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Technical Manual
CHAPTER 7
Potable Water
CHAPTER 7
Potable Water
Bennett P. Boffardi, Ph.D.
Table of Contents
1.0
Regulations
1.1
National Secondary Drinking Water Regulations
7-1
7-23
2.0
Water Sources
2.1
Water Quality
2.2
Water Chemistry
2.2.1
Description of Common Impurities
2.2.2
Suspended Solids
2.2.3
Dissolved Gases
2.2.4
Dissolved Solids
2.2.5
Microorganisms
2.2.6
pH
2.2.7
Solubility
2.2.8
Conductivity
2.2.9
Common Impurities
2.2.10 Hardness
2.2.11 Magnesium
2.2.12 Alkalinity
2.2.13 Bicarbonate
2.2.14 Carbonate
2.2.15 Hydroxide
2.2.16 Sodium/Potassium
2.2.17 Silica
2.2.18 Iron
2.2.19 Manganese
2.2.20 Aluminum
2.2.21 Fluoride
2.2.22 Lead
2.2.23 Arsenic
2.2.24 Nitrate
2.2.25 Zinc
2.2.26 Sulfide
2.2.27 Organics
7-26
7-26
7-27
7-27
7-27
7-28
7-28
7-28
7-29
7-29
7-29
7-29
7-29
7-30
7-30
7-30
7-30
7-30
7-30
7-30
7-30
7-31
7-31
7-31
7-31
7-31
7-32
7-32
7-32
7-32
7-1
CHAPTER 7
Potable Water
3.0
7-33
7-35
7-35
7-36
7-37
7-37
7-37
7-39
7-42
7-42
7-42
7-42
7-42
7-42
7-43
7-43
7-43
7-43
7-43
7-44
7-44
7-44
7-45
7-49
7-51
4.0
Filtration
4.1
Types of Filtration Systems
4.2
Direct Filtration
4.3
Auxiliary Scour
7-53
7-53
7-53
7-56
5.0
Disinfection
5.1
Destroying Pathogens in Water
5.2
Disinfection Methods
5.2.1 Heat Treatment
5.2.2 Radiation Treatment
5.2.3 Chemical Treatment
5.2.4 Chlorine
5.3
Concentration and Contact Time
5.3.1 Chloramination
5.3.2 Ozone
5.3.3 Chlorine Dioxide
5.3.4 Potassium Permanganate
5.4
Disinfection By-Products
7-58
7-60
7-60
7-60
7-60
7-61
7-63
7-63
7-64
7-64
7-64
7-65
7-66
7-2
CHAPTER 7
Potable Water
6.0
Indices
6.1
Larson-Skold Index
6.2
Driving Force Index
6.3
Casil Index
6.4
Aggressive Index
6.5
Calcite Saturation Index
7-67
7-70
7-71
7-71
7-71
7-72
7.0
Lead
7.1
The Problem
7.2
Health Effects
7.3
Lead Chemistry
7.3.1 Corrosion
7.3.2 Effect of Flow
7.3.3 Effect of Dissolved Oxygen
7.3.4 Effect of Chlorine
7.3.5 Effect of Hardness Ions
7.3.6 Effect of pH-Alkalinity
7.3.7 Effect of Temperature
7.3.8 Effect of Orthophosphate Ions
7.3.9 Effect of Polyphosphate
7.3.10 Effect of Sulfate, Chloride and Nitrate
7.4
Treatment Strategies
7.4.1 Nonchemical Treatment Options
7.4.2 Chemical Treatment Options
7.4.2.1 Ph/Alkalinity Option
7.4.2.2 Inhibitors
7.4.2.3 Orthophosphate
7.4.2.4 Zinc/Polyphosphate
7.4.2.5 Silicates
7-73
7-73
7-74
7-74
7-74
7-75
7-75
7-75
7-76
7-76
7-76
7-77
7-78
7-78
7-78
7-79
7-79
7-79
7-80
7-80
7-83
7-84
8.0
7-85
7-87
9.0
Copper
9.1
Copper Reactions
9.1.1 Copper Corrosion
9.1.1.1 General Corrosion
9.1.1.2 Localized Corrosion
9.1.2 Pitting
9.1.2.1 Pit Initiation
9.1.2.2 Pit Propagation
9.1.2.3 Pit Formation
9.2
Solder Flux
9.3
Aluminosilicate
9.4
Treatment
7-89
7-89
7-90
7-90
7-92
7-94
7-96
7-96
7-97
7-98
7-98
7-98
7-3
CHAPTER 7
Potable Water
10.0 Corrosion
10.1 Uniform or General Corrosion
10.2 Galvanic Corrosion
10.2.1 Area Effect
10.3 Pitting
10.3.1 Steel
10.3.2 Initiation
10.3.3 Propagation
10.3.4 Termination
10.3.5 Reinitiation
10.4 Copper
10.5 Tuberculation
10.6 Flow Assisted Corrosion
10.7 Impingement
10.8 Cavitation
10.9 Dealloying
7-102
7-103
7-103
7-104
7-105
7-105
7-105
7-105
7-106
7-106
7-106
7-106
7-107
7-108
7-109
7-109
7-111
7-112
7-119
7-120
7-122
7-4
CHAPTER 7
Potable Water
CHAPTER 7
Potable Water
1.0
Regulations
The National Primary Drinking Water Regulations (NPDWRs or primary standards) are
legally enforceable standards that apply to public water systems (40 CFR Part 141).
Primary standards protect public health by limiting the levels of contaminants in drinking
water.
Listed below in Tables 1-1 through 1-6 are the regulated contaminants and their
Maximum Contaminant Levels (MCLs) for:
Microorganisms
Disinfectants
Disinfection Byproducts
Inorganic Chemicals
Organic Chemicals
Radionuclides
7-5
CHAPTER 7
Potable Water
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Cryptosporidium
zero
TT 3
Giardia lamblia
zero
TT3
Heterotrophic
Plate Count
n/a
TT3
HPC measures a
range of bacteria that
are naturally present in
the environment
Legionella
zero
TT3
Found naturally in
water; multiplies in
heating systems
Total Coliforms
(including fecal
coliform and E.
Coli)
zero
5.0%4
Turbidity
n/a
TT3
Soil runoff
Viruses (enteric)
zero
TT3
7-6
Sources of
Contaminant in
Drinking Water
CHAPTER 7
Technical Manual
Potable Water
Contaminant
MRDL1
(mg/L)2
Potential Health
Effects from
Ingestion of Water
Sources of
Contaminant in
Drinking Water
Chloramines
(as Cl2)
MRDLG=41
MRDL=4.01
Eye/nose irritation;
stomach discomfort,
anemia
Water additive
used to control
microbes
Chlorine (as
Cl2)
MRDLG=41
MRDL=4.01
Eye/nose irritation;
stomach discomfort
Water additive
used to control
microbes
Chlorine
dioxide (as
ClO2)
MRDLG=0.81
MRDL=0.81
Water additive
used to control
microbes
MCL
or TT1
(mg/L)2
Bromate
zero
0.010
Byproduct of
drinking water
disinfection
Chlorite
0.8
1.0
Byproduct of
drinking water
disinfection
Haloacetic acids
(HAA5)
n/a6
0.060
Byproduct of
drinking water
disinfection
Total
Trihalomethanes
(TTHMs)
none7
---------n/a6
0.10
---------0.080
Byproduct of
drinking water
disinfection
Contaminant
7-7
Sources of
Contaminant in
Drinking Water
CHAPTER 7
Potable Water
MCL or
TT1
(mg/L)2
Potential Health
Effects from
Ingestion of Water
Sources of
Contaminant in
Drinking Water
0.006
0.006
Increase in blood
cholesterol; decrease in
blood sugar
Discharge from
petroleum refineries; fire
retardants; ceramics;
electronics; solder
07
0.010
as of
01/23/06
Skin damage or
problems with
circulatory systems,
and may have
increased risk of getting
cancer
Erosion of natural
deposits; runoff from
orchards, runoff from
glass & electronics
production waste
7 million
fibers
per liter
7 MFL
Increased risk of
developing benign
intestinal polyps
Decay of asbestos
cement in water mains;
erosion of natural
deposits
Increase in blood
pressure
Discharge of drilling
wastes; discharge from
metal refineries; erosion
of natural deposits
Beryllium
0.004
0.004
Intestinal lesions
Cadmium
0.005
0.005
Kidney damage
Corrosion of galvanized
pipes; erosion of natural
deposits; discharge from
metal refineries; runoff
from waste batteries and
paints
Contaminant
Antimony
Arsenic
Asbestos
(fiber >10
micrometers)
Barium
7-8
CHAPTER 7
Technical Manual
Potable Water
Table 1-4: Inorganic Chemicals, Continued
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Chromium
(total)
0.1
0.1
Copper
1.3
TT8;
Action
Level=1.3
Contaminant
Potential Health
Effects from
Ingestion of Water
Sources of
Contaminant in
Drinking Water
Allergic dermatitis
Corrosion of household
plumbing systems;
erosion of natural
deposits
0.2
0.2
Nerve damage or
thyroid problems
Discharge from
steel/metal factories;
discharge from plastic
and fertilizer factories
Fluoride
4.0
4.0
7-9
CHAPTER 7
Technical Manual
Potable Water
Table 1-4: Inorganic Chemicals, Continued
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Potential Health
Effects from
Ingestion of Water
Sources of
Contaminant in
Drinking Water
Lead
zero
TT8;
Action
Level=0.015
Corrosion of household
plumbing systems;
erosion of natural
deposits
Mercury
(inorganic)
0.002
0.002
Kidney damage
Erosion of natural
deposits; discharge from
refineries and factories;
runoff from landfills and
croplands
10
10
Contaminant
Nitrate
(measured as
Nitrogen)
7-10
CHAPTER 7
Technical Manual
Potable Water
Table 1-4: Inorganic Chemicals, Continued
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Selenium
Thallium
Contaminant
Nitrite (measured
as Nitrogen)
Potential Health
Effects from
Ingestion of Water
Sources of
Contaminant in
Drinking Water
0.05
0.05
Discharge from
petroleum refineries;
erosion of natural
deposits; discharge from
mines
0.0005
0.002
7-11
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Potential
Health Effects
from
Ingestion of
Water
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Acrylamide
zero
TT9
Nervous system
or blood
problems;
increased risk of
cancer
Alachlor
zero
0.002
Eye, liver,
kidney or spleen
problems;
anemia;
increased risk of
cancer
Atrazine
0.003
0.003
Cardiovascular
system or
reproductive
problems
Benzene
zero
0.005
Anemia;
decrease in
blood platelets;
increased risk of
cancer
Discharge from
factories; leaching from
gas storage tanks and
landfills
Benzo(a)pyrene (PAHs)
zero
0.0002
Reproductive
difficulties;
increased risk of
cancer
Carbofuran
0.04
0.04
Problems with
blood, nervous
system, or
reproductive
system
Leaching of soil
fumigant used on rice
and alfalfa
Contaminant
7-12
Sources of
Contaminant in
Drinking Water
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals, Continued
Potential
Health
Effects from
Ingestion of
Water
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Carbon
tetrachloride
zero
0.005
Liver problems;
increased risk
of cancer
Discharge from
chemical plants and
other industrial
activities
Chlordane
zero
0.002
Liver or
nervous
system
problems;
increased risk
of cancer
Residue of banned
termiticide
Chlorobenzene
0.1
0.1
Liver or kidney
problems
Discharge from
chemical and
agricultural chemical
factories
2,4-D
0.07
0.07
Kidney, liver, or
adrenal gland
problems
Dalapon
0.2
0.2
Minor kidney
changes
1,2-Dibromo-3chloropropane (DBCP)
zero
0.0002
Reproductive
difficulties;
increased risk
of cancer
Runoff/leaching from
soil fumigant used on
soybeans, cotton,
pineapples, and
orchards
Contaminant
7-13
Sources of
Contaminant in
Drinking Water
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Potential Health
Effects from
Ingestion of
Water
MCLG
(mg/L)2
MCL or
TT1
(mg/L)2
o-Dichlorobenzene
0.6
0.6
Liver, kidney, or
circulatory system
problems
p-Dichlorobenzene
0.075
0.075
Anemia; liver,
kidney or spleen
damage; changes
in blood
1,2-Dichloroethane
zero
0.005
Increased risk of
cancer
1,1-Dichloroethylene
0.007
0.007
Liver problems
cis-1,2-Dichloroethylene
0.07
0.07
Liver problems
trans-1,2-Dichloroethylene
0.1
0.1
Liver problems
Dichloromethane
zero
0.005
Liver problems;
increased risk of
cancer
1,2-Dichloropropane
zero
0.005
Increased risk of
cancer
Di(2-ethylhexyl) adipate
0.4
0.4
Contaminant
7-14
Sources of
Contaminant in
Drinking Water
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Potential
Health Effects
from
Ingestion of
Water
Sources of
Contaminant in
Drinking Water
Di(2-ethylhexyl) phthalate
zero
0.006
Reproductive
difficulties; liver
problems;
increased risk of
cancer
Dinoseb
0.007
0.007
Reproductive
difficulties
Dioxin (2,3,7,8-TCDD)
zero
0.00000003
Reproductive
difficulties;
increased risk of
cancer
Diquat
0.02
0.02
Cataracts
Endothall
0.1
0.1
Stomach and
intestinal
problems
Endrin
0.002
0.002
Liver problems
Residue of banned
insecticide
Epichlorohydrin
zero
TT9
Increased cancer
risk, and over a
long period of
time, stomach
problems
7-15
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Potential
Health Effects
from
Ingestion of
Water
Sources of
Contaminant in
Drinking Water
Ethylbenzene
0.7
0.7
Liver or kidneys
problems
Discharge from
petroleum refineries
Ethylene dibromide
zero
0.00005
Problems with
liver, stomach,
reproductive
system, or
kidneys;
increased risk of
cancer
Discharge from
petroleum refineries
Glyphosate
0.7
0.7
Kidney
problems;
reproductive
difficulties
Heptachlor
zero
0.0004
Liver damage;
increased risk of
cancer
Residue of banned
termiticide
Heptachlor epoxide
zero
0.0002
Liver damage;
increased risk of
cancer
Breakdown of heptachlor
Hexachlorobenzene
zero
0.001
Liver or kidney
problems;
reproductive
difficulties;
increased risk of
cancer
Hexachlorocyclopentadiene
0.05
0.05
Kidney or
stomach
problems
7-16
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
0.0002
0.0002
Methoxychlor
0.04
Oxamyl (Vydate)
Contaminant
Lindane
Potential
Health Effects
from
Ingestion of
Water
Sources of
Contaminant in
Drinking Water
Liver or kidney
problems
Runoff/leaching from
insecticide used on
cattle, lumber, gardens
0.04
Reproductive
difficulties
Runoff/leaching from
insecticide used on fruits,
vegetables, alfalfa,
livestock
0.2
0.2
Slight nervous
system effects
Runoff/leaching from
insecticide used on
apples, potatoes, and
tomatoes
Polychlorinated
biphenyls (PCBs)
zero
0.0005
Skin changes;
thymus gland
problems;
immune
deficiencies;
reproductive or
nervous system
difficulties;
increased risk of
cancer
Pentachlorophenol
zero
0.001
Liver or kidney
problems;
increased cancer
risk
Picloram
0.5
0.5
Liver problems
Herbicide runoff
Simazine
0.004
0.004
Problems with
blood
Herbicide runoff
7-17
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Potential
Health Effects
from
Ingestion of
Water
Sources of
Contaminant in
Drinking Water
Styrene
0.1
0.1
Liver, kidney, or
circulatory
system problems
Tetrachloroethylene
zero
0.005
Liver problems;
increased risk of
cancer
Nervous system,
kidney, or liver
problems
Discharge from
petroleum factories
Toxaphene
zero
0.003
Kidney, liver, or
thyroid problems;
increased risk of
cancer
Runoff/leaching from
insecticide used on
cotton and cattle
2,4,5-TP (Silvex)
0.05
0.05
Liver problems
Residue of banned
herbicide
1,2,4-Trichlorobenzene
0.07
0.07
Changes in
adrenal glands
1,1,1-Trichloroethane
0.20
0.2
Liver, nervous
system, or
circulatory
problems
1,1,2-Trichloroethane
0.003
0.005
Liver, kidney, or
immune system
problems
Toluene
7-18
CHAPTER 7
Technical Manual
Potable Water
Table 1-5: Organic Chemicals
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Potential
Health Effects
from
Ingestion of
Water
Sources of
Contaminant in
Drinking Water
Trichloroethylene
zero
0.005
Liver problems;
increased risk of
cancer
Vinyl chloride
zero
0.002
Increased risk of
cancer
Xylenes (total)
10
10
Nervous system
damage
Discharge from
petroleum factories;
discharge from chemical
factories
7-19
CHAPTER 7
Potable Water
Contaminant
MCLG1
(mg/L)2
MCL or
TT1
(mg/L)2
Sources of
Contaminant in
Drinking Water
Alpha particles
none7
15
Increased risk of cancer
---------- picocuries
zero
per Liter
(pCi/L)
Erosion of natural
deposits of certain
minerals that are
radioactive and may
emit a form of
radiation known as
alpha radiation
Beta particles
and photon
emitters
none7
---------zero
none7
---------zero
Uranium
zero
4
Increased risk of cancer
millirems
per year
5 pCi/L
Erosion of natural
deposits
Notes
1
Definitions:
Maximum Contaminant Level (MCL) - The highest level of a contaminant that is allowed in
drinking water. MCLs are set as close to MCLGs as feasible using the best available treatment
technology and taking cost into consideration. MCLs are enforceable standards.
