ASPE Water Treatment, Conditioning, and Purification

Water Treatment,
Conditioning,
and Purification
CEU 318
April 2023
Continuing Education from the

American Society of Plumbing Engineers
education.aspe.org/RLE
READ, LEARN, EARN: Water Treatment, Conditioning, and Purification
Note: In determining your answers to the CE questions, use only the material presented in the corresponding continuing education article. Using information from other
materials may result in a wrong answer.
Water Treatment, Conditioning,

and Purification
Reprint from Plumbing Engineer Design Handbook, Volume 2 – Chapter 11
All rights reserved.
Water treatment, conditioning, and purification are generally considered to be as follows:

• Water treatment is any process that improves the quality of water to make it appropriate for a specific end use.
• Water conditioning is the process of altering or removing minerals, chemicals, and contaminants from a water source.
• Water purification is the process of removing undesirable chemicals, biological contaminants, suspended solids, and gases from water.
The goal is to produce water that is fit for specific purposes.
REGULATIONS, CODES, AND CONSENSUS STANDARDS

The U.S. Environmental Protection Agency (EPA) has established regulations defining the purity requirements for potable water. For the
purposes of discussion here, it is assumed that all incoming water supplies meet EPA primary drinking water requirements. Potable water
treatment shall comply with the Safe Drinking Water Act and subsequent amendments. The EPA also has identified treatment technologies
with given contaminant removal efficiencies for potable water.
Water treatment and purification systems are designed to comply with one or more of the following consensus standards or legally enforceable
specifications, depending on the industry served and the purity of the water desired:
• EPA National Primary Drinking Water Regulations
• College of American Pathologists (CAP), Clinical and Laboratory Standards Institute (CLSI), and ASTM International standards for
reagent- and laboratory-grade water
• U.S. Pharmacopeia (USP) requirements for pharmaceutical and hemodialysis grades of water
• 21 CFR 210: Current Good Manufacturing Practice in Manufacturing, Processing, Packing, or Holding of Drugs; General
• 21 CFR 211: Current Good Manufacturing Practice for Finished Pharmaceuticals
• Association for the Advancement of Medical Instrumentation (AAMI) standards for water for hemodialysis
• Semiconductor Equipment and Materials International (SEMI) and ASTM D5127 electronics-grade water standards for integrated
circuit and microelectronics manufacturing
• U.S. Food and Drug Administration (FDA) Guide to Inspections of High-Purity Water Systems
• International Society for Pharmaceutical Engineering (ISPE) Baseline Guide Volume 4: Water & Steam Systems
• ISPE Good Practice Guide: Sampling for Pharmaceutical Water, Steam, and Process Gases
• International Organization for Standardization (ISO) standards
BASIC WATER CHEMISTRY

Water to be treated is known generally as raw water, feed water, or source water. Water that has been treated, conditioned, or purified is
known as treated water, conditioned water, or product water. There are many uses for treated water, such as drinking, industrial water supply,
irrigation, river flow maintenance, water recreation, or many other uses, including being safely returned to the environment. Conditioned and
purified water can be found in the development of pharmaceuticals, in chemical and biological laboratories, in semiconductor manufacturing,
in automotive lead acid battery manufacturing, and many other applications.
Incoming water supplies may contain dissolved solids, liquids, or gases or other materials. Solids, chemicals, or substances that dissolve in
water can be described as being electrolytes or non-electrolytes. Electrolytes (also called salts) are chemicals that dissolve in water and separate
into ions, such as sodium chloride (Na+Cl-) and magnesium sulfate (Mg2+SO42-). Non-electrolytes are chemicals that dissolve in water but do
not separate into ions, such as ethanol (C2H5OH), sugars, and many organic materials. The positively charged electrolytes are called cations
because they migrate to a cathode, and the negatively charged electrolytes are called anions because they migrate to an anode. The ions dissolved
in solution act almost independently. For example, magnesium sulfate separates in solution to form positive magnesium ions and negative
sulfate ions. These electrolytes often are referred to as salts or total dissolved solids (TDS).
When an electrolyte compound dissolves in water, the molecules of the compound separate, disperse among the water molecules, and are
completely dissolved. As such, dissolved materials will never settle or fall out of solution up to their maximum solubility. When a compound’s
2 Read, Learn, Earn April 2023
maximum solubility is reached, excess amounts of these compounds will not

