 MeV
sum peak. Cascade summing may be reduced by increasing the source to
detector distance.
The resolution of a gamma detector is the effective limit to its utility even
when complex data reduction methods are used. A typical 76- by 76-cm
sodium iodide (thallium) detector will give full widths at half maximum
(FWHM) of about 60 keV at 662 keV gamma energy and about 90 keV at
1.33 MeV gamma energy.
Apparatus
Sodium Iodide Detector Assembly—A 76- by 76-mm sodium iodide de-
tector is activated with about 0.1 percent thallium iodide, cylindrical, with or
without an inner sample well, optically coupled to a multiplier phototube and
hermetically sealed in a light tight container. The sodium iodide (thallium)
crystal should contain less than 5 ppm of potassium and be free of other
radioactive materials. In order to establish freedom from radioactive mater-
ials, the manufacturer shall supply a gamma spectrum of the background
of the detector between 0.08 and 3.0 MeV. The resolution of the detector
for the cesium-137 gamma at 0.662 MeV should be less than 60 keV FWHM
or less than 9 percent.
Shielding for the detector shall be constructed as needed from low-
radioactivity-level lead or steel. A thickness equivalent to 10.16 cm of lead
usually provides adequate shielding. If the shield is made of lead; a graded
liner should be used unless the shield-to-detector distance is more than 254
mm.
High-voltage Power Supply—500 to 2000 V dc regulated to 0.1 percent
with a ripple of not more than 0.01 percent.
Preamplifier: Linear Amplifier System—to amplify the output from the
multiplier phototube to a maximum output of 10 V.
Analyzer with Sealer and Timer—A single-channel discrimination system
will accept all or any part of the output from the amplifier and pass it to the
sealer. Any pulses lying outside the preset limits are rejected. The lower limit
is usually referred to as the "threshold" and the difference between the two
limits is the "window."
Sample mounts and containers may consist of any reproducible geometry
container which is commerically available. Other considerations are cost,
ease of use, disposal, and effective containment of radioactivity for pro-
tection of the workplace and personnel from contamination.
438 MANUAL ON WATER
Source Preparation
Samples must be prepared in an identical manner to the standards and
counted in the same geometry under identical conditions. For gamma
counting, samples may be liquid, solid, or gaseous form in suitable con-
tainers.
The evaporation of liquid samples to dryness before counting is not
necessary. However, samples which have been evaporated to dryness for
gross beta counting can also be gamma counted. Evaporation may also be
used as a sample concentration technique, especially with pure water such as
evaporator condensates where large samples may be evaporated to small
volume and counted with a higher efficiency.
Gaseous samples can be collected in any type of gas container, but care
must be taken to ensure that all the gas containers of a particular type have a
constant wall thickness. Wall thickness variation can be a significant prob-
lem in counting radioactive xenons which have gammas of 80 keV and 250
keV energy.
Calculations
Results may be expressed in observed counts per minute per millilitre for
comparing relative activities of a group of samples as in tracer experiments
where
N = number of counts accumulated,
t = sample counting period, min,
NB = number of background counts accumulated,
tB = background counting period, min,
V = volume of initial sample, ml, and
C = net counts per minute per millilitre (cpm/ml).
where
C = net counter per minute per millilitre (cpm/ml), and
CHAPTER 18 ON PRACTICES FOR MEASUREMENT OF RADIOACTIVITY 441
where
N' = number of counts accumulated,
B = background in counts per minute, (cpm),
D = disintegrations per minute per millilitre (dpm/ml),
E = efficiency of counter for specific nuclide (cpm/ dpm),
V = millilitres of test specimen,
Y = recovery of species (unity in cases where complete recovery is
assumed), and
/ = count period, min.
where
A = concentration, microcuries per millilitre,
D = disintegration rate per minute per millilitre (dpm/ml), and
2.22 X 106 = conversion factor, disintegrations per minute per microcurie.
References
[7] Annual Book of ASTM Standards, Part 31.
[2] Annual Book of ASTM Standards, Part 41.
[5] Pate, B. D. and Yaffe, L., Canadian Journal of Chemistry, Vol. 33, 1955, pp. 15, 610,929,
1656.