Maximum Contaminant Level Goal (MCLG) - The level of a contaminant in drinking water
below which there is no known or expected risk to health. MCLGs allow for a margin of safety
and are non-enforceable public health goals.
Maximum Residual Disinfectant Level (MRDL) - The highest level of a disinfectant allowed in
drinking water. There is convincing evidence that addition of a disinfectant is necessary for
control of microbial contaminants.
7-20
CHAPTER 7
Potable Water
Maximum Residual Disinfectant Level Goal (MRDLG) - The level of a drinking water
disinfectant below which there is no known or expected risk to health. MRDLGs do not reflect
the benefits of the use of disinfectants to control microbial contaminants.
Units are in milligrams per liter (mg/L) unless otherwise noted. Milligrams per liter are
equivalent to parts per million.
3
EPAs surface water treatment rules require systems using surface water or ground water
under the direct influence of surface water to: 1) disinfect their water, and 2) filter their water or
meet criteria for avoiding filtration so that the following contaminants are controlled at the
following levels:
Cryptosporidium: (as of 1/1/02 for systems serving >10,000 and 1/14/05 for systems
serving <10,000) 99 % removal
Giardia lamblia: 99.9 % removal/inactivation
Viruses: 99.99 % removal/inactivation
Legionella: No limit, but EPA believes that if Giardia and viruses are
removed/inactivated, Legionella will also be controlled
Turbidity: At no time can turbidity (cloudiness of water) go above 5 nephelolometric
turbidity units (NTU); systems that filter must ensure that the turbidity go no higher
than 1 NTU (0.5 NTU for conventional or direct filtration) in at least 95 % of the daily
samples in any month. As of January 1, 2002, turbidity may never exceed 1 NTU,
and must not exceed 0.3 NTU in 95 % of daily samples in any month.
HPC: No more than 500 bacterial colonies per milliliter.
Long Term 1 Enhanced Surface Water Treatment (Effective Date: January 14,
2005); Surface water systems or (GWUDI) systems serving fewer than 10,000
people must comply with the applicable Long Term 1 Enhanced Surface Water
Treatment Rule provisions (e.g. turbidity standards, individual filter monitoring,
Cryptosporidium removal requirements, updated watershed control requirements for
unfiltered systems).
Filter Backwash Recycling: The Filter Backwash Recycling Rule requires systems
that recycle to return specific recycle flows through all processes of the systems
existing conventional or direct filtration system or at an alternate location approved
by the state.
More than 5.0 % samples total coliform-positive in a month. (For water systems that collect
fewer than 40 routine samples per month, no more than one sample can be total coliformpositive per month.) Every sample that has total coliform must be analyzed for either fecal
coliforms or E. coli if two consecutive TC-positive samples, and one is also positive for E.coli
fecal coliforms, system has an acute MCL violation.
5
Fecal coliform and E. coli are bacteria whose presence indicates that the water may be
contaminated with human or animal wastes. Disease-causing microbes (pathogens) in these
wastes can cause diarrhea, cramps, nausea, headaches, or other symptoms. These pathogens
7-21
CHAPTER 7
Potable Water
may pose a special health risk for infants, young children and people with severely
compromised immune systems.
6
Although there is no collective MCLG for this contaminant group, there are individual MCLGs
for some of the individual contaminants:
MCLGs were not established before the 1986 Amendments to the Safe Drinking Water Act.
Therefore, there is no MCLG for this contaminant.
8
Lead and copper are regulated by a treatment technique that requires systems to control the
corrosiveness of their water. If more than 10 % of tap water samples exceed the action level,
water systems must take additional steps. For copper, the action level is 1.3 mg/L and for lead
is 0.015 mg/L.
9
Each water system must certify, in writing, to the state (using third-party or manufacturers
certification) that when acrylamide and epichlorohydrin are used in drinking water systems, the
combination (or product) of dose and monomer level does not exceed the levels specified, as
follows:
7-22
CHAPTER 7
Technical Manual
1.1
Potable Water
Secondary Standard
Aluminum
Chloride
250 mg/L
Color
15 (color units)
Copper
1.0 mg/L
Corrosivity
noncorrosive
Fluoride
2.0 mg/L
Foaming Agents
0.5 mg/L
Iron
0.3 mg/L
Manganese
0.05 mg/L
Odor
pH
6.5-8.5
Silver
0.10 mg/L
Sulfate
250 mg/L
500 mg/L
Zinc
5 mg/L
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Pursuant to the Consumer Confidence Rule, once a year the public water utility
suppliers that serve some community water systems are required to distribute a drinking
water quality report (or Consumer Confidence Report) containing the following
information (40 CFR Part 141, Subpart O):
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Water Sources
Water, in the process of falling rain and washing to the earth, will dissolve minerals,
gasses and liquids.
Part of the rainfall that percolates through the soil and rock strata eventually enters the
aquifer strata to become ground water. This ground water is commonly called well
water.
Other rainfall forms drainage pools and small streams that eventually swirl together to
form rivers and lakes. These bodies of water flow downhill at every opportunity until
they find their way to the sea. Collectively, the streams, rivers and lakes are called
surface waters.
Warm, dry air will evaporate the seawater and other surface waters to form clouds,
which will once again bring water back to the land to fall as rain.
All theses bodies of water differ in the type and amount of dissolved substances which
they carry. Thus, no two sources of water are identical.
Potable water, or water that is considered suitable for drinking and other domestic uses,
is referred to as municipal water. The US Geological Survey classifies ground or
surface waters by their hardness. Soft waters have hardness between 0 and 60 mg/L as
calcium carbonate (CaCO3). Moderately hard waters have hardness between 60 and
120 mg/L as CaCO3. Hard waters have hardness between 120 and 180 mg/L as
CaCO3. Very hard waters have hardness greater than 120 mg/L as CaCO3.
2.1
Water Quality
Pure water does not exist in nature. Water has a strong affinity for dissolving minerals
and other substances with which it comes in contact. This dissolving activity begins
when rain and snow fall to the earth and the water flows into streams or seeps into
underground strata.
Surface streams have little opportunity to pick up an appropriate amount of minerals,
but they tend to sweep away a lot of mud and silt, and therefore contain large amounts
of suspended solids.
Water that trickles through the earth has suspended material filtered out as it passes
through the ground, but it dissolves minerals such as calcium, magnesium and silica.
Water quality is judged by the type and level of dissolved material it contains. There are
many constituents that may be present in the water. Some of these constituents occur
in nature, and some are generated by human technology. Some of the more commonly
used parameters for measuring municipal water quality are:
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Suspended solids
Dissolved gases
Dissolved solids (minerals and organic matter)
Microorganisms
Dissolved oxygen
High turbidity
Lower levels of hardness
Lakes, while they are similar to other surface waters, may have additional
characteristics:
They often have areas of restricted flow or shallow basins where slimy
masses of organisms can thrive.
They tend to have lower turbidity than streams because there is more
opportunity for the suspended solids to settle.
Higher alkalinity
Higher hardness
Greater concentrations of iron and manganese
In addition, dissolved solids from chemical spills and dumping can infiltrate surface
waters and ground waters. No water supply is ever totally free from the danger of this
type of contamination.
2.2
Water Chemistry
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2.2.6 pH
pH is a measurement of the hydrogen ion concentration of the water. The pH scale is
from 0 to 14. A pH of 7 is considered neutral. pH below 7 are considered acidic and
above 7 are alkaline. pH is very important in water chemistry because it has a direct
affect on calcium solubility, the corrosion of the steel distribution system and the
homeowners copper system. For example, the higher the pH, the lower will be the
calcium solubility or the greater the scaling tendency of the water.
2.2.7 Solubility
Solubility refers to the amount of substance that can be dissolved in water. When the
solubility level of a compound is exceeded, precipitation or scale deposition may result.
2.2.8 Conductivity
Conductivity is a direct method of measuring the dissolved solids content of water by
measuring its ability to conduct an electrical current. The higher the dissolved solids
content, the higher the conductivity. Conductivity units are usually expressed as
microSiemen/cm (S/cm).
2.2.9 Common Impurities
Common Impurities normally found in potable water supplies are shown in Table 2-1.
Table 2-1 Common Impurities
Cations
Calcium, Ca2+
Magnesium, Mg2+
Sodium, Na+
Potassium, K+
Iron, Fe2+, Fe3+
Manganese,
Mn2+
Aluminum, Al3+
Arsenic, As+5
Lead, Pb+2
Zinc, Zn2+
Anions
Carbonate, CO32Chloride, ClSulfate, SO42Phosphate, PO43Nitrate, NO3Fluoride, FSilica, SiO2
Bicarbonate,
HCO3Sulfide, S2Hydroxide, OH-
2.2.10 Hardness
Hardness is a term originally used to describe the soap-consuming power of water.
Hardness is commonly defined as the concentration of calcium and magnesium salts in
water, expressed as calcium carbonate (CaCO3). Calcium hardness is a major problem
because it precipitates readily out of the water to form a layer of calcium carbonate
deposits on piping, tanks and other hot surfaces.
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2.2.11 Magnesium
Magnesium salts behave almost identically as calcium salts. The magnesium salts all
tend to have slightly greater solubilities than their calcium counterparts, and this,
coupled with the normally lower concentration of magnesium in potable waters, reduces
the amount of magnesium found in scale.
2.2.12 Alkalinity
Alkalinity is the measurement of OH- , CO32-, and HCO- anions in a water sample. At any
given pH, there will be a mixture of these three species. Alkalinity is very important in
water chemistry because it defines the corrosiveness or scale-forming tendency of the
water. Alkalinity and pH are related, but they are not the same.
2.2.13 Bicarbonate
Bicarbonate ions are very soluble in water and the reaction of calcium with bicarbonate
to form calcium bicarbonate is slow. As bicarbonate, there is little tendency for scaling.
However, the bicarbonate ion decomposes at high pH and/or high heat to yield
carbonate, so what starts as bicarbonate is detected as calcium carbonate. As calcium
carbonate, this salt is less soluble and can lead to deposition problems.
2.2.14 Carbonate
When a carbonate ion combines with calcium to form calcium carbonate, it is the least
soluble of all the calcium salts in potable waters. As a result, calcium carbonate
becomes the most serious and commonly encountered scale.
2.2.15 Hydroxide
Hydroxide refers to OH- radical alkalinity in water. OH- alkalinity does not exist at a pH
below 8.3.
2.2.16 Sodium/Potassium
Sodium and potassium ions are very soluble compounds in potable waters and cause
minimal, if any problems. Sodium ions can increase hypertension in humans and
therefore, their concentration must be restricted. This restriction can apply to hard
water that has been softened using a water softener (sodium cycle ion exchange).
2.2.17 Silica
Silica refers to silica dioxide (SiO2). Its common form is sand and it is the major
component in the manufacture of glass. Silica dissolves in water to form a very weakly
ionized species, silicic acid, that may be represented by the formula SiO22H2O. Silica
is a natural inhibitor in potable waters.
2.2.18 Iron
Surface water systems will usually contain less than 0.5 mg/L iron in a soluble form
(Fe2+), but may contain several mg/L of insoluble iron (Fe3+). Well waters may contain
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0.1 to 10 mg/L dissolved iron, as well as several mg/L of non-dissolved iron. Once the
well water reaches atmospheric oxygen, the dissolved iron will convert to insoluble iron,
producing red water.
The other source of iron originates from corrosion of steel surfaces. This iron comes
into solution as the ferrous ion and is rapidly converted to the ferric state in which it
becomes an insoluble particle.
2.2.19 Manganese
Manganese ions behave very much like iron ions. In surface waters, manganese can
be present in both a soluble (Mn2+) and insoluble form (MnO2), but the insoluble form is
much more likely to occur. The soluble form is more likely to occur in well waters that
are low in oxygen content. The insoluble manganese oxide is responsible for producing
black water. Manganese scale will usually be seen as a black film or coating on steel
surfaces.
2.2.20 Aluminum
Aluminum is not usually found in natural waters except at very low concentrations.
However, appreciable levels can enter the potable water system through the use of
alum [(Al)2(SO4)314H2O] used to facilitate clarification.
2.2.21 Fluoride
Fluoridation of potable waters has been practiced since 1945. It is added in small but
controlled amounts to lessen tooth decay. Optimal fluoride concentration in potable
waters is 1.0 mg/L. The most common methods of adding fluoride to the public water
works is through the addition of sodium fluoride (NaF), sodium silicofluoride (Na2SiF6),
or hydrofluosilicic acid (H2SiF6).