dissolve into water and exist as suspended solids that may settle, although no TABLE 11-1(A)
Important Elements and Acid Radicals in Water Chemistry
chemical reaction occurs. Dissolved materials cannot be removed by filtration.
By contrast, particles and suspended solids can be removed by filtration and, if Atomic Equivalent
Element Symbol Valence
large enough, may settle under the influence of gravity. However, as the size of Weight Weight
suspended solids decreases, they may become so small that they will never settle. Aluminum Al 27.0 3 9.0
Many liquids mix well with water, but some liquids are not soluble in
Barium Ba 137.4 2 68.70
water. They may float, sink, or break down into extremely small particles and
then disperse into the water even though they do not dissolve. These liquids Calcium Ca 40.1 2 20.05
are called immiscible liquids. Carbon C 12.0 Variable —
All acidic compounds referred to in water chemistry consist of a hydrogen
ion (H+) combined with a negatively charged conjugate base, or anion. Since the Chlorine Cl 35.46 -1 35.46
conjugate base moves around as a unit, it is convenient to view the conjugate Fluorine F 19.0 -1 19.0
base as an integral anion unit. When a positively charged metallic ion and a
Iron (ferrous) Fe 2+
55.8 2 27.9
negatively charged conjugate base combine, they form a class of chemicals
called salts. When a positively charged metallic ion and a negatively charged Iron (ferric) Fe3+ 55.8 3 18.6
hydroxide anion (OH-) combine, they form a class of chemicals called bases.
Hydrogen H 1.0 1 1.0
All electrolytes can be classified as either acids, bases, or salts. An acid is
any compound capable of giving up a hydrogen ion or proton, thus lowering Magnesium Mg 24.3 2 12.15
the pH. The acid’s conjugate base, or anion, is the compound remaining after Nitrogen N 14.0 Variable —
the loss of the H+: HCl conjugate base = Cl-. A base is any compound capable
of accepting a hydrogen ion or giving up a hydroxide (OH-) ion, thus raising Potassium K 39.1 1 39.1
the pH. The conjugate acid, or metal, is the compound left after the loss of the Oxygen O 16.0 -2 8.00
OH-: NaOH conjugate acid = Na+. A salt separates into cations (a conjugate
Phosphorus P 31.02 Variable —
acid) and anions (a conjugate base) without altering the pH of the solution.
The valence of any element is a measure of its chemical-combining power Sodium Na 23.0 1 23.0
compared to that of a hydrogen atom, which has the assigned value of 1. The Sulfur S 32.0 Variable —
valence is the number of electrons in an atom that are free to share, give, or
take from other atoms. An element with a value of +2 can replace two hydrogen Silicon Si 28.06 4 7.01
atoms in a compound, or an element with a valence of -2 can react with two Conjugate Molecular Equivalent
Formula Valence
hydrogen atoms. When atoms combine to form compounds, a cation atom Base Weight Weight
must combine with an anion atom, and in addition, the sum of valences of the
Bicarbonate HCO3 61.0 -1 61.0
two basic elements must equal zero to form a stable compound.
Most of the chemical reactions occurring in water treatment consist of Carbonate CO3 60.0 -2 30.0
rearranging cation and anion atoms using their valences. As can be seen in Table Chloride Cl 35.46 -1 35.46
11-1(A), hydrogen has a valence of 1, and sulfate has a valence of -2. When
combined to form sulfuric acid, two hydrogen atoms are required to form the Nitrate NO3 62.0 -1 62.0
combination, resulting in the formula H2SO4. The chief exception is the case Hydroxide OH 17.0 -1 17.0
where carbonates and bicarbonates are converted by heating or aeration, giving
Phosphate PO4 95.0 -3 31.66
off carbon dioxide gas in the process, or converting a highly soluble bicarbonate
to a much less soluble carbonate. Sulfite SO3 80.0 -2 40.0
One of the most important equilibria to understand water treatment, Sulfate SO4 96.06 -2 48.03
conditioning, or purification is the carbonic acid, carbon dioxide, bicarbonate,
and carbonate equilibrium, which alters the abundance of each component as a FIGURE 11-1
function of pH (see Figure 11-1). This equilibrium helps regulate and stabilize Relationship of the Abundance of Carbon Dioxide, Bicarbonate,
the pH of ocean waters, and it also plays a major role in boiler water treatment and Carbonate as a Function of pH
and many other applications.
Equivalent weight is the weight, in grams, of any element that could
combine with or displace 1.008 grams of hydrogen or 8 grams of oxygen.
Since the valence of an element is proportional to its combining power, the
equivalent weight is affected by its valence. This is illustrated in Table 11-1(A).
WATER IMPURITIES
While natural, municipal, or source water usually meets EPA drinking water
requirements, it is never chemically pure H2O. Water by itself is an incredibly
aggressive solvent that begins dissolving materials with anything it contacts.
Water vapor begins dissolving materials as soon as it condenses in the sky,
where it picks up gases and dust as it becomes precipitation (rain or snow).
Once it reaches the ground, water will dissolve ionic compounds and minerals