[4] Blanchard, R., Kahn, B., and Birkoff, R. D., Health Physics, Vol. 2, 1960, p. 246.
[J] Hallden, N. A. and Fisenne, I. M., "International Journal of Applied Radiation and
Isotopes, VoL 14, 1963, p. 529.
\6\ Merritt, J. S., Taylor, J. G. V., and Campion, P. J., Canadian Journal of Chemistry, Vol.
37, 1956, p. 1109.
[7] Gunnick, R., Colby, L. J., and Cobble, J. W., Analytical Chemistry, Vol. 31, 1959, p. 796.
[8] Friedlander, G., Kennedy, J. W., and Miller, J. M., Nuclear and Radiochemistry, 2nd
ed., Wiley, New York, 1964.
[9] Price, W. J., Nuclear Radiation Detection, 2nd ed., McGraw-Hill, New York, 1964.
[10] Campion, P. J., Taylor, J. G. V., and Merritt, J. S., "'International Journal of Applied
Radiation and Isotopes, Vol. 8, 1960, p. 8.
[77] Friedlander, G., Kennedy, J. W., and Miller, J., Nuclear and Radiochemistry, 2nd ed.,
Wiley, New York, 1964; Overman, R. T. and Clark, H. M., Radioisotope Techniques,
McGraw-Hill, New York, 1960; Price, W. J., Nuclear Radiation Detection, McGraw-
442 MANUAL ON WATER
Hill, New York, 1964; Flynn, K. F., Glendenin, L. E., and Pradi in Organic Scintillators
and Liquid Scintillation Counting, D. L. Horrocks and Chim-Tzu Peng, Eds., Academic
Press, New York, 1971, p. 687.
[72] Curtis, M. L., Heyd, J. W., Olt, R. G., and Eichelberger, J. F., Nucleonics, Vol. 13, May
1955, p. 38.
[73] Watt, D. E. and Ramsden, O., High Sensitivity Counting Techniques, MacMillan, New
York, 1964.
[14] Crouthamel, C. E., Adams, F., and Dams, R., Applied Gamma-Ray Spectrometery, 2nd
ed., Pergamon Press, New York, 1970.
[75] Nielson, J. M. in Gamma-Ray Spectrometry in Physical Methods of Chemistry, A.
Weissberger and B. W., Rossiter, Eds. Vol. 1, Part 3 D, Chapter 10, Wiley, New York,
1972.
[16] Perkins, R. W., Nuclear Instruments and Methods, Vol. 33, 1965, p. 71; Wogman, N. A.
and Perkins, R. W., Nuclear Instruments and Methods, 1968.
[77] Cooper, J. A., Ranticelit, L. A., Perkins, R. W., Haller, W. A., and Jackson, A. L., "An
Anti-Coincidence Shielded Ge(Li) Gamma-Ray Spectrometer and Its Application to
Neutron Activation Analyses," Report BNWL-SA-2009, Pacific Northwest Laboratory,
Richland, Wash., 1968.
[18] "Metrology of Radionuclides," Proceedings, Symposium, International Atomic Energy
Agency, Vienna, 14-16 Oct. 1959.
[79] Nielsen, J. M. and Kornberg, H. A. in Radioisotope Sample Measurement Techniques
in Medicine and Biology, Proceedings, Symposium, International Atomic Energy
Agency, Vienna, 24-28 May 1965, p. 3.
[20] Lapp, R. E. and Andrews, H. L., Nuclear Radiation Physics, Prentice Hall, New York,
1948; 2nd ed., Englewood Cliffs, N. J., 1954.
[27] Jarrett, Allen A., "Statistical Methods used in the Measurement of Radioactivity with
Some Useful Graphs and Nomographs," Atomic Energy Commission U-262.
[22] Bell, C. G. and Hayes, F. N., Liquid Scintillation Counting, Pergamon Press, New York,
1958.
[23] Birks, J. B., The Theory and Practice of Scintillation Counting, Pergamon Press,
New York, 1964.
[24] The Current Status of Liquid Scintillation Counting, E. Bransome, Jr., Ed., Greene
and Straiten, New York, 1970.
[25] "Environmental Radioactivity Surveillance Guide," ORP/SID 72-2, U. S. Environ-
mental Protection Agency, 1972.