2.2.22 Lead
Lead is a metal found in natural deposits and in household plumbing. The greatest
exposure to lead is swallowing or breathing in lead paint chips and dust. Lead is
rarely found in source waters. It is also known to enter drinking water through the
corrosion of plumbing materials. Lead can cause a variety of adverse health effects.
In babies and children, exposure to lead in potable water above the action level of
0.015 mg/L at the consumers tap can result in delays in physical and mental
development, along with slight deficits in attention span and learning abilities. In
adults, it can cause increases in hypertension, and if consumed over many years,
can lead to kidney problems.
2.2.23 Arsenic
Arsenic is a silver-grey brittle crystalline solid and is found in many rock-forming
minerals. It can also be present in many water sources, typically where water has
flowed through arsenic-rich rocks. If ingested, arsenic can lead to skin disorders
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including hyper/hypopigmentation changes, keratosis and skin cancer. The characteristic chemical features of the high-arsenic ground waters are high iron, manganese,
bicarbonate and often phosphorus concentrations. The maximum contaminate level
(enforceable) for arsenic in potable water is 0.05 mg/L.
2.2.24 Nitrate
Nitrate is increasingly polluting ground and surface waters primarily as a result
of diffuse pollution from agricultural fertilizers. Nitrate is an oxidized inorganic
contaminant which is very soluble in water. Health problems associated with nitrate
appeared in the 1940s where infants who had ingested high nitrate water had
developed methaemoglobinaemia (blue-baby syndrome). The maximum
contaminate level (enforceable) for nitrate in potable water is 10 mg/L measured as N.
2.2.25 Zinc
Zinc may be present in potable waters as a component of the corrosion inhibitor
program. Orthophosphate is also often present in potable waters from the treatment
chemicals.
These two combine to form zinc phosphate. Zinc phosphates solubility decreases as
the pH and temperature increases. Therefore, when using both zinc and
orthophosphate, it is important to control pH to avoid precipitation. Zinc phosphate salt
is extremely insoluble, as is the compound zinc hydroxide. The secondary maximum
contaminate level for zinc in potable water is 2 mg/L. The maximum contaminate
level for phosphate is 10 mg/L as PO4. The zinc concentration overrides the PO4
concentration.
2.2.26 Sulfide
Sulfides accelerate corrosion by reacting with metal piping surfaces to form nonprotective insoluble metal sulfides. It attacks iron, copper and galvanized steel piping to
produce black water even though oxygen is absent.
2.2.27 Organics
Low concentration (mg/L range) organic compounds are commonly found in surface
waters. These organics generally come from decaying organic material such as tenants
and vary seasonally in concentration. These compounds are usually negatively
charged and therefore are removed through clarification. Organics can be very difficult
to measure and/or identify. Organic loading can be determined by measuring Total
Organic Carbon (TOC), and inferred by monitoring turbidity.
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Raw water clarification is the chemical and physical treatment of naturally occurring
waters for the removal of suspended solids, colloidal particles and dissolved
materials, which render the water hazardous or objectionable for use as potable
water.
Potable water must be purified through clarification to eliminate contaminants, which
cause:
Taste and odor
Color
Hazy appearance
Water-borne disease
Excessive hardness
Corrosion of distribution system
The specific equipment and chemicals required for clarification are dependent on the
source of the water and the nature of the contaminants.
Naturally occurring waters contain a broad range of impurities such as suspended
particles, colloidal color bodies, and dissolved organic and inorganic compounds. The
quantity and ratio of these compounds varies with the specific source of the water, and
may also vary significantly from season to season, or even from day to day.
The most common sources of raw water are surface waters such as lakes and rivers,
and ground water from wells.
In general, river waters contain the most variable source of water, as they consist
of a moving body of water which can keep much of the suspended material in
suspension. As the river travels farther from its origin, more suspended matter, as well
as contributions from tributaries, may be picked up. River waters are also prone to
short term fluctuations in the amount of solids due to rain water run-off.
In contrast, the long residence time of a lake allows the majority of settleable
solids to drop out. The natural process leaves the water lower in suspended solids and
the remaining solids with very low particle size. Some lakes are very prone to seasonal
color problems due to algae formation during the summer months or from the decay of
fallen leaves during the winter months. Lakes can also be affected by rain causing
short-term increases in turbidity.
Well waters are typically low in suspended solids, although they may contain sufficient
iron and manganese to impart color and turbidity to the water. Well waters are also
higher in dissolved minerals than many surface waters. Seasonal changes in
well water quality may be related to the fluctuations in the depth of the water table,
although short term effects from rain water run-off are less pronounced.
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The process of raw water clarification involves both physical and chemical treatments of
a water source for the removal of these impurities.
Although each of these processes uses different purity standards, a water treatment
plant may be required to supply water from a single clarification process.
Therefore, the finished water quality would have to meet the standards of the most
demanding process.
Raw water clarifiers are designed to remove two categories of impurities from the influent
water source:
Suspended solids, which range in size from coarse silt to very small particles such
as bacteria and colloidal silica
Color bodies, which may consist of colloidal or dissolved organic and inorganic
compounds
Suspended solids in water are usually measured as turbidity, which is an index of the ability of
particles in the water to scatter light, causing a hazy appearance.
Color in water is measured as the amount of light which is absorbed by the water,
usually at a specific wavelength.
It is quite possible for a specific water to be high in color and low in turbidity or vice
versa. In addition, a raw water source will contain dissolved organic and inorganic
compounds which are not typically removable during clarification, but may be addressed
by additional treatment steps following the clarifiers.
There is a class of polymers called polyelectrolytes that are used to aid in various
liquid/solids separation applications. A polyelectrolyte is a polymer producing highly
charged ions. There are three types of polyelectrolytes:
Cationic: Positively charged polymers
Anionic: Negatively charged polymers
Neutral: Containing both cationic and anionic sites on the polymer
Cationic polymers are polyelectrolytes that produce positively charged ions when
dissolved in water. Cationic polymers are widely used because most suspended
colloidal solids are negatively charged.
Anionic polymers are polyelectrolytes that produce negatively charged ions when
dissolved in water. These polymers are primarily used with aluminum and iron
coagulants.
Neutral polymers are polyelectrolytes that are balanced or neutral in charge. Upon
dissolving in water they release both positive and negative charged ions.
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All three types of polyelectrolytes can be used to aid in various liquid/solids separation
applications.
3.1
3.2
Particle Charge
Most solids present in water are negatively charged. This charge is electrostatic in
nature, and the degree of charge depends upon the types of solids and the electrolytic
environment. When a colloidal particle is dispersed in water, it can ionize, absorb and
attract low molecular weight ions to its surface. Most of these adsorbed counter ions
are held tightly to the colloidal surface (Stern layer). The remainder will be attracted to
the particle and extend into the solution (diffuse layer or Gouy-Chapman layer) until
electroneutrality is established, as shown in Figure 3-1.
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Particle Size
Suspended solids in water can vary in size from 1x10-6 to 0.1 mm (0.001 to 100
microns) in diameter as shown in Table 3-1.
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occurs can also be better understood. Colloidal solids removal can be achieved by any
of the following steps:
Destabilization
Microfloc formation
Agglomeration
Physical entrapment
To coalesce colloids, the interparticle repulsion forces must be neutralized. Certain
cationic chemicals can be used to decrease the net negative charge. This is
destabilization, as shown by Figure 3-2.
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low, such as, for low turbidity waters. Under these conditions, particle collision rates
are low and hence flocculation, even for fully destabilized particles, would be slow.
The formation of many new particles (hydroxide precipitates) gives considerable
enhancement to the flocculation rate. The charge neutralization of stable particles
is rapid and can be achieved at quite low coagulant dosages, but the dosage
should be proportional to the contaminant concentration. Sweep flocculation should
occur at higher dosages and is much slower, but the required dosage should not be
greatly dependent on particle concentration.
The different mechanisms outlined above have led to the definition of four zones of
coagulant dosage, with the following consequences for negatively charged particles:
Zone 1: Very low coagulant dosage; particles still negative and hence, stable
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Treatment Process
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The high energy mixing is then followed by a period of low energy mixing, which allows
for continued particle contact, building large settleable floc. If the low energy mixing is
of too high an energy level, the flocs will be sheared, limiting their size and settling
velocity.
Once a large settleable floc is formed, it must be handled gently and allowed to settle. If
it is subjected to a period of turbulence, the floc may be sheared apart into smaller floc,
reducing its settling rate.
3.9.5 Sedimentation Time
The purpose of coagulation and flocculation is to increase the settling velocity of very
small particles by bringing them together into flocs, which have a larger effective
diameter and so a higher settling velocity. Once this is accomplished, the flocs are
permitted to settle out in the sedimentation basin, allowing clarified water to pass on.
3.9.6 Filtration
Following sedimentation, some small particles may remain in suspension. These are
often removed by passing the water through sand filters, which capture the remaining
floc.
In some cases, filtration will directly follow the coagulation step if the solids
concentration of the water is fairly low.
3.10
Clarification equipment designs vary, but systems may incorporate most of all the
following steps:
1. A pump and influent piping to transfer water from the source to the clarifier
2. Chlorination, powdered carbon, or permanganate feed for organic and biological
control
3. Primary coagulant addition in an area of high energy mixing to coagulate solids
4. pH adjustment chemical to replace alkalinity lost to the coagulant chemical
5. A period of low energy mixing for floc development
6. Coagulant aid addition to build large settleable floc
7. A period of settling to separate the solids from the water
8. A rake to scrape solids to a hopper for removal from the bottom of the unit
9. Overflow weirs to remove clarified water from the surface of the settling area
10. Filters to remove remaining fine particles
11. A holding tank or clearwell to provide a reservoir of clarified water
12. Additional chlorination and pH adjustment for biological and corrosion control
Raw water clarifier design falls into two major categories:
Conventional
Solids Contact
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consumption in the plant can result in an instant flow surge to the clarifier, which can
cause a short term upset.
Another aspect of the operation is the removal of settled solids from the settling basins.
This may be accomplished on a regular basis through the use of a bottom sludge
scraper and sludge discharge pump. In other cases the sludge is removed on an
intermittent basis by taking a basin out of service and washing the sludge down a drain
to be disposed of. Sludge removal is an important operation as a buildup of solids will
reduce the effective volume of the basin, shortening the settling time.
The sludge which is removed from the basins must be disposed of and will often be
dewatered to reduce the volume prior to disposal. Conventional water clarifiers are very
effective at providing for chemical coagulation of turbid waters. Due to their reliance on
long settling periods for solids removal, they require a large area of land being taken up
for flocculators, settling basins, filters and a clearwell. Where the land area is available,
conventional clarifiers are cost-efficient for chemical usage and require minimal operator
involvement. Figures 3-7 to 3-10 are examples of typical clarifiers.
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An upflow blanket clarifier will initially provide for coagulation and flocculation in a
central mixing chamber. This typically consists of a cone or bell shaped hood which is
suspended in the center of the clarifier. The flow must then pass out from under the
hood and rise up to the surface of the clarifier where it is collected in the effluent
launders.
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However, as the flow leaves the hood it will encounter a slurry of previously treated
solids, which will provide for a high amount of interparticle contacts with the flocculated
turbidity. This increases the density of the floc and ultimately incorporates it into the
slurry or sludge blanket.
As the flow rises upward toward the surface, the flow velocity or rise rate is slowed
down due to the geometry of the clarifier. This allows the sludge blanket to separate
from the hydraulic flow of the water as the settling velocity of the floc reaches
equilibrium with the rise rate of the water. Below this level the slurry is maintained in
suspension by the flow of the water, while above this level the water is moving too slow
to carry the floc any higher. This can result in a very well defined interface between the
slurry and the clarified water.
As the hydraulic loading changes, the blanket level will adjust itself to a new equilibrium
level. As long as this level does not change too quickly, or if it is not below the level of
the hood, the unit can absorb some flow fluctuations.
Although a sludge blanket is built up from previously treated solids, the total amount of
solids must be maintained within narrow limits to assure stable operation. Therefore,
sludge solids are discharged regularly to maintain equilibrium. Effectively, the same
amount of solids must be blown down from the unit as are added from the influent
solids, as well as any chemical solids which are added. Many of these units incorporate
a sludge concentrator section into which a portion of the sludge blanket is allowed to
settle. This section is then emptied occasionally by opening a valve which allows the
solids to be discharged. Another design allows excess solids to accumulate in a hopper
at the bottom of the unit for discharge.
Solids recycle clarifiers also use slurry of previously treated floc to provide for increased
particle contact. However, it takes the process one step further by drawing a portion of
the sludge blanket into the reaction hood so it is in contact with the influent solids during
the flocculation stage. This provides for more vigorous particle contact and a very
efficient turbidity removal.
To recycle the solids into the reaction hood, many clarifiers make use of a turbine pump
in a draft tube, which draws slurry from the bottom of the clarifier up through the draft
tube and into contact with the influent water. The slurry and influent water then mix in
the reaction hood to drive the reaction. Many of these units have a slurry pumping rate
which is greater than the influent flow rate so the slurry is cycling around through the
reaction zone at a high rate.
Large recycle clarifiers will use a bottom sludge rake to drive the slurry toward the
turbine so it can be drawn up into the reaction zone. As the flow and slurry leave the
reaction hood, they may encounter a hydraulically suspended blanket in the same
manner as in an upflow blanket clarifier. However, due to the high flocculation
efficiency, it is less dependent on the action of this sludge bed for turbidity capture.
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In fact, some solids recycle clarifiers discharge the flow and slurry in such a way that the
flow does not pass up through a blanket at all. As the flow leaves the reaction hood, the
slurry drops to the bottom of the unit to be recycled while the clarified water rises up and
out of the unit through the effluent launders.
As with the upflow blanket clarifiers, it is necessary to discharge excess sludge regularly
to maintain stable operation. In addition, the operation of a solids recycle clarifier
requires a balance between slurry recycle rates and sludge blanket inventory as the
efficiency of the reaction is dependent on the solids to strip turbidity out of the influent
water. For this reason, solids contact clarifiers will typically require a greater operator
involvement than a conventional clarifier.
3.10.3 Dissolved Air Flotation
Dissolved air flotation (DAF) is a process for the removal of particles/flocs by making
the solid particles float rather than sink, as in clarification. The process functions
by attaching air bubbles to particles so as to reduce the density of the combined bubble
- particle agglomerate. When the density is reduced to below that of water, the
particles rise to the surface where sludge accumulates and can be removed by
skimming. The more bubbles that are attached per particle, the faster the particle
will rise and subsequently the higher the loading rate at which the process can be
operated. The success of the process depends on two factors:
1.) Generation of enough bubbles and
2.) Conditions under which the bubbles and particles stick together
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A typical DAF plant is split into two key components as shown in Figure 3-11.
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Filtration
After the raw water has been treated in a clarifier, it is passed through filters to further
remove the remaining suspended solids. Since some upsets always occur in clarifiers,
the filters are installed downstream of the clarifier unit to entrap the carried particulate
matter.