[26] Sill, C. W. and Olson, D. G., Analytical Chemistry, Vol. 42, 1970, 1956.
[27] Puphal, K. W. and Olson, D. R., Analytical Chemistry, Vol. 44, Feb. 1972.
[2«] Mitchell, R. F., Analytical Chemistry, Vol. 32, 1960, pp. 326-328.
[29] Bell, C. G., and Hayes, F. N., Liquid Scintillation Counting, Pergamon Press, New York,
1958.
[30] Moghissi, A. A. in Organic Scintillators and Liquid Scintillation Counting, Academic
Press, New York, 1971 (in preparation).
[37] Horrocks, D. L., Review of Scientific Instruments, Vol. 55, 1964, p. 334.
[32] Bogen, D. C. and Welford, G. A., Proceedings, International Symposium of Rapid
Methods for Measuring Radioactivity in the Environment, LAEA-SM-148/3, 1971, p.
383.
[33] Harley, J. H., Hallden, N. A., and Fisenne, I. M., Nucleonics Vol. 20, 1962, p. 59.
[34] Flynn, K. F., Glendenin, E., Steinberg, E. P., and Wright, P. M., Nuclear instruments
and Methods, Vol. 27, 1964, p. 13.
[35] "Tables for the Analyses of )8 Spectra," National Bureau of Standards Applied Mathema-
tics Series Reports No. 13, U. S. Government Printing Office, Washington, D. C., 1952.
[36] Flynn, K. F. and Glendenin, L. E., Physical Review, Vol. 146, 1959, p. 744.
[37] Heath, R. L., "Scintillation Spectrometry Gamma-Ray Spectrum Catalog," Government
Report Nos. IDO 16880 and ANCR-1000.
STP442A-EB/Jul. 1978
Appendix—Reference Tables
and Curves
The following values apply to elements as they exist in materials of terrestrial origin and
to certain artificial elements. They are based on the assigned relative atomic mass of carbon-12
and when used with regard to the footnotes they are considered reliable to ± 1 in the last digit,
or ±3 if that digit is a subscript. These values are accepted by the International Union of
Pure and Applied Chemistry, Division of Inorganic Chemistry Commission on Atomic
Weights, and are the 1971 data revised in 1973.
Arsenic As 33 74.9216'
Astatine At 85
Barium Ba 56 137.34
Berkelium Bk 97
Beryllium Be 4 9.01218*
Bismuth Bi 83 208.9804"
Boron B 5 10.81c:d:e
Bromine Br 35 79.904C
Cadmium Cd 48 112.40
Cesium Cs 55 132.9054"
Calcium Ca 20 40.08*
Californium Cf 98
Carbon C 6 12.01 lb'd
Cerium Ce 58 140.12
Chlorine Cl 17 35.453C
Chromium Cr 24 51.996C
Cobalt Co 27 58.9332'
Copper Cu 29 63.54*c'd
Curium Cm 96
Dysprosium Dy 66 162.5o
(Continued)
443
Copyright© 1978 by ASTM International www.astm.org
444 MANUAL ON WATER
Viscosity of water.
Temperature, Viscosity,
°C Pascal-second
10 0.0013077
15 0.0011404
20 0.0010050
25 0.0008937
30 0.0008007
35 0.0007225
446 MANUAL ON WATER
Density of water."