Water filtration is a physicochemical process for separating suspended and colloidal
impurities from water by passage through a bed of granular media. Filtration is
comprised of three principal mechanisms:
1. Transport mechanisms, which move the particles through the voids in the filter
media so that they come in contact with the surface of the filter media or the
existing deposit
2. Attachment mechanism, by which the transported particles adhere to the surface
of the filter media or the existing deposit
3. Detachment mechanism, created by the hydrodynamic forces of the water
flowing through the filter bed. These forces detach certain parts of the previously
adhered particles, which are less strongly linked to the filter media or previous
deposits. The detached particles then move further into or through the filter.
The interrelationship of the clarifier process upstream of the filters shows up very
strongly in the performance of the filtration process. If the operation of the clarifiers is
carried out poorly, the colloids will pass through the best of filters. If the quality of the
incoming water is such that the floc particles have little resistance to shear stresses, floc
will penetrate completely through the filters. If any of these pretreatment processes
cause large quantities of strong floc to reach the filters, there may be little floc
penetration into the filters and very short filter runs will result.
4.1
Types of Filtration Systems
4.2
Direct Filtration
The gravity type filter is most commonly used in potable water systems. The filtering
media usually consists of the following:
Sand
Anthracite coal
Dual Media (coal + sand)
Mixed Media (coal + sand + garnet)
These media are usually supported by different grades of gravel or very coarse
anthracite. These supporting layers are called subfill. The suspended matter is
entrapped within the voids of the filtering media grains. The accumulating load of
suspended particulate matter causes an increasing loss of pressure during the filter run.
When this loss reaches a predetermined limit, the filter is taken off line for cleaning. The
filter is then cleaned by "back-washing" or reversing the flow from the bottom. By
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backwashing, the suspended matter is washed out of the filter. The backwash effluent
may either be collected for pumping back to the clarifier, or may be discharged to the
sewer.
Backwashing is carried out at high flow rates that range from 10-20 gpm/ft2, depending
on the water temperature. The rapidity with which the pressure loss builds up during a
filter run depends on the hydraulic loading (gpm/ft2), the size of the filter media grains,
and the amount and nature of the suspended matter removed from the water.
The size of the filtering media grains is usually given by the effective size and the
uniformity coefficient. Effective size is that size in millimeters where 10 % by weight of
the filter media particles are finer and 90 % by weight are larger. The uniformity coefficient is the ratio of that size of filter media particles in millimeters, which has 60 % of
the sample by weight finer than itself to the effective size.
Gravity type filters are either rectangular or circular, and are made of steel, wood or
concrete. They are open at the top and operate at atmospheric pressure. In the bottom
is an underdrain collection system which collects the filtered water and distributes the
backwash water, as shown in Figure 4-1.
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Once a suspended particle has penetrated this top layer of fine sand, its chances are
greatly increased for passing through the entire bed because the void spaces become
larger and opportunities for contact decrease as the particle travels downwards. This is
the limitation of rapid sand filters.
The depth of the single filter media, either sand or anthracite, ranges between 24 to 36
inches on top of the subfill and underdrain collection system. The depth of the subfill
can range anywhere from 15 to 21 inches.
Pressure filters are essentially the same as sand filters except that they are round steel
shells and operate under the pressure of incoming water, which may be as high as 150
psi. Anthracite coal has special merits over fine sand. Because of its lower density,
which is a little more than half that of sand (specific gravity of coal is 1.4 and that of
sand is 2.65), and its irregular shape, the filter bed is more porous compared to sand
and is easily backwashed. Because of the angular grains of anthracite coal, the area is
greater per unit volume than the area of sand grains, which are more spherical. This
offers better floc entrapment and allows the use of a coarser anthracite media than the
sand.
Because of the coarse grain size (usually 0.68-0.72 mm), deeper parts of the bed are
effective in filtration as compared to the sand filter media. Also, higher filtration rates, up
to 3-4 gpm/ft2, may be used and longer runs are possible before excessive head loss is
experienced.
Because of the limitations with the sand filter media, where almost 90 % of the
particulate matter is entrapped within the top few inches of the filter bed, dual media and
triple media filter beds were developed.
The dual media concept was the first step toward development of coarse-to-fine
filtration. Basically, this provides a two layer filter in which the coarse upper layer of coal
acts as a roughing filter to reduce the load of the suspended particulate matter applied
to the sand below. Because of the different specific gravities of coal and sand, coal of
proper size in relation to sand remains on top of the sand during backwash. The dual
media depth should range between 18 to 24 inches for coal and 6 to 12 inches for sand.
The triple media filters use coal (specific gravity 1.4), sand (specific gravity 2.65), and
garnet (specific gravity 4.2). The total filter media depth (coal, sand, and garnet) varies
between 30-42 inches in an approximate proportion of 60, 30, and 10 %, respectively.
The effective size for coal is usually 0.84 to 2.0 mm, sand 0.4 to 0.8 mm, and garnet 0.2
to 0.4 mm.
Dual and triple media filters can be operated at 4 to 6 gpm/ft2 flow rates and produce
high water quality (turbidity less than 0.5 NTU). This may be the same as for sand
filters, if not better, but will result in longer runs.
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It is very important to select sizes of sand and coal that are compatible to each other
during backwashing. The size of the lower layers of sand (the size of the particle from
which 90 % are finer) should be such that it requires approximately the same or somewhat lower flow rates for fluidization than the size in the lower layers of coal (90 % finer
size). This would help in the fluidization of the entire bed at the selected backwash flow
rate.
Dual media filters can retain more removed material than a sand filter. In the dual coalsand media filters, performance in filtration and backwashing is better if both these
medias have good mixing near the interface of the two materials, rather than a distinct
layering. Because of intermixing, there is a gradual decrease in the voids of the filter
bed from layers of coal to coal + sand and sand. In order to have good intermixing at the
interface to achieve the goal of coarse-to-fine filtration, the effective size of the sand
should be properly selected. With the specific gravity of coal in the typical range of 1.40
to 1.75, the ratio of 90 % finer coal size to 10 % finer sand size (the effective size)
should be approximately equal to 3. If the ratio is 4, there will be considerable mixing,
and if the ratio is 2 to 2.5, it will result in a sharp interface.
4.3
Direct Filtration
With water having low turbidities (10-20 NTU), direct filtration can be carried out with,
and at times without, the use of synthetic organic polymers. Many cooling water side
stream filters are operated on this principle. These polymers act like filtration aids and
form a microscopic film on the filter media grains where removal of particulate matter
occurs by its deposition on the surface. These polymers also increase the strength of
the floc. Because of high velocity in the filter bed, good opportunities for contact exist
and, therefore, the polymer may be added directly to the filter influent and not in any
upstream flocculator. Generally these polymers are fed at very low dosage rates,
usually less than 0.1 mg/L. However, for good results, the polymer dosages should be
controlled precisely.
4.4
Auxiliary Scour
Since backwashing alone does not provide efficient cleaning of the filter media due to
very little abrasion between the particles, an auxiliary scouring arrangement should
always be provided. Even with sufficient backwash rates, the deposited filtered matter
may break up into large masses which may transport to the bottom and form mud balls.
An auxiliary scour efficiently cleans the filter media. Hydraulic surface or subsurface
washing and air lancing are the most common types of auxiliary scour techniques.
The surface wash arrangement can be a fixed type or a rotary type. In the case of a
fixed type surface wash arrangement, the wash water is introduced at 45-75 psig
through nozzles installed on the fixed piping grid. In the case of a rotary washer, the
orifices are installed on two radial pipe arms supported in the center on a fixed swivel.
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These surface washers are located about 1-2 inches above the filter bed. The wash
water flow rate is approximately 0.5 gpm/ft2 in the case of a rotary washer and
2-4 gpm/ft2 in the case of a fixed washer. Rotary surface washers offer better cleaning
than the fixed type surface washers. Because of the water jet reaction coming out of the
nozzles, the arms rotate, resulting in sweeping and scouring of the entire top of the bed.
The sub-surface wash arrangement is stationary and is located 6 to 12 inches below the
top of the bed. It has four radial arms with nozzles installed on each arm. The water jets
scour the upper layers from below. The surface and sub-surface washers are usually
started about one minute before starting the backwash and are turned off a minute or
two before the termination of the backwash step.
Air scouring is carried out by distributing the air from the bottom of the filter media so
that it flows and scours the entire media. Air may be introduced to the filter through a
separate header-lateral distributor assembly, or may be introduced through the common
underdrain system that distributes both the air and water, either simultaneously or
sequentially.
When air scouring is used simultaneously with backwash water, there is a possibility of
losing the filter media to the drain. Therefore, it is always safer to carry out air scouring
sequentially. The water level should be lowered approximately 6-8 inches above the
filter bed before starting the air scouring to prevent the loss of filter media. Then the
filter should be backwashed. To prevent the disturbance in the subfill, the air should be
introduced at 1-1.5 SCFM/ft2, followed by two step backwash - the first step at
2-3 gpm/ft2 and the second step at 7-8 gpm/ft2.
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Disinfection
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Table 5-1: Common Waterborne Diseases
Waterborne
Disease
Gastroenteritis
Typhoid
Dysentery
Causative
Organism
Salmonella
(bacteria)
Salmonella
typhosa
(bacteria)
Shigella (bacteria)
Source of Organism
in Water
Symptom
Human feces
Inflamed intestine,
enlarged spleen,
high temperature fatal
Human feces
Human feces
Human feces,
Shellfish grown in
polluted waters
Yellowed skin,
enlarged liver,
abdominal pain,
low mortality,
last up to 4 months
Human feces
Mild diarrhea,
chronic dysentery
Cholera
Vibrio comma
(bacteria)
Infectious hepatitis
Virus
Amoebic
dysentery
Entamoeba
Histolytica
(protozoan
Giardiasis
Giardia lamblia
(protozoan)
Cryptosporidiosis
Cryptosporidium
(protozoa)
Legionellosis
Legionella
pneumophila and
related bacteria
Acute diarrhea,
abdominal pain, vomiting,
low grade fever
Acute respiratory illness
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Most pathogens are accustomed to living in the temperatures and conditions found in
humans and other warm-blooded animals. In general, they do not survive outside warmblooded animals. However, there are some significant exceptions. Of those pathogens
that do not survive for very long, significant numbers can still survive in potable waters
long enough to cause sickness, or even death, if ingested. In addition, certain viruses
and protozoans that form cysts can survive for long periods, even under adverse
conditions. Some pathogenic organisms also tend to be resistant to disinfection
processes, therefore, disinfection alone cannot always be assumed to ensure safe
potable water.
Some pathogens can be destroyed by simply storing water in open tanks for extended
periods of time. Some pathogens are removed by sedimentation in those tanks and
others experience natural die-off. This is not usually a practical treatment method
because of the large investment required for the storage facilities. In addition, other
nuisance organisms, such as algae, can actually multiply in the water while it is in
storage.
A significant number of pathogens are removed during the processes of coagulation,
flocculation, sedimentation and filtration. As a result, these processes are normally
required in addition to disinfection if the source water turbidity and pathogen loading are
significant.
5.2
Disinfection Methods
There are three methods that can be utilized to disinfect potable waters:
Heat treatment
Radiation treatment
Chemical treatment
However the most common method is chemical treatment using chlorine or other
oxidizing chemicals.
5.2.1 Heat Treatment
This procedure is not used by the supplier of potable water as a means of disinfection.
When potable water supplies are suspected of contamination, a boil-out order is
suggested by the water supplier to the public as a means to provide safe water.
5.2.2 Radiation Treatment
Ultraviolet radiation (UV) can be used to disinfect potable waters. UV radiation is
readily absorbed and scattered by turbidity in the water. Thus, the water flow must be
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close to the radiation source to be effective. There are no residual effects from the
radiation. The killing action occurs during the brief exposure to UV radiation.
There is a growing interest in the use of UV, as it has been shown to inactivate a
wide range of microorganisms including Cryptosporidium without producing any
disinfection by-products.
The UV spectrum is arbitrarily divided into three radiation bands. The lowest
wavelength, and therefore highest frequency radiation, is the UVC band, that has the
strongest biocidal properties. The wavelengths for the three bands are shown in
Table 5-2.
Table 5-2: UV Wavelengths
Band
UVA
UVB
UVC
Visible
Wavelength (nm)
400-315
315-280
280-200
400-700
UV radiation owes its bactericidal effect to its ability to penetrate the cell wall and
act directly on the nuclear DNA. The radiation does not destroy the bacterial cell
material, but disrupts the DNA by causing adjacent chemical groups on the double
helix of the DNA molecule to fuse and prevent the molecule from replicating. This
means that the bacterium is unable to reproduce and is thus inactivated or not viable.
The bacterium is not killed by the radiation.
Chlorine residual should still be used for disinfection, with UV as the primary
disinfectant and a chlorine residual providing protection in the distribution system.
5.2.3 Chemical Treatment
Chlorine is the most common oxidant used in potable water treatment. However, it is
not the only chemical used for disinfection. Other oxidants used include:
Chlorine/chloramine
Ozone
Chlorine dioxide
Potassium permanganate
The general effectiveness of these oxidants is shown in Table 5-3, as well as their
advantages and disadvantages in Table 5-4.
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KMnO4
E
E
S
S
S
S
S
S
S
Advantages
Strong oxidant,
Easy to feed,
Persistent residual,
Disadvantages
Chlorinated by-products,
Taste and odor,
Effectiveness influenced by pH
Chloramine
No trihalomethane formation,
Persistent residual,
Easy to feed
Ozone
Strong oxidant,
No trihalomethane formation,
No total organic halide formation,
No taste and odor,
Little pH effect,
Coagulant aid
Weak oxidant,
Possible total organic halide
formation,
Effectiveness influenced by pH,
Taste and odor
Short half-life,
On-site generation,
Complex generation and
feeding,
Energy intensive,
Corrosive
Chlorine dioxide
Strong oxidant,
Persistent residual,
No trihalomethane formation,
No pH effect
Easy to feed,
No trihalomethane formation
Potassium
permanganate
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5.2.4 Chlorine
Chlorine is by far the most common oxidant used to disinfect potable waters. It is
supplied either under pressure as a liquefied gas (Cl2); as sodium hypochlorite (NaOClbleach) containing about 13 % available chlorine; as solid calcium hypochlorite
[Ca(OCl)2] containing 30 % available chlorine. The advantage of chlorine disinfectants
is that they form a residual, which remains in the water for long periods and protects it
against bacterial contamination in the distribution system.
Chlorine gas dissolves in water to form hypochlorous acid (HOCl), which further
dissociates to form hypochlorite ions (OCl):
Cl2 + H2O HOCl + HCl
HOCl H+ + OCl
At pH levels below 5, almost all the hypochlorous acid is undissociated, while at pH
levels above 9, dissociation is almost complete. Hypochlorous acid disinfects by
penetrating the bacterial cell walls and attacking the cytoplasmic layer. In the unionized
form, hypochlorous acid diffuses more readily through the cell wall than hypochlorite
(OCl) ion and therefore hypochlorous acid is a more efficient biocide.
Chlorine is usually fed at concentrations of 0.5-1.0 mg/L to provide a residual of
0.1-0.2 mg/L at the end of the distribution system. At these concentrations, there is
negligible chlorine after taste.