Density of Water, kg/m3 at T deg C
Temperature
Deg°C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0 999. 8396 8463 8528 8591 8653 8713 8771 8827 8882 8934
1 8985 9034 9082 9127 9171 9213 9254 9293 9330 9365
2 9398 9430 9460 9489 9516 9541 9564 9586 9606 9625
3 9642 9657 9670 9682 9692' 9701 9708 9713 9717 9719
4 9720 9719 9716 9712 9706 9699 9690 9680 9668 9654
5 9639 9622 9604 9584 9563 9540 9516 9490 9462 9433
6 9403 9371 9338 9303 9266 9229 9189 9148 9106 9062
7 9017 8970 8922 8873 8822 8769 8715 8660 8603 8545
8 8485 8424 8362 8298 8233 8166 8098 8029 7958 7886
9 7812 7737 7661 7583 7504 7424 7342 7259 7174 7088
10 7001 6913 6823 6732 6639 6545 6450 6354 6256 6157
11 6056 5955 5852 5747 5642 5535 5427 5317 5206 5094
12 4981 4866 4751 4634 4515 4396 4275 4153 4029 3905
13 3779 3652 3523 3394 3263 3131 2998 2863 2728 2591
14 2453 2313 2173 2031 1888 1744 1599 1452 1305 1156
15 1006 0855 0702 0549 0394 0238 0081 9923* 9763* 9603*
16 998. 9441 9278 9114 8949 8783 8615 8447 8277 8106 7934
17 7761 7587 7412 7235 7058 6879 6699 6518 6336 6153
18 5969 5784 5597 5410 5221 5031 4841 4649 4456 4262
19 4067 3870 3673 3475 3275 3075 2874 2671 2467 2263
20 2057 1850 1642 1433 1223 1012 0800 0587 0373 0158
21 997. 9942 9725 9506 9287 9067 8846 8623 8400 8176 7950
22 9724 9496 7268 7039 6808 6577 6344 6111 5877 5641
23 5405 5167 4929 4690 4449 4208 3966 3723 3478 3233
24 2987 2740 2492 2243 1993 1741 1490 1237 0983 0728
25 0472 0215 9958* 9699* 9439* 9179* 8917* 8655* 8391* 8127*
26 996. 7862 7596 7329 7061 6792 6522 6251 5979 5706 5433
27 5158 4883 4607 4329 4051 3772 3492 3211 2929 2647
28 2363 2079 1793 1507 1220 0932 0643 0353 0062 9770*
29 995. 9478 9184 8890 8595 8299 8002 7704 7405 7106 6805
30 6504 6202 5899 5595 5290 4984 4678 4370 4062 3753
31 3443 3132 2820 2508 2195 1880 1565 1249 0932 0615
32 0296 9977 9657 9336 9014 8691 8368 8044 7718 7392
33 994. 7066 6738 6409 6080 5750 5419 5087 4755 4421 4087
34 3752 3416 3079 2742 2403 2064 1724 1383 1042 0700
35 0356 0012 9668* 9322* 8976* 8628* 8280* 7932* 7582* 7232*
36 993. 6880 6529 6176 5822 5468 5113 4757 4400 4043 3684
37 3325 2966 2605 2244 1881 1518 1155 0790 0425 0059
38 992. 9692 9324 8956 8587 8217 7846 7475 7103 6730 6356
39 5982 5606 5230 4854 4476 4098 3719 3339 2959 2577
40 2195 1813 1429 1045 0660 0274 9888* 9500* 9112* 8724*
41 991. 8334 7944 7553 7161 6769 6376 5982 5587 5192 4796
_42 4399
"ASTM Designation E-500.
APPENDIX—REFERENCE TABLES AND CURVES 447
K* 73.52
Na* 50.11
H+ 349.82
.NH4+ 73.4
'/* Ca" 59.5
to Mg" 53.06
Cb 76.34
NO3- 71.44
to SO4~ 79.8
OH- 198
HCO3- 44.48
to C02- 83
HS- 72
HSO3- 71
to SOr 80
H2PO4- 29
to HPO4- 60
'/3 PO*- 78
"Xo = Ionic equivalent conductance at infinite dilution.
448 MANUAL ON WATER
Percentage of silica in steam versus boiler drum pressure at selected boiler water pH.
Interconversion factors from milligrams per litre to equivalents per million of the
common ions.
Multiplier Multiplier
mg/ litre epm to mg/ litre epm to
Ion toepm mg/ litre Ion to epm mg/ litre -
AT" 0.1112 8.99 Cn" 0.03843 26.02
&r 0.014S6 68.68 0.03333 30.00
or
C03=
0.04990 20.04 F 0.05263 19.00
Cu" 0.03148 31.77 HCOf 0.01639 61.02
Fe" 0.03581 27.92 H2por 0.01031 96.99
Fe"* 0.05372 18.62 HS' 0.03024 33.07
It 0.9921 1.008 HPO4= 0.02084 47.99
K+ 0.02558 39.10 HS04" 0.01030 97.07
Mg" 0.08224 12.16 HSO3" 0.01233 81.07
Mn" 0.03640 27.47 r 0.00788 126.91
Mn~ 0.07281 13.735 NO3" 0.01613 62.01
+
Na 0.04350 22.99 N02" 0.02174 46.01
+
NH 0.05543 18.04 OH" 0.05880 17.01
Pb" 0.00965 103.60 P04= 0.03159 31.66
Sr" 0.02282 43.81 S= 0.06237 16.03
Zn" 0.03059 32.69 SiO4F 0.02172 46.04
=
Br~ 0.01251 79.92 S04 0.02082 48.03
cr 0.02820 35.46 SCh =
0.02498 40.03
Analyses of typical public water supplies in the United States.
(From U. S. Geological Survey Water Supply Paper 1812)
(milligrams per litre)
Water supply," 1 2 3 4 5 6 7 8
Date of collection 4/17/62 8/24/61 7/21/61 5/16/61 3/16/61 1/8/62 7/11/61 8/25/61
Silica (SiO2), mg/ litre 3.1 1.3 4.5 2.0 5.7 7.1 2.7 4.8
Iron (Fe), mg/ litre 0.04 0.05 0.02 0.06 0.06 0.12 0.03 0.00
Manganese (Mn), mg/ litre 0.00 0.09 0.00 0.00 0.00 0.00
Calcium (Ca), mg/ litre 4.5 32 20 6.9 27 1.0 3.2 40
Magnesium (Mg), mg/ litre 0.4 11 7.8 1.0 3.9 0.6 0.6 8.8
Sodium (Na), mg/ litre 2.4 4.0 18 1.8 4.7 i.l 2.9 8.2
Potassium (K), mg/ litre 0.8 0.8 2.8 0.5 2.8 0.4 0.4 1.9
Bicarbonate (HCOa), mg/ litre 8 128 36 13 32 8 11 106
Carbonate (CO3), mg/ litre 0 0 0 0 0 0 0.3 0
Sulfate (SO4), mg/ litre 7.0 20 46 9.0 43 0.8 1.5 45
Chloride (Cl), mg/ litre 3.5 8.0 32 3.8 16 2.2 3.6 15
Fluoride (F), mg/ litre 0.0 1.0 0.2 0.0 0.8 0.0 0.1 0.9
Nitrate (NO3), mg/ litre 0.0 0.4 1.4 0.9 3.6 0.2 0.0 1.2
Dissolved solids, mg/ litre 31 149 187 41 130 22 27 198
Hardness as CaCOs, mg/ litre 13 125 82 21 84 5 10 137
Noncarbonate hardness as CaCo3,
mg/ litre 6 20 52 11 58 0 1 50
Specific conductance
(micromhos at 25° C) 434 275 352 540 464 516 2,180 477 803 221 125 161
pH 7.6 7.2 7.5 7.2 7.3 7.9 7.5 7.7 7.8 7.7
Color 10 5 18
"Surface waters are identified as follows:
1. Delaware River at Trenton, N. J. (Water-Supply Paer-1941). 5. Mississippi River at St. Francisville, La. (WSP-1944).
2. Roanoke River at Jamesville, N. C. (WSP-1941). 6. Colorado River at Austin, Tex. (WSP-1944).
3. Ohio River at Lock and Dam 53, near Grand Chain, 111. (WSP-1942). 7. Colorado River near Grand Canyon, Ariz. (WSP-1945).