The concentration of chlorine required is dependent on the water source, the organism
and the required kill rate. The chlorine residual and contact times vary depending on the
species of bacteria, viruses and amoebic cysts present in the water, and generally a
safety factor is applied to take into account a more resistant species.
5.3
Concentration, C
Contact Time, T
The destruction of the pathogens or kill is proportional to C x T. This means that if the
chlorine concentration is decreased, the contact time, the length of time the chlorine and
the organisms are in physical contact, must be increased to ensure that the kill remains
the same. Similarly, as the chlorine concentration increases, the contact time needed
for a given kill decreases.
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5.3.1 Chloramination
Chloramines can be generated by deliberately adding ammonia, usually in the form of
ammonium salt, such as ammonium sulfate [(NH4)2SO4], simultaneously with chlorine, a
process called chloramination.
Chloramines are less active disinfectants than chlorine, but are very stable and are
often used in distribution systems which have a large capacity and long retention time.
The reaction between ammonium ions and chlorine initially generates monochloramine,
then dichloramine and finally trichloramine, which are known collectively as combined
chlorine.
HOCl + NH4+ NH2Cl + H2O + H+
HOCl + NH2Cl HNCl2 + H2O
HOCl + NHCl2 NCl3 + H2O
The rate formation is pH dependent and chloramination is normally carried out using a
chlorine:ammonia (as N) ratio of 5 : 1 by weight, which minimizes both the free chlorine
residual and the free ammonia concentration. The presence of free ammonia in the
distribution system can give rise to the growth of nitrifying bacteria (Nitrosomonas),
which can result in an increase in nitrite concentration in the water with attendant health
risks.
5.3.2 Ozone
Ozone is a colorless gas that is produced by passing a high voltage electrical corona
discharge through dry air or oxygen. It is a more powerful oxidant than hypochlorous
acid and is approximately 5 times more effective as a disinfectant.
Practical ozone generation systems have maximum gaseous ozone concentrations of
about 50 mg/L; thus, the maximum practical solubility of ozone in water is about
40 mg/L.
Upon addition to water, ozone reacts with hydroxide ions to form hydroxyl radicals and
organic radicals. These radicals cause increased decomposition of ozone and are
responsible for nonselective oxidation of a variety of organic materials. Ozone
decomposition process occurs in second to minutes.
5.3.3 Chlorine Dioxide
Chlorine dioxide can be used as a primary or secondary disinfectant, and it is used for
controlling taste and odor, as well as zebra mussel control. Chlorine dioxide rapidly
inactivates most micro-organisms over a wide pH range. It is typically more effective
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than chlorine but is less effective than ozone. Chlorine dioxide is a powerful oxidant and
will react with a wide range of organic and inorganic compounds. It is used by some
municipalities as an initial oxidant for water having high humic and fulvic substance
levels in order to reduce the formation of THMs. In some cases, it is used only when
the THM precursor level in the raw water is high. The main cause of THMs is
chlorination of precursors, primarily humic and fulvic acids, found in raw water.
Chlorine dioxide is generated on-site. During its production, a small amount of chlorate
(ClO3) and chlorite (ClO2) is formed. There is evidence that these substances can
cause adverse health effects in some individuals.
Chlorine dioxide is capable of oxidizing iron and manganese, removing color, and
lowering THM formation potential. It also oxidizes many organic and sulfurous
compounds that cause taste-and-odor problems. Chlorine dioxide does add a specific
taste to water that is objectionable to some individuals. The maximum residual that does
not cause tastes or odors is usually about 0.4 -0.5 mg/L as ClO2.
5.3.4 Potassium Permanganate
Potassium permanganate is an oxidant that was first used in 1910 for water treatment in
London. However, widespread use of potassium permanganate did not occur until the
1960s, when its effectiveness for controlling tastes and odors had become recognized.
When added to water, permanganate turns the water purple until it finally dissipates
after the completion of the oxidizing action. For this reason, it should be fed as early in
the treatment process as possible to allow completion of the reaction before the water
enters the distribution system. Concentrations as low as 0.05 mg/L permanganate may
still have some noticeable color.
Permanganate is frequently used as the initial chemical fed into surface water systems
because it will control many taste-and-odor-causing substances in the raw water. In
particular, it will eliminate a number of taste-and-odor conditions that will not be
controlled or may be accentuated by chlorine. It also effectively removes hydrogen
sulfide, iron, and manganese. When permanganate alone is not completely successful
in controlling tastes and odors, it may be used in combination with activated carbon.
Permanganate is also being used for trihalomethane control. Feeding permanganate as
the initial oxidant allows chlorine to be applied later in the treatment process, when the
precursors have been reduced. THMs can usually be significantly reduced by this
process. Permanganate is also widely used by groundwater systems to oxidize iron
and manganese. It has also been found effective for controlling zebra mussels and
algae in reservoirs.
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Disinfection By-Products
Disinfection by-products (DBPs) are formed when chemical disinfectants react with
natural organic matter. These by-products are varied and can include the
trihalomethanes (THMs) and haloacetic acids (HAAs). These two groups of DBPs in
particular have led to concern by the USEPA regulators, since theses by-products have
been shown to cause cancer in animals.
U.S. EPA has published the Stage 1 Disinfectants/Disinfection By-Products Rule to
regulate total THM at a maximum allowable annual concentration of 0.08 mg/L. The
EPA has also imposed a limit on the total of five HAAs (monochloro-, dichloro-, trichloro, monobromo- and dibromo-acetic acids) to 60 g/L. While THMs and HAAs are often
the major DBPs formed, recent studies have identified over 500 different DBPs. Which
one is formed will be very dependent on the water quality and the disinfectant used. The
chemical structures of the major groups of DBPs are shown in Figure 5-1.
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Indices
In 1936, W. F. Langelier developed the Langelier Saturation Index (LSI). The LSI is
based on the theoretical tendency of water to deposit or dissolve calcium carbonate.
The index is derived from the solubility product of calcium carbonate, the
dissociation constant of water, the second dissociation constant of carbonic acid
H+ + CO3 HCO3
and stoichiometric equilibrium between alkalinity and protons versus the carbonate,
bicarbonate, and hydroxyl species.
By restricting the applicable pH to 6.5-9.5, a saturation pH, known as pHs, is
determined as:
pHs = (pK'2 pKs) + pCa + pAlk
Where: pX = log (X), or log(1/X)
Ca = calcium ion concentration in moles/liter
Alk = total alkalinity as equivalents/liter
K'2 = second dissociation constant of H2, CO3, corrected for ionic strength and
temperature
Ks = solubility product of CaCO3, corrected for ionic strength and temperature
The Langelier Saturation Index is:
LSI = pH - pHs
It is a logarithm of the ratio of the hydrogen ion concentration that the water must have if
saturated with calcium carbonate to the actual hydrogen ion concentration. A negative
value indicates an undersaturation of CaCO3 and, hence, a tendency to dissolve any
existing CaCO3 coating. A positive value indicates oversaturation, a tendency to
precipitate CaCO3 and to form a protective layer.
When using the LSI, it is imperative to remember that this parameter states a
difference between actual pH and a pH at which CaCO3 equilibrium is theoretically
achieved for that water. It provides no information on the driving force or tendency for
the CaCO3 to dissolve or crystallize in the given water.
Differences between observed conditions and prediction may result from temperature
effects, specific uncharged or ionic constituents in the water, or crystal growth
inhibition. Increased temperatures will decrease the solubility of calcium carbonate, as
well as increase reaction velocities, and consequently, establish local equilibrium
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Ryzner also developed a curve based upon field observations, showing carbonate
scale or corrosion of distribution mains as a function of the index. This curve is shown
in Figure 6-1.
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Figure 6-1: Ryznar Stability Index for various degrees of scale and corrosion
Calculations of the LSI or RSI can be accomplished using the equation for pHs
pHs = (9.3 + A + B) (C + D)
The values for A, B, C, and D are shown in Table 6-1.
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6.1
Larson-Skold Index
The Larson-Skold index is based upon evaluation of in situ corrosion of the steel
distribution lines transporting Great Lakes waters. The index is the ratio of equivalents
per million (epm) of sulfate (SO42) and chloride (Cl-) to the epm of alkalinity in the form
bicarbonate plus carbonate:
Larson-Skold index = (epm Cl- + epm SO42) / (epm HCO3 + epm CO32)
Extrapolation to waters other than the Great Lakes, such as those of low alkalinity or
extreme alkalinity, goes beyond the range of the original data. Unlike the LSI, this
index does not refer to the solubility of CaCO3 but rather to the faster rates of steel
corrosion because of conductivity effects. It is not applicable to waters that are soft or
have a low dissolved solids concentration. The Larson-Skold index might be interpreted
by the following guidelines:
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Index < 0.8: chlorides and sulfates probably will not interfere with
natural film formation.
0.8 < index < 1.2: chlorides and sulfates may interfere with natural
film formation. Higher than desired corrosion rates might be
anticipated.
Index > 1.2: the tendency toward high corrosion rates of a local
type should be expected as the index increases.
The Casil Index is a modification to the calcium carbonate solubility indices that
accounts for the effect of other parameters for soft waters. It is defined as:
CI = Ca2+ + Mg2+ + HSiO3 (Anions/2)
where each concentration is expressed in milliequivalents per liter (meq/L).
Negative values are considered indicators of very corrosive water, values between 0
and 0.1 indicate slightly corrosive waters; and values above 0.1 indicate noncorrosive
conditions.
6.4
The aggressive index was formulated to determine the quality of water that can be
transported through asbestos-cement pipe without adverse structural effects. However,
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it does not incorporate temperature or TDS effects, nor does it indicate the tendency of
the pipe to release fibers or allow Ca(OH)2 leaching.
Aggressive Index = pH + log (AH)
Where A = total alkalinity as mg/L CaCO3
H = calcium hardness as mg/L CaCO3
According to the AI, values greater than 12 define nonaggressive waters; values less
than 10 define highly aggressive waters; and values between 10 and 12 define
moderately aggressive waters.
6.5
With the advent of computers, a more realistic approach has been developed to
calculate the degree of calcium carbonate saturation. This approach is based upon
thermodynamic principles.
The solubility of calcium carbonate is defined as:
[Ca2+] x [CO32] = Ksp
where Ca2+ is the activity of the calcium ion; CO32 is the carbonate activity; and Ksp is
the thermodynamic solubility product for the temperature under study.
[Ca2+] x [CO32] is also known as the Ion Activity Product (IAP), and at equilibrium:
IAP =Ksp
The degree of calcite saturation can be expressed as:
CSI = IAP/Ksp
If water is undersaturated with respect to calcite, then IAP < Ksp; fi the water is at
equilibrium, then IAP = Ksp; if the water is oversaturated, then IAP > Ksp.
To calculate the activities of calcium and carbonate, all of the ion-pairs of each species
must be taken into account. For example, calcium ions will ion-pair with bicarbonate,
carbonate, phosphate, sulfate, and other anionic species in the water. The same is true
for sulfate. Sulfate ions will ion-pair with all cations in solution. These calculations are
easily performed with proprietary software. As a rule of thumb, the logarithm of the CSI
is approximately equal to LSI.
Log (CSI) = LSI
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Lead
The Safe Drinking Water Act (SDWA) passed by Congress in 1974 required the U. S.
Environmental Protection Agency to protect public health by setting drinking water standards for public water supplies. These standards are the recommended maximum
contaminant levels (MCLs) for each contaminant which may have an adverse effect on
human health. The SDWA also required that revised National Primary Drinking Water
Regulations (NPDWR) establish maximum contaminant level goals (MCLGs) and
related MCLs. MCLGs are non-enforceable health-based goals. MCLs are enforceable
limits, set as close as feasible to MCLGs.
In late 1985, the EPA proposed regulations to set MCLGs for other contaminants. Lead
was included for regulation in the NPDWR. New amendments to the SDWA were
signed into law in June 1986. The Act contains a provision banning the use of materials
containing lead in public water supplies and in residences connected to public water
supplies. The amendment forbids the use of pipe, solder or flux that is not lead-free in
the installation or repair of any public water system or in any plumbing system providing
water for human consumption. The term lead-free means solder and fluxes must
contain not more than 0.2 percent lead, and pipes and fittings not more than 8 percent
lead.
Public notice is required when construction materials are used in contact with public
water supply that contain lead and/or where the water is sufficiently corrosive to cause
lead leaching. Both the prohibition of lead usage and the public notice requirements
were effective June 19, 1988.
7.1
The Problem
The major source of lead in drinking water is the result of the corrosive action of the
water on materials containing lead in the distribution system, and not from the source
water, per se. Water leaving the potable water treatment plant is usually relatively leadfree. However, pipes, solder, fluxes and alloys containing lead (brass faucets and
bronze fittings) are corroded by water, thereby causing lead to be discharged from the
consumers tap.
New homes, particularly those with newly-installed soldered piping, generally have high
lead levels in the drinking water. The highest lead contamination occurs during the first
24 months following installation and levels off after five years. The release of lead from
solder joints is also attributed to galvanic corrosion occurring between the solder and
copper pipe.
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Health Effects
Lead Chemistry
7.3.1 Corrosion
Lead is one of the worlds oldest metals. It had been used to transport water since the
days of the Roman Empire and only recently has been banned for use as a water
conduit. Its passive oxide makes lead highly resistant to corrosion and attack by natural
waters. However, even though only minute amounts of lead dissolve in water, lead is an
active accumulative toxicant, and when consumed through drinking water, adversely
affects human health.
The corrosion reaction for lead can be represented as:
Pb0 Pb+2 + 2e
This oxidation reaction takes place at the anodic sites. Simultaneously, a reduction
reaction occurs at the cathodic sites. In water having neutral to alkaline pH, the cathodic
reaction is the reduction of dissolved oxygen:
1/2 O2 + H2O +2e 2OH
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However, it must be stressed that there are many other factors that influence lead
corrosion. These include both the physical and chemical characteristics of the water,
such as velocity, residence time, temperature, pH, hardness and alkalinity.
Galvanic corrosion also will occur with lead. Lead, and more specifically soft solder
(50:50 tin:lead), is anodic to copper. Galvanic attack at lead/copper joints will cause a
leaching of lead from the solder into the drinking water. It is the corrosion products from
galvanic attack that raise lead levels in first-drawn waters that have lain stagnant within
household plumbing for a period of time.
7.3.2 Effect of Flow
Lead concentrations in waters exposed to lead surfaces generally will be higher in
standing water than in flowing water. A rapid pickup of lead occurs within a short period
of time in non-flowing water systems. The NPDWR action level of 0.015mg/L can be
exceeded in standing water within 1.5 hours. Thus, allowing water to flow through
household plumbing for a few minutes before being used may reduce the lead levels
below the action level.
7.3.3 Effect of Dissolved Oxygen
Lead corrosion increases with the oxygen content of the water. Figure 7-1 shows that
lead corrosion in distilled water is directly proportional to the oxygen content in air above
the water.
CHAPTER 7
Potable Water
compounds could act as oxidants. If lead chloramines do form, they may increase lead
solubility by dissociating into lead amine complexes.