4. Missouri River at Nebraska City, Nebr. (WSP-1943). 8. Columbia River near The Dalles, Ore. (WSP-1945).
Temperature conversion___«~-
tables (-100 TO 1000 deg)
C F C F C F C F
-73.3 -100 -148 5.0 41 105.8 33.3 92~~ 197.6 211 530 986
Interpolation -67.8 -90 -130 5.6 42 107.6 33.9 93 199.4 282 540 1004
Factors -62.2 -80 -112 6.1 43 109.4 34.4 94 201.2 288 550 1022
-56.7 -70 -94 6.7 44 111.2 35.0 95 203.0 293 560 1040
C F -51.1 -60 -76 7.2 45 113.0 35.6 96 204.8 299 570 1058
-45^6 -50 -58 7.8 46 114.8 36.1 97 206.6 304 580 1076
0.56 1 K8 -40 -40 -40 8.3 47 116.6 36.7 98 208.4 310 590 1094
-34.4 -30 -22 8.9 48 118.4 37.2 99 210.2 316 600 1112
-28.9 -20 -4 9.4 49 120.2 37.8 100 212 321 610 1130
1.11 2 3.6 -23.3 -10 14 10.0 50 122.0 43.0 110 230 327 620 1148
-17.8 0 32 10.6 51 123.8 49.0 120 248 332 630 1166
-17.2 1 33.8 11.1 52 125.6 54.0 130 266 338 640 1184
1.67 3 5.4 -16.7 2 35.6 11.7 53 127.4 60.0 140 284 343 650 1202
-16.1 3 37.4 12.2 54 129.2 66.0 150 302 349 660 1220
-15.6 4 39.2 12.8 55 131.0 71.0 160 320 354 670 1238
2.22 4 7.2 -15.0 5 41.0 13.3 56 132.8 77.0 170 338 360 680 1256
-14.4 6 42.8 13.9 57 134.6 82.0 180 356 366 690 1274
-13.9 7 44.6 14.4 58 136.4 88.0 190 374 371 700 1292
2.78 5 9.0 -13.3 8 46.4 15.0 59 138.2 93.0 200 392 377 710 1310
-12.8 9 48.2 15.6 60 140.0 99.0 210 410 382 720 1328
100.0 212 413
-12.2 10 50.0 16.1 61 141.8 104.0 220 428 388 730 1346
3.33 6 10.8 -11.7 11 51.8 16.7 62 143.6 110.0 230 446 393 740 1364
-11.1 12 53.6 17.2 63 145.4 116.0 240 464 399 750 1382
-10.6 13 55.4 17.8 64 147.2 121 250 482 404 760 1400
3.89 7 12.6 -10.0 14 57.2 18.3 65 149.0 127 260 500 410 770 1418
-9.4 15 59.0 18.9 66 150.8 132 270 518 416 780 1436
-8.9 16 60.8 19.4 67 152.6 138 280 536 421 790 1454
4.44 8 14.4 -8.3 17 62.6 20.0 68 154.4 143 290 554 427 800 1472
-7.8 18 64.4 20.6 69 156.2 149 300 572 432 810 1490
-7.2 19 66.2 21.1 70 158.0 154 310 590 438 820 1508
5.00 9 16.2 -6.7 20 68.0 21.7 71 159.8 160 320 608 443 830 1526
-6.1 21 69.8 22.2 72 161.6 166 330 626 449 840 1544
-5.6 22 71.6 22.8 73 163.4 171 340 644 454 850 1562
S.S6 10 18.0 -5.0 23 73.4 23.3 74 165.2 177 350 662 460 860 1580
-4.4 24 75.2 23.9 75 167.0 182 360 680 466 870 1598
-3.9 25 77.0 24.4 76 168.8 188 370 698 471 880 1616
To convert from any Celsius -3.3 26 78.8 25.0 77 170.6 193 380 716 477 890 1634
temperature to the -2.8 27 80.6 25.6 78 172.4 199 390 734 482 900 1652
Fahrenheit equivalent, -2.2 28 82.4 26.1 79 174.2 204 400 752 488 910 1670
select the temperature C -1.7 29 84.2 26.7 80 176.0 210 410 770 493 920 1688
from the center (boldface) -1.1 30 86.0 27.2 81 177.8 216 420 788 499 930 1706
columns, then read -0.6 31 87.8 27.8 82 179.6 221 430 806 504 940 1724
temperature F to the 0 32 89.6 28.3 83 181.4 227 440 824 510 950 1742
right. To convert from F 0.6 33 91.4 28.9 84 183.2 232 450 842 516 960 1760
to C, select the tempera- 1.1 34 93.2 29.4 85 185.0 238 460 860 521 970 1778
ture F from the center 1.7 35 95.0 30.0 86 186.8 243 470 878 527 980 1796
(boldface) columns, and 2.2 36 96.8 30.6 87 188.6 249 480 896 532 990 1814
read equivalent tempera- 2.8 37 98.6 31.1 88 190.4 254 490 914 538 1000 1832
ture C to the left. Use 3.3 38 100.4 31.7 89 192.2 260 500 932
factors above for inter- 3.9 39 102.2 32.2 90 194.0 266 510 950
polations.