7.3.5 Effect of Hardness Ions
It is well known that soft waters are more corrosive than hard waters. This statement
applies essentially to all metals. The impact of water hardness ions on lead corrosion is
shown in Figure 7-2. The data shows a decrease in lead concentration with an increase
in hardness. In most natural waters, an increase in hardness is associated with the
buildup of an adherent calcium carbonate barrier. This type of protective layer is
sufficient to suppress lead corrosion. Hard waters (hardness greater than 120 mg/L as
CaCO3) are less corrosive to lead than soft waters. However, irrespective of water
hardness, waters containing carbonic acid will dissolve calcium carbonate deposits and
accelerate corrosion.
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water lines may have leached lead over many years of use and/or a more stable salt
may have formed on solder joints (i.e., lead carbonate and/or calcium carbonate).
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mg Pb/L
0.398
0.316
0.251
0.200
0.158
0.126
0.100
0.079
0.063
0.050
Log mg Pb/L
-0.14
-0.15
-0.16
-0.17
-0.18
-0.19
-0.20
-0.21
-0.22
-0.23
mg Pb/L
0.040
0.032
0.025
0.020
0.016
0.013
0.010
0.008
0.006
0.005
Treatment Strategies
There are several approaches that can be used to control lead solubility. However, lead
is only one of the many different alloys in the distribution and household system.
Consideration must be given to control not only lead corrosion, but also prevent
deterioration of the entire system. Corrosion by-products, per se, can affect the quality
of the potable water since all waters are corrosive to some degree. How aggressive
water is depends upon its physical and chemical characteristics, as well as those of the
materials with which the water comes in contact. Consideration must be given to
whether a particular treatment option is beneficial to only one aspect of the system or is
it an optimization taking into account all possible effects. Remember, not all effects
need be a problem and may be beneficial.
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There are relatively few options available to minimize lead and/or control
corrosion/scale in both the distribution and house plumbing systems. These include the
use of lead-free solder, which is now mandated (95:5 tin:antimony solders), replacing
lead lines, flushing the system prior to use and chemical treatment. Chemical treatment
can consist of pH control, alkalinity control and the addition of specific corrosion
inhibitors.
7.4.1 Nonchemical Treatment Options
A method to minimize lead in drinking water is to use lead-free materials which do not
require lead-soldered joints, and to use lead-free solders to join copper lines in new
plumbing. The 1986 amendments to the Safe Drinking Water Act requires the use of
lead-free materials (e.g., soft solder) in public water systems. There are solders
available that contain little or no lead and have sufficiently low melting points to allow
the use of the same heating methods used to join copper plumbing as the 50:50 tin:lead
solders. These new solders include 95:5 tin:antimony, 96.5:3.5 and 95:5 tin:silver, 95:5
tin:copper and solders containing the combination of these materials.
Another method to reduce lead levels in potable water is to replace the lead service line
or lead plumbing in both the distribution and home plumbing systems. This approach
suffers from the inordinate cost associated with replacing lead service lines in the
distribution system by the utility. Also, homeowners are reluctant to replace expensive
residential plumbing systems.
Since the high lead levels in first-drawn water are the result of stagnant water, flushing
the system prior to water consumption will reduce the lead concentrations. This is an effective method to reduce lead in drinking water. The homeowner must be proactive and
flush the water from the faucet prior to consumption. Flushing takes time and results in
higher water usage. The consumer is not likely to follow this procedure because the
consumer most likely wants to minimize the amount of water wasted. Only in the
morning will first-drawn water probably be flushed.
7.4.2 Chemical Treatment Options
Chemical treatment is the most viable approach to minimize lead in drinking water and
also control both corrosion and deposits to improve the water's aesthetic quality.
Corrosion products leached from the distribution or household systems can render
potable water undesirable by altering the taste or color or increasing its staining
characteristics. Some of these contaminants include iron, manganese, copper, zinc and
the buildup of deposits which constrict flow.
7.4.2.1
pH/Alkalinity Option
Modifying water quality through pH and/or alkalinity adjustments is the most common
method of reducing corrosion in water distribution systems. In low-alkaline waters, lead
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lower pH-orthophosphate approach (pH 7.2, 1 mg/L to 2 mg/L PO4) results in more
effective disinfection with chlorine while reducing THM formulations.
Although zinc/orthophosphate has no additional benefit compared to orthophosphate
alone in reducing lead solubility, zinc/orthophosphate is beneficial in suppressing
corrosion of other plumbing materials used in the total distribution system.
Zinc/orthophosphate is used primarily in waters where the potential for the formation of
calcium carbonate scale is low, because the inhibitor has no scale inhibitory properties.
These waters are usually soft and slightly acidic. Thus, they are considered to be
aggressive waters. Zinc/orthophosphate corrosion control programs are capable of suppressing attacks on low carbon steel, have some efficacy towards cast iron, mild
inhibition towards copper, and are capable of suppressing the release of asbestos fibers
from asbestos-cement pipe.
Boston, Massachusetts, undertook a corrosion control program using
zinc/orthophosphate to control lead solubility. Bostons water is highly corrosive, having
a pH of 6.7, low alkalinity and soft with a hardness of 14 mg/L as CaCO3. The city has a
significant number of lead service pipes still is use. Because of the widespread
existence of lead materials (piping, solder), the lead content in the drinking water coming from the consumers tap exceeds 0.05 mg/L MCL for a significant portion of the
citys residents. To combat the high lead levels, Boston began to treat its system with
zinc/orthophosphate. Unfortunately, the treatment was unsuccessful. The city then
began pH adjustment using NaOH. This treatment approach was extremely effective. A
review of the data from the zinc/orthophosphate program indicates that the failure was
due to the low pH (6.7). It is extremely important that a pH of 7.2 to 7.4 be maintained
when using zinc/orthophosphate to control steel corrosion and lead solubility. Be aware
that in the Boston study, low pH was the reason the zinc/orthophosphate treatment was
unsuccessful.
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polyphosphate a calcium carbonate scale inhibitor and not effective as an inhibitor for
lead. Their position is that polyphosphates are an antagonist to lead increasing the
release of lead into the water.
The addition of zinc/polyphosphate greatly reduces tuberculation in the distribution
system, and hence, head losses (head losses is the pressure drop resulting from
moving water from one point to another). Waters that are prone to form calcium
carbonate scale can develop thick barrier layers which are non-uniform and porous,
resulting in underdeposit corrosion. The addition of zinc/polyphosphate inhibits the
formation of these barrier deposits.
7.4.2.5
Silicates
Treatments utilizing silicates seem to have a retarding effect on lead solubility, but
require a relatively long period of time (approximately 8-9 months) to show reductions in
lead concentrations. This long-term effect can be explained by the slow formation of a
kinetically-inhibited lead silicate film. Silicates are known to act as cementing agents
over corrosion products, and thus become effective only over long term exposure.
Silicate treatments historically have been used as corrosion inhibitors in soft, lowalkaline waters. Their effectiveness has not matched that of phosphate-based
treatments for protecting iron and steel. Silicate treatments are not recommended for
control of lead solubility in distribution systems.
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Iron and manganese are common impurities in well waters. Arsenic is a common
impurity in some of the wells found in the western states in the U.S.
For iron and manganese removal, the objective is primarily to convert dissolved or
reduced impurities to oxidized forms of these constituents to form Fe(OH)3 and MnO2
precipitants, which are filterable in subsequent unit operations. The most common
methods for small systems include aeration/filtration, cation exchange (softening), and
manganese greensand. Figure 8-1 summarizes some of these technologies.
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It is important to note that what may be considered a proven technology for iron and
manganese removal may not be appropriate for high efficiency arsenic removal, which
is discussed later in this chapter.
8.1
Arsenic Removal
The Final Arsenic Rule establishes an arsenic MCL of 0.01 mg/L (10 g/L or 10 ppb)
(40 CFR 141.62(b)(16)). The compliance date is January 23, 2006 (40 CFR 141.6(j)).
The USEPA has identified seven Best Available Technologies (BAT) that can be used
for the removal of arsenic from drinking water.
1. Activated Alumina
2. Coagulation/Filtration (not a BAT for systems with fewer than 500 service
connections)
3. Ion Exchange
4. Lime Softening (not a BAT for systems with fewer than 500 service connections)
5. Reverse Osmosis
6. Electrodialysis
7. Oxidation/Filtration
Dissolved arsenic must be oxidized to an arsenate [As(V)] state before it can be
removed. Both chlorine (Cl2) and potassium permanganate (KMnO4) are effective in
oxidizing dissolved arsenic to arsenate. Care should be taken when applying chemical
oxidation to dissolved arsenic to produce arsenate, because such oxidation may also
produce trihalomethanes (THMs), haloacetic acids (HAAs) and bromates (BrO3), which
are potentially harmful by-products to human health. Table 8-2 describes the
methodologies to remove arsenate.
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Arsenate
Removal Technologies
Activated Alumina
Comments
Long history as an absorptive treatment for arsenic removal
Arsenic removal is pH-dependent, maximum removal capacity
is at pH 5.5
Adsorption capacity for arsenic decreases outside pH range
5-6
Fluoride, selenium, phosphate and other inorganic materials
compete for adsorption sites
Coagulation/Filtration
Ion Exchange
Lime Softening
Reverse Osmosis
Removes > 90 % As
Not selective and removes all dissolved matter
Electrodialysis
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Copper
National Primary Drinking Water Regulations require that no more than 10 % of tap
water samples exceed the action level of 1.3 mg/L of copper. If this action level is not
achieved, then a treatment technique is required to control the corrosiveness of the
water.
Copper piping has had extensive use in home distributions systems since the end of
World War II, with over 6 million miles of copper plumbing placed into service. It
should be noted that only a relatively few cases of actual plumbing failures have
occurred.
The use of copper plumbing in homes is the result of coppers natural protective oxide,
its flexibility, its ease of joining and installation, and its relative corrosion resistance to a
variety of waters. As noted above, corrosion does occur under certain conditions, all of
which are not well understood. Pitting corrosion may lead to failure from pin-hole leaks.
Some of the problems caused by copper corrosion can be summarized as follows:
Concentrations greater than 1.0 mg/L react with soap to produce insoluble
green "curds."
Traces of copper ions can accelerate the corrosion of both low carbon steel
and galvanized steel.
Traces of copper ion can cause pitting of aluminum pots and pans.
9.1
Copper Reactions
Copper corrosion in potable water systems occurs through the following reactions:
Cu0 Cu+ + e
Cu+ Cu2+ + e
Note that in an oxygenated environment, cuprous ions (Cu+) are unstable and are
transformed into cupric ions (Cu2+).
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9.1.1.2
Localized Corrosion
Erosion-Corrosion
The natural protective cuprous oxide film is subject to erosion-corrosion from
increasing water velocity and temperature, as shown in Figure 9-2.
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Type II Pitting
(Cold Water)
(Hot Water)
(Soft Water)
Pit shape
Scale
morphology on
attacked surface
Water quality
Initiating factors
Stagnation early in
pipe life, deposits
within pipe, high
chlorine residual,
water softeners, alum
coagulation
Higher temperatures,
high chlorine residual,
alum coagulation,
particles
Ameliorating
factors
Natural organic
matter (NOM)
Lower temperature
Treatments
Table 9-1 should only be considered as a rule-of-thumb. Type I pitting (cold water) has
been observed to form under Type II conditions (hot water), and Type II pitting has
occurred under Type I conditions. In the final analysis, all pits include a layer of basic
copper salts overlaying a cupric layer, with the basic salt being predominately malachite
in cold-water pits and bronchantite in hot-and soft-water pits.
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9.1.2.1
Pit Initiation
The sequence of events leading to copper pitting is poorly understood. However, the
key to pit initiation has been thought to be formation of a porous cuprous oxide
membrane over a cuprous chloride layer lying adjacent to the copper surface. Once
formed, this structure presumably localizes certain corrosion processes and is selfperpetuating. It differs from the Cu2O film formation in general corrosion in that it has
physical breaks or other structural characteristics that confer porosity, allowing physical
migration of dissolved species directly to solution.
Formation of cuprous chloride under Cu2O is hypothesized to proceed as follows. First,
a film of cuprous chloride forms immediately when copper is immersed in potable
water containing chloride ion. This cuprous chloride is normally removed from the
surface via a number of pathways, including hydrolysis to Cu 2O, oxidation and
formation of cupric salts, and dissolution into bulk solution. These reactions typically
lead to formation of a passivating scale. Occasionally, however, cuprous chloride is
produced at a rate exceeding its loss via the aforementioned reactions. Under these
unusual conditions cuprous chloride will form under the Cu2O, and pitting will begin.
According to this theory, pit formation will be encouraged by conditions that decrease
loss of cuprous chloride or increase its production.
Several factors known to induce pitting are hypothesized to act via this mechanism. For
instance, pits frequently form on copper surfaces exposed to by-products of general
copper corrosion. Such sites include the base of copper tanks, lower surfaces of
horizontal pipes, and sections of horizontal pipe immediately underneath a section of
vertical pipe. Uniform copper corrosion above these sites produces certain by-products
that are believed to stimulate production of cuprous ions on the lower surface (the
identity of these compounds or their mechanism of action is not understood). This, in
turn, may increase the rate of cuprous chloride formation and initiate pitting attack.
9.1.2.2
Pit Propagation
Current theory of pit propagation is credited to Lucey, who in 1967 postulated that a
membrane cell was the driving force for copper pitting attack. The essential structural
components of this cell are a cuprous chloride deposit lying against the corroding
copper surface with an overlying cuprous oxide membrane.
Luceys theory was that copper pitting corrosion was markedly different from the way
other metals pit. It had been assumed that the anodic pit was surrounded by a large
cathodic surface. Since reduction of oxygen at the cathode produces hydroxyl ions,
which in turn precipitate calcium carbonate from hard waters, the anodes should tend to
be surrounded by thicker calcium carbonate deposits than those that occur elsewhere.
However, Lucey found on examining a large number of failed pipes and tanks that no
more calcium carbonate was deposited around the pits than on other parts of the
surface quite remote from the pitting. There was, however, a large amount of calcium
carbonate present in the tubercle above the pit. This suggested that the reduction of
oxygen took place immediately above the pit and not on the surrounding surface.
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Lucey postulated that the thin cuprous oxide present across the mouth of most copper
pits acted as a bipolar membrane electrode, with the under surface acting anodically
and the upper surface cathodically. Cuprous chloride produced within the pit is believed
to be anodically oxidized to cupric on the underside of the membrane, and the cupric
ions thus produced can further attack copper within the pit to form cuprous ions. The
sequence of reactions is illustrated in Figure 9-6.
Pit Formation
CuCl Cu2+ + e + Cl
beneath Cu2O
Cu2+ + Cu0 2Cu+
Cu2+ + e 2Cu+
outside surface Cu2O
+
4Cu + O2 2Cu2O
Inside the pit cavity there coexists Cu, CuCl and Cu2O at a pH of 3.5.
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9.2
Solder Flux
Pitting in copper piping can also be induced by soldering flux. The pits that develop
usually contain significant amounts of chlorides, but no zinc. The active component in
the soldering flux is primary ammonium chloride. Regardless of the chloride used in the
flux, copper chloride coexists with cuprous oxide in the pit. Soldering flux pitting can be
mitigated by improved workmanship in removing the excess flux prior to sweat-fitting.