4.4 40 104.0 32.8 91 ,195.8 271 520 968
Volume conversion factors.
\ to-
from \ cm3 litres m3 in.3 ft3 yd3 Fluid oz Fluid pt Fluid qt gaUU.S.) gal (U.K.)
cmf 1 0.001 1 X 10~6 0.06102 353 X 10"5 1.3X 10"6 0.03381 0.00211 0.00106 2.64 X 10"4 2.2 X 10"4
litre 1000 1 0.001 61.02 0.03532 0.00131 33.81 2.113 1.057 0.2642 0.220
m3 1 X 106 1000 1 6.1 X 104 35.31 1.308 3.38 X 104 2113 1057 264.2 220
in3 16.39 0.01639 1.64X 10' 1 5.79 X 104 2.14X 10'5 0.5541 0.03463 0.01732 0.00433 0.00360
ft 3 283 X 104 28.32 0.02832 1728 1 0.03704 957.5 59.84 29.92 7.481 6^.229
yd3 7.65 X 10s 764.5 0.7646 4.67 X 104 27 1 259 X 104 1616 809.7 202.0 108.2
fluid oz 29.57 0.02957 2.96 X 10"5 1.805 0.00104 3.87 X 10~5 1 0.0625 0.03125 0.00781 0.00651
fluid pt 473.2 0.4732 4.73 X 10~4 28.88 0.01671 6.19X 10'4 16 1 0.50 0.1250 0.1041
fluid qt 946.4 0.9463 9.46 X 10~4 57.75 0.03342 0.00124 32 2 1 0.25 0.2082
gal (U.S.) 3785 3.785 0.00379 231.0 0.1337 0.00495 128 8 4 1 0.8327
gal (U.K.) 4546 4.546 0.00455 277.4 0.1605 0.00595 153.7 9.608 4.804 1.201 1
APPENDIX—REFERENCE TABLES AND CURVES 457
Maximum boiler water silica concentration versus drum pressure at selected boiler water pH.
(Based on maintaining 0.02 mg/litre SiO2 maximum in steam.)
Index
A Sources, 196
Alpha radioactivity, 290-291, 190,
Abbe condenser, 290 411-417
Absorption, 75, 76 Counting, 411
Band, 303 Rays, 289
Characteristics, 294 Alumina, 183
Spectroscopy, 298-306 Aluminum, 141, 191, 210, 314
Acid mine drainage, 105 Amines, 120, 121, 188, 218
Acidity, 16, 68, 69, 200 Ammonia, 40-41, 176, 16, 185, 211
Chemistry, 200 Nitrogen, 212
Sources, natural, 68, 200 Ammonium, 185, 211, 212
Actinomycetes, 265 Analysis
Control, 266 Checking results, 247, 288
Activated carbon, 273 Deposits, 309
Adsorption, 188 Ground waters, 8
Activated sludge, 79-82 Interpretation of results, 249, 250
Activation, 208 Programs, 158, 160-166
Corrosion products, 374 Public waters, 314-315
Of water, 371 Reporting results, 284, 246
Water additives, 373 Scheme, 310
Water impurities, 372 Selecting methods, 159
Activity, induced, 208, 338 Surface waters, 8, 314, 315
Adsorption, 75, 76 Systematic, 279
Agglomeration, 49 Units of expression, 312, 313, 246
Air contact affects, 184, 185 Water, scheme for, 162-166
Air coolers, 93 Analytical programs
Alarm systems, 159, 160 Factors in selection, 178, 183
Algae control, 73, 266 Methods, checking analysis, 247,
Alkalinity, 15,189, 196,197,199, 201 248
Accuracy, 201 Nature and scope, 178
Chemistry, 197 Planning, 181
Concentration range, 201 Primary considerations in
Methods, 189, 20r planning, 181
pH relationship, 199 Reporting results, 246
459
Copyright© 1978 by ASTM International www.astm.org
460 MANUAL ON WATER
3 =1151 Q O D L 4 D 2 7 2 3