9.3
Aluminosilicate
The use of alum to generate aluminum hydroxide [Al(OH)3] as a coagulant to
precipitate silica is a common practice in potable water clarification. Silica is
naturally present in water at 5 to 50 mg/L as SiO2.
There are strong indications that the combinations of aluminum, free chlorine, low
organic matter (NOM), and a pH greater than 8.0 can initiate pitting with throughwall pinholes on copper pipe. The aluminum in the water can catalyze the cathodic
reaction between copper and chlorine after the aluminum is deposited on the copper
surface.
For pitting to occur, the aluminum concentration in the water must be between 10
and 500 g/L (ppb), chlorine level of 0.5-2 mg/L and a pH above 8.2 but below 10.
9.4
Treatment
There are two approaches to reduce the release of copper ions from copper piping.
The first approach is to increase the pH of the potable water to approximately 8. As
the pH of the water increases, the corrosion rate decreases. This is shown in
Figure 9-7.
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Figure 9-8: Copper(II) solubility for different DIC levels with orthophosphate
addition, assuming formation of Cu(OH) 2 (s) and Cu 3 (PO 4 ) 2 2H 2 O(s) at 25C:
a) DIC = 4.8 mg C/L, I = 0.005;
b) DIC = 14.4 mg C/L,I=0.005;
c)DIC=48mg C/L, I = 0.01;
d) DIC = 96mg C/L, I = 0.02.
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Dissolved inorganic carbonate (DIC) is the total concentration of all dissolved inorganic
carbonate species, including carbonic acid, bicarbonate, carbonate, complexes and ion
pairs. DIC is calculated from total alkalinity, pH, temperature, and ionic strength (see
Standard Methods, edition after 1989).
From the data shown in Figure 9-8, the required orthophosphate dosage is
approximately 1-3 mg/L at pH 7, while 3-5 mg PO4/L may be required at pH 8. Note
that there is no approved chemistry to control calcium orthophosphate precipitation in
potable waters.
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Corrosion
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Within the normal pH range of 5.5 to 9 for potable waters, corrosion rates on steel will
decrease with increasing pH. However, the reduction in corrosion with increasing pH is
not sufficient to eliminate the need for chemical treatment as shown in Figure 10-1.
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compared with the uncoupled condition, and the more noble material will act as the
cathode and be protected.
Metals and alloys can be arranged in order of their tendency to be anodic, resulting in a
series called the Galvanic Series, shown in Table 10-1.
Active end
Platinum
Gold
Silver
Titanium
Stainless Steel (passive)
Nickel (passive)
Copper Alloys
Nickel (active)
Tin
Lead
Stainless Steel (active)
Steel
Cadmium
Aluminum
Zinc
Magnesium
The greater the difference between metals listed in the galvanic series, the greater the
driving force for corrosive attack. Coupling steel and magnesium in water will cause the
magnesium to corrode. This is the concept behind cathodic protection. The more
active metal corrodes (anode) and protects the more noble metal (cathode). Corrosion
occurs only at the anode and not at the cathode.
10.2.1 Area Effect
Another important factor in galvanic corrosion is the area relationship between the
cathodic to anodic areas. The larger the cathodic area compared to the anodic area,
the more oxygen reduction will occur, and hence the greater the galvanic current. Thus,
from a practical consideration, the most favorable ratio to limit galvanic corrosion should
be large anodic area to small cathodic area.
Consider the impact of coupling lead to copper. When soft solder is used to connect the
copper pipe to a copper fitting, the solder wets the narrow space between the copper
pipe and the fitting. Excess solder flows from the fitting to the inside of the copper pipe
in contact with potable water. Lead from soft solder is anodic to copper as shown in
Table 9-1. Also, the area where the excessive amount of soft solder is adhering to the
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copper pipe is extremely small compared to the total amount of copper surface in the
system. Thus, the area ratio is between the anode (lead) and the cathode (copper) is
unfavorable. Lead from the soft solder will corrode and leach into the potable water.
Galvanized steel (zinc coated steel) used to transport potable water will provide
corrosion protection as long as the zinc coating remains intact. Zinc is anodic to steel.
Over time, the zinc coating will dissolve in the water leaving behind bare (uncoated)
steel. The water will eventually attack the uncoated steel producing tubercles on the
steel surface.
10.3 Pitting
10.3.1 Steel
Pitting attack is a local form of corrosion. Pitting is an insidious, autocatalytic (selfsustaining), attack on most metal and alloys. Pits usually grow in the direction of
gravity. That is, pits develop and grow downward from horizontal surfaces. Fewer pits
develop on vertical surfaces, and rarely do they grow upward from the bottom of
horizontal surfaces.
Pitting attack occurs in stages:
Initiation
Propagation
Termination
Reinitiation
10.3.2 Initiation
The initial attack on steel surfaces is the result of a momentary increase in metal
dissolution at the surface due to an impurity, a broken surface film, or a random
variation in the water composition at a particular site. Some of the ions that can initiate
pitting on steel are: copper ions at concentrations greater than 0.1 mg/L,
orthophosphate ions at a few milligrams per liter in the absence of a cathodic inhibitor
(zinc or polyphosphate), and high concentrations of chlorine, which generates chloride
ions that are capable of piercing protective oxide surfaces.
10.3.3 Propagation
Once the pit has been initiated, it continues to grow by a self-sustaining mechanism. Pit
propagation is provided by ferrous ions (anodic reaction) being dissolved in the water:
Fe0 Fe2+ + e
The counter oxygen reduction cathodic reaction is occurring on the adjacent iron
surface:
O2 + 2H2O + 4 e 4OH
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The increase concentration of positive charges from the iron ions within the pit results in
the migration of chloride ions (Cl) to maintain electrical neutrality. The ferrous chloride
(FeCl2) that is formed hydrolyzes to ferrous hydroxide and hydrochloric acid:
Fe2+ + 2Cl Fe(OH)2 + HCl
The generation of HCl drops the pH within the pit to as low as 1.5, while the bulk
potable water remains neutral.
Hydrochloric acid stimulates further attack, which increases the dissolved ions within the
pit. As ions dissolve within the pit, the solution becomes more conductive. Corrosion
increases with conductivity. Eventually, the salt concentration within the pit becomes
highly concentrated. Since the solubility of oxygen in concentrated salt solutions is
virtually nil, no oxygen reactions occur within the pit. Thus, there is a difference in
oxygen concentration between the adjacent iron surface and within the pit. The area
with the lower oxygen content is the anode. Thus, a differential oxygen cell also exists
within the pit, further stimulating corrosion. There are at least three modes of attack
occurring within the pit: acid attack, increased conductivity, and oxygen differential
corrosion cell. Pitting is autocatalytic.
10.3.4 Termination
Pit development ceases when there is through-wall penetration or when the salt
concentration within the pit is extremely high and there is no more ionic mobility. Once
ionic mobility becomes limited, the internal resistance within the pit develops into a
resistor and corrosion stops.
10.3.5 Reinitiation
When the pit surface dries, the pit is no longer active and will terminate. When the pit is
rewetted, it may reinitiate due to the reestablishment of the conditions during the
propagation stage.
10.4 Copper
The chemistry of both general corrosion and pit formation on copper piping are
discussed in the section on Copper.
10.5 Tuberculation
Tuberculation is a form of crevice corrosion (oxygen concentration corrosion cell), which
occurs over the surface of steel in knob-like structure. Tuberculation is also known as
under deposit corrosion.
There are five structural features of a tubercle:
Outer crust
Inner shell
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Core material
Fluid-filled cavity
Corroded floor
The outer crust consists primarily of iron oxide (hematite), with other precipitates from
the water (carbonates, silicates, and other insolubles). The inner shell has a layer of
magnetite. The shell provides a barrier to oxygen. Outside the shell, the potable water
is saturated with oxygen. Beneath the shell, there is a very low oxygen concentration in
the fluid-filled cavity. The core material consists of ferrous hydroxide [Fe(OH)2] and
ferrous carbonate (FeCO3). The fluid-filled cavity is acidic from the hydrolysis of ferrous
hydroxide producing hydrochloric acid (HCl). The steel surface under the tubercle is the
corroded floor. The lower oxygen concentration in the tubercle caused the floor to be
anodic. The floor is also attacked by the acid. The attacked surface is broad but not
deep. The surface has a gouge appearance.
Tuberculation is under cathodic control. This means that the oxygen reduction reaction
is the driving force for tubercles. Chemical treatment programs that interfere with the
oxygen reduction reaction (cathodic inhibitors) will reduce the rate of tubercle formation.
Polyphosphates are cathodic inhibitors since they interfere with the oxygen reduction
reaction.
The internal volume of a tubercle is essentially devoid of oxygen. This environment is
very conducive for anaerobic bacteria. The most common microorganism to exist under
these conditions is sulfate reducing bacteria. The bacteria will reduce the sulfates to
sulfides. The overall reaction is:
4Fe + SO42 + 4H2O 3Fe(OH)3 + FeS + 2OH
Ferrous sulfide (FeS) is anodic to steel and will further stimulate corrosion.
10.6 Flow Assisted Corrosion (FAC)
Linear flow of potable water over smooth steel or copper surfaces will cause corrosion
to occur uniformly. At the water-metal surface interface, there is a static layer of water
molecules, which form a semiprotective film over the surface and remain stable.
If the flow over the metal surface is turbulent, the liquid motion impinges upon the
surface and removes the semiprotective film. Additional attack occurs by reacting with
the water. The constant corrosive attack and reformation of the semiprotective film
results in flow assisted corrosion. Mechanical factors play an important part in this
mode of attack. The semiprotective film is mechanically removed by the flowing water,
followed by reestablishment of the film. Film formation is formed from the minute
corrosive attack on the surface. Figure 10-2 shows the flow profile for both linear and
turbulent flow.
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Figure 10-2: Flow profile for linear (a) and turbulent flow (b)
The fluid dynamics in erosion-corrosion by potable waters can be an important factor in
determining the rate of material loss. When erosion-corrosion occurs, the effect of
velocity on the corrosion rate usually exhibits a breakaway phenomenon, wherein a
maximum velocity can be withstood without removal of the protective films. Above this
limiting breakaway velocity, the corrosion rates increase very rapidly.
Copper alloys, in general, are not very resistant to erosion-corrosion in potable water
where the velocity exceeds 5 ft/s.
10.7 Impingement
Impingement is localized erosion-corrosion caused by turbulence or impinging water
flow. Entrained air bubbles tend to accelerate this action, as do suspended solids. This
type of corrosion occurs in pumps, valves, and orifices, and at elbows and tees in
copper pipelines.
Impingement corrosion usually produces a pattern of localized attack with directional
features. With erosion-corrosion, attack occurs over the surface of the metal. The pits
or grooves tend to be undercut on the side, away from the source of water flow.
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The loss of iron from cast iron is known as graphitization. This form of corrosion
selectively leaches out the iron from cast iron, leaving behind graphite still in place. The
cast iron is now weakened at the site because graphite has minimal strength. This form
of attack occurs in soils containing sulfates or sulfate-reducing bacteria and acid waters.
The destruction of water mains occurs at sites where graphitization of cast iron has
occurred.
Another example is the removal of tin from lead-tin solders used in sweat fitting of
copper pipes. This form of attack causes lead to leach into the drinking water.
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Chemical Treatment
There are three basic chemicals used to control corrosion, scale, deposition and metal
stabilization in potable water: inorganic phosphate, zinc and silicates. There are a
multitude of combinations using these three chemical building blocks. For any chemical
treatment program to be used in potable waters, it must be approved by a certifying
agency. At present there are two certifying agencies: NSF and Underwriters
Laboratory.
NSF: changed name from National Sanitation Foundation
ANSI: American National Standards Institute
UL: Underwriters Institute
The NSF/UL Water Treatment and Distribution System Program are responsible for the
certification of drinking water treatment chemicals and drinking water system
components to ensure that these products do not contribute contaminants to drinking
water that could cause adverse health effects.
ANSI/NSF/UL Standard 60: Drinking Water Treatment Chemicals-Health Effects is an
American National Standard, which means that the NSF/UL Standard and the
processes used to develop it conform to ANSIs requirements for voluntary consensus
standards. The standards are copyrighted, but may be used by any organization or
individual for the purpose of product/material evaluation, testing and certification
ANSI/NSF/UL Standard 60 covers corrosion and scale control chemicals; pH
adjustment, softening, precipitation, and sequestering chemicals; coagulation and
flocculation chemicals; well-drilling products; disinfection and oxidation chemicals; and
miscellaneous and specialty chemicals for treatment of drinking water. The standard
addresses the health effect implications of treatment chemicals and related impurities.
Both the treatment chemical and the related impurities are considered contaminants for
evaluation purposes. The two principal questions addressed are:
1. Is the chemical safe at the maximum dose, and
2. Are impurities below the maximum acceptable levels?
Reaction by-products such as the disinfection by-products of chlorine, ozone, hydrogen
peroxide, or other chemicals are not covered by the scope of the standard.
The Standard sets the maximum phosphate content allowed in potable waters
expressed as orthophosphate (PO43) at 10 mg/L.
Maximum zinc content allowed in potable waters expressed as zinc ions (Zn2+) is
2 mg/L. The level of zinc in potable waters is primary compared to the phosphate
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content. That means a product that contains 5 percent zinc as Zn2+ and 10 percent
phosphates as PO43 can only add a maximum of 40 mg/L (2 mg/L Zn2+) even though
the phosphate level is 4 mg/L as PO43.
11.1 Polyphosphates
Polyphosphate is an inorganic phosphate added to potable water. The term
polyphosphate refers to commercially available condensed phosphates. The range of
materials within this classification is broad, extending from the simple diphosphate
(pyrophosphate) to linear long-chain polymeric structures consisting of about 21
repeating O-P units. Only linear polyphosphates are used in potable water, even though
cyclic structures (metaphosphates) and branched chains (ultraphosphates) exist.
The condensed inorganic polyphosphates can be viewed as coming from the
dehydration of orthophosphate. The manufacturing scheme usually involves reacting
phosphoric acid with a base such as sodium hydroxide or sodium bicarbonate to form
slurry with a carefully adjusted Na2O/P2O5 ratio. It is heated to controlled temperatures
in a furnace which thermally dehydrates the slurry to produce the desired product. The
dewatering results in the formation of the typical phosphorus-oxygen linkage. This
condensation reaction gives rise to the term "condensed phosphate." The condensed
phosphates can be either crystalline or glassy, depending upon reactant ratio
Na2O/P2O5 and furnace temperatures. The crystalline materials have a defined crystal
structure, whereas the glassy condensed phosphates are amorphous, devoid of a
defined crystal structure. A simple phosphate conversion scheme is shown in Figure 11-1.
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Potable Water
The crystalline orthophosphate and condensed phosphates used in potable water are
disodium phosphates (Na2HPO4), tetra potassium pyrophosphate (K4P2O7) and sodium
tripolyphosphates (Na5P3O10). The glassy condensed phosphates manufactured by the
fusion of orthophosphate require higher furnace temperatures than needed for the
production of crystalline condensed phosphates. The Na2O:P2O5 ratio which defines the
average chain length is shown in Table 11-1.
Table 11-1: Molecularly Dehydrated Phosphates
Na2O:P2O5
3:1
2:1
5:3
1.1:1
1:1
Compound
Na2PO4 Trisodium phosphate
Na4P2O7 Tetrapotassium
pyrophosphate
Na3P3O10 Sodium Tripolyphosphate
(NaPO3)n Sodium polyphosphate
(SHMP)
(NaPO3)n Sodium polyphosphate
Chain Percent
Length
P2O5
0
42
2
53
Form
Crystalline
Crystalline
3
12-14
57
67
Crystalline
Glass
infinite
68
Glass
Both the crystalline and glassy condensed phosphates have a linear chain structure
with a -P-O-P- backbone as shown in Figure 11-2. When the polymeric n group equals
0, the orthophosphate species exists (Na3PO4); with n equal to 1, the pyrophosphate
composition exists (Na4P2O7); with n equal to 2, tripolyphosphate species exist
(Na5P3O10). As the number of polymeric groups increases and the Na2O:P2O5 ratio
approaches 1:1, a family of glassy condensed phosphates (polyphosphates) are
formed. Commercial glassy polyphosphates used in potable water systems have an n
value of about 4 to 20, and more typically 12 to 14 with a 1.1:1 Na2O:P2O5 ratio.
Therefore, the terms sodium hexametaphosphate or SHMP which are common terms
in the water utility industry are a misnomer. The term implies six repeating units, where
in actuality it contains 12 to 14 repeating units due to the Na2O:P2O5 ratio of 1.1:1. A
longer chain polyphosphate having approximately 20 repeating units is called Glass H.
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Polyphosphates are used in a wide variety of applications in the water utility industry.
These include corrosion control, scale control, metal ion stabilization and dispersion.
Polyphosphates, when used alone, are good steel corrosion inhibitors. Relatively high
levels of polyphosphates are required to provide good corrosion protection. A minimum
concentration of calcium ions is needed to form the protective film on steel with a weight
ratio of at least 1:5 calcium:polyphosphate. The critical factor for inhibition by
polyphosphates is the calcium:polyphosphate ratio and not the polyphosphate
concentration per se. Since the calcium polyphosphate complexes are such large
molecules, diffusion of these species is too slow a process to provide adequate
protection. Thus, flow or turbulence is needed to provide rapid supply of inhibitor to the
metal surface. Since polyphosphates have surface active properties, they will adsorb on
old deposits. These deposits compete for the polyphosphate, thereby decreasing the
available supply for the formation of a protective film. This problem is overcome by initial
high dosage or pretreatment. Normal dosage levels of polyphosphate are 3 to 5 mg/L.
At this concentration, steel corrosion rates range between 4-2 mpy, respectively.
Care must be taken not to over feed, since loose deposits will be dislodged and
dispersed. Iron oxide deposits are susceptible to this action, causing increased red
water problems for a short period of time. Old, tightly adherent corrosion by-products
are not affected by the dispersion action of polyphosphates.
The optimum pH range to control steel corrosion is from 6.5 to 7.8. Polyphosphates are
cathodic inhibitors; that is, they interfere with the oxygen reduction reaction.
O2 + 2H2O + 4e 4OH
The need for calcium ion (or other multivalent ions) suggests the formation of a
positively charged complex which migrates to the cathode, forming an amorphous
polymeric phosphate film which is self-limiting. The cationic complex is accounted for by
assuming that the calcium ion lies in between the polyphosphate chain. The colloidal
particles are then the result of numerous cationic complexes loosely knit one to another
through the calcium ions. This film provides a diffusion barrier for oxygen to reach the
metal surface.
Calcium carbonate scale forms in municipal and homeowner distribution systems
because the water contains calcium and bicarbonate ions which react to produce the
scale or deposit:
Ca2+ + HCO2 CaCO3 + H+
Deposition occurs because the solubility of the reaction product has been exceeded.
The reduction in solubility can occur through an increase in temperature, as in the
homeowners hot water system because CaCO3 solubility decreases with an increase in
temperature. Scale can also develop at the interface of the bulk water and the
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distribution pipe. The solid/liquid interface becomes a favorable site for nucleation and
crystal growth. At the interface, the pH of the water is higher than bulk pH because the
oxygen reduction reaction produces hydroxyl ions. Calcium carbonate solubility
decreases with an increase in alkaline pH.
One of the attributes of polyphosphate is the control of calcium carbonate scale by
threshold treatment, as shown in Table 11-2.
Table 11-2: Calcium Carbonate Scale Control
Percent Calcium Carbonate Inhibition
Concentration as
1:10
Polyphosphate
1:3
PO4 mg/L
Zinc:Polyphosphate
(SHMP)
Zinc:Orthophosphate
0.1
14
10
0
0.2
55
58
0
0.3
71
69
0
0.4
81
80
0
0.5
95
93
0
0.6
100
97
0
0.7
100
0
Conditions: 500 mg/L calcium hardness; 500 mg/L alkalinity; pH =8.0; 65 C; 24 hours,
LSI=2.0; calcite saturation=53x.
The term threshold treatment applies to the use of polyphosphates in substoichiometric
quantities to control the precipitation of calcium carbonate. The dramatic retardation of
calcium carbonate scale by threshold substoichiometric concentrations of
polyphosphates cannot be explained by mole-to-mole relationships in the bulk water.
However, threshold mechanism can be viewed to be surface related; that is, critical
nuclei formation is stymied and sub-crystallite crystal growth is retarded.
Since calcium and the bicarbonate ions are charged particles, they tend to form ion
pairs. Also, in this same aqueous phase, the polyphosphate molecule has a net
electrical charge. As the ion pairs gather together in overall clusters, the polyphosphate
molecule is attracted to this cluster of calcium and bicarbonate ions. The arrival of the
polyphosphate molecule upsets the tentative energy equilibrium of the sub-nuclei-sized
ion clusters causing the individual calcium and bicarbonate ions to go back into solution.
The individual polyphosphate molecule is available to search out other clusters of
potential calcium carbonate nuclei. Thus, only one polyphosphate species can nullify
many groups of calcium carbonate clusters.
Another mechanism of threshold scale inhibitors occurs if the ion clusters are able to
reach a critical nuclei stage, form subcrystallites or eventually calcium carbonate
crystals. In this situation, the electrically charged polyphosphate molecule is attracted to
the growth of the crystallite and further growth is inhibited. Figure 11-4 represents a
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idealized crystal surface. Atoms, ions, or molecules may be adsorbed onto a smooth
surface at an edge, step, or a kink. The Greek letter Tau () shows crystallites
descending and adsorbing on a surface or diffusion of a crystallite to the edge of a
terrace.
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0.5
6
7
3
1.0
82
84
13
1.5
88
87
18
2.0
100
100
25
Conditions: 2.0 mg/L Fe(II); pH=7.0; 25 C; 25 micron filtration
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1:1
Orthophosph
ate:
Polyphosphat
e
27
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Table 11.4: Manganese Stabilization
Concentrati
on
as PO4
mg/L
1:1
Orthophosph
ate:
Polyphosphat
e
100
100
100
0.5
85
75
79
1.0
92
85
85
1.5
95
98
90
2.0
100
100
97
2.5
100
Conditions: 2.0 mg/L Mn(II); pH=8.0; 25 C; 5 mg Cl2/L; 25 micron filtration
CHAPTER 7
Potable Water
by zinc ions, the problem of red water in dead end areas is largely eliminated. Zinc
polyphosphates will deposit over tuberculated pipe, reducing the frequency of
mechanical cleaning. Zinc-polyphosphate provides good to excellent steel corrosion
inhibition. With 0.30 mg/L zinc and 3.0 mg/L polyphosphate, steel corrosion rates
average 3.5 mpy. Increasing the level of zinc to 0.5 mg/L with 5 mg/L polyphosphate,
corrosion rates decrease to as low as 1 mpy.
Zinc-polyphosphate treatments can be fed as two separate liquid feeds: zinc (as zinc
chloride or zinc sulfate) and polyphosphate. Physical mixture also can be used, which
consists of zinc oxide and a polyphosphate glass. A high pH liquid zinc-polyphosphate
formulation developed by a manufacturer consists of zinc and pyrophosphate. The use
of the two phosphorous containing polyphosphates (pyrophosphate) provides excellent
corrosion protection similar to using separate feeds with the higher phosphorus chain
molecule, or a physical mix.
It should be noted that the high pH liquid zinc-pyrophosphate will provide calcium
carbonate scale protection, iron/manganese stabilization, and reduced rates of
reversion. The decrease in reversion is the result of the shorter polymer chain length
plus improved stabilization from zinc being incorporated into the polymer.
If mechanical cleaning is necessary, the zinc-polyphosphate inhibitor will provide
immediate protection to the freshly exposed metal at low treatment concentrations.
Zinc-orthophosphate is a very effective multi-metal corrosion control treatment. It provides
corrosion protection to steel, copper and lead. Common ratios of zinc to orthophosphate
vary from 1:3 to 1:6. Excellent steel corrosion protection is afforded by various ratios of
zinc to orthophosphate. Zinc-orthophosphate treatments also form a rapid protective film
on metal surfaces, consequently preventing corrosion and "red water" problems. Its utility
lies in low hardness and low to moderate alkalinity waters. Zinc-orthophosphate has little
to no calcium carbonate scale inhibitory properties as shown in Table 11-2. The various
zinc:orthophosphate treatment programs will not stabilize iron but will stabilize
manganese, thus eliminating "black" water problems. A 1:3 zinc:orthophosphate
treatment program for iron/manganese stabilization are shown in Tables 11-3 and 11-4.
Steel corrosion rates for zinc-orthophosphate concentrations are excellent with zinc values
of approximately 0.5 mg Zn/L with various orthophosphate levels having ratios of
approximately 1:3 to 1:6 (1.5 mg PO4/L to 3 mg PO4/L). Under these conditions corrosion
rates are 1-2 mpy.
11.3
In essence there are three non-zinc chemical inhibitor treatment programs that are
applicable to potable water systems: 1) polyphosphate, 2) blended polyphosphateorthophosphate, and 3) silicates.
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12.0
Potable Water
Over the years the U.S. EPA has promulgated many rules regulating the level of various
constituents in drinking water for the purpose of protecting human health and well being.
Also of concern to the U.S. EPA is the impact of the land application of waste water/sludge
discharge (or bio-solids) on landfill, and the contaminants that could potentially leach into
the ground water. Under the Clean Water Act of 1974, the U.S. EPA on February 19,
1993 promulgated a final rule to protect human health and the environment from hazards
posed by the disposal and use of sewage sludge applied to agricultural land. The rule is
commonly called the Section 503 Rule because the standards promulgated under the rule
are codified at 40 CRF (Code of Federal Regulations) Section 503.13.
The 503 Rule establishes requirements for final use and discharge of sewage from publicly
owned treatment works (POTWs) under three scenarios: 1) when the sludge is applied to land
for beneficial purposes; 2) when it is disposed of in surface impoundments; and 3) when it is
incinerated. The rule does not apply to the processing of sewage sludge before its ultimate
use or disposeal. It only applies to sewage sludge generated or treated by POTWs that treat
domestic sewage and municipal waste water.
The rule includes specific numerical limits for 10 pollutants for the land application of sewage
sludge. The 10 regulated pollutants are: arsenic, cadmium, chromium, copper, lead, mercury,
molybdenum, nickel, selenium and zinc. Tables 12-1 through 12-4 list their ceiling
concentration, cumulative loading rates, monthly average concentrations and annual loading
rates.
mg/kg
Arsenic
75
Cadmium
85
Chromium
3000
Copper
4300
Lead
840
Mercury
57
Molybdenum
75
Nickel
420
Selenium
100
Zinc
7500
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Arsenic
41
Cadmium
39
Chromium
3000
Copper
1500
Lead
300
Mercury
17
Molybdenum
18
Nickel
420
Selenium
100
Zinc
2800
Monthly Average
Concentration (mg/kg)
Arsenic
41
Cadmium
39
Chromium
1200
Copper
1500
Lead
3600
Mercury
17
Molybdenum
18
Nickel
42
Selenium
36
Zinc
2800
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Annual Loading
Rates (kg per hectare
Arsenic
Cadmium
1.9
Chromium
150
Copper
75
Lead
15
Mercury
0.85
Molybdenum
0.90
Nickel
21
Selenium
Zinc
140
The pollutant of most concern is zinc, since it plays a dominant role in corrosion control of
potable water systems. Shown in Tables 12-5 and 12-6 are the type of calculations
performed to determine the acreage for safe land application. The calculations are shown
for a 100,000 gallon per day and a one million gallon per day (MGD) distribution system.
For a 0.1 MGD plant, using a zinc polyphosphate program, as little as 0.15 acres per year
is needed to dispose of the sludge. A 1 MGD plant will require 1.52 acres per year. Zinc
orthophosphate treatments require a higher concentration of zinc for corrosion control than
the zinc polyphosphate treatment. Therefore, more acreage is needed for sludge
application. A 0.1 MGD and a 1.0 MGD plant, practicing corrosion control with 0.25 mg
Zn/L and 1 mg PO4/L, will require 0.38 and 3.81 acres respectively for sludge application.
It is not uncommon for some utilities to treat their system based upon zinc concentration at
the end of the distribution system. This approach will increase the loading of zinc at the
waste water plant, thus requiring even more acreage for sludge application.
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140 Kilogram/Hectare
2800 Kilogram/Hectare
2.205 lbs/Kilogram
2.47 acres/hectare
Annual
140
2.505
308.7
2.47
125
Kg/hectare
lbs/Kg
lbs/hectare
acres/hectare
lbs/acre
20-year life
0.1
x 8.34
x 0.1
= 0.083
x 0.7
= 0.058
x 365
= 21.31
140
= 0.15
Cumulative
2,800
2.505
6,174
2.47
2,500
MGD
lbs/gallon
mg Zn/L residual (zinc polyphosphate treatment)
lbs/day of zinc
percent of water going to waste water plant
lbs/day of zinc
days/year
lbs zinc/year
lbs/year maximum annual load rate
Acres per year required for safe land application
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140 Kilogram/Hectare
2800 Kilogram/Hectare
2.205 lbs/Kilogram
2.47 acres/hectare
Annual
140
2.505
308.7
2.47
125
Kg/hectare
lbs/Kg
lbs/hectare
acres/hectare
lbs/acre
20-year life
1.0
x 8.34
x 0.1
= 0.834
x 0.7
= 0.584
x 365
= 213.1
140
= 1.52
Cumulative
2,800
2.505
6,174
2.47
2,500
MGD
lbs/gallon
mg Zn/L residual (zinc polyphosphate treatment)
lbs/day of zinc
percent of water going to waste water plant
lbs/day of zinc
days/year
lbs zinc/year
lbs/year maximum annual load rate
Acres per year required for safe land application
Since polyphosphates, orthophosphate and silicates are not among the pollutants
regulated under the USEPA 503 rule, they will have no impact on sewage sludge disposal
practices.
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