Equivalent weight is the weight, in grams, of any element that could combine with or displace
1.008 grams of hydrogen or 8 grams of oxygen. Since the valence of an element is proportional to its
as it meets the ground, surface, or mineral formations as it percolates through the

earth. Water is classified as surface water when it is obtained from sources such TABLE 11-1(B)
Important Acids and Miscellaneous Compounds in Water
as lakes and rivers and as groundwater when it is obtained from wells or other Chemistry
aquifers originating underground. It is important to understand that these two
Molecular Equivalent
water sources will have different properties, and any water treatment, conditioning, Acid Formula
Weight Weight
or purification efforts must carefully consider the water source.
The following water impurities are discussed in alphabetical order and not Carbonic acid H2CO3 62.0 31.0
necessarily in order of importance, which will vary from one application to the next. Hydrochloric acid HCI 36.46 36.46
Alkalinity Phosphoric acid H3PO4 98.0 32.67
Alkalinity is a measurement of the quantity of dissolved earth minerals in water as
well as the water’s ability to neutralize acids or resist pH changes. All natural water Sulfuric acid H2SO4 98.1 49.05
contains some measure of alkalinity. It is mainly the sum of carbonate, bicarbonate, Sulfurous acid H2SO3 82.1 41.05
and hydroxide ions in water, with borate, phosphate, and silicate ions partially
Molecular Equivalent
contributing to the total. It is reported as parts per million (ppm) equivalent of Compound Formula
Weight Weight
calcium carbonate. Alkalinity is regarded as an important characteristic of water
in determining its scale-forming tendency because unlike most chemicals, calcium Aluminum
Al(OH)3 78.0 26.0
carbonate solubility decreases above 100°F. Additionally, the presence of chemical hydroxide
additives in a plant boiler water system tends to raise the pH of the water, which Calcium
Ca(HCo3)2 162 81.0
converts more bicarbonate alkalinity to a less soluble form, carbonate alkalinity, bicarbonate
which increases the scale-forming characteristics of the water (see Figure 11-1). Calcium
Alkalinity is measured using two end-point pH indicators in a titration with CaCO3 100 50.0
carbonate
acid. The phenolphthalein alkalinity, or P alkalinity, measures the strong alkali
Calcium sulfate CaSO4 136 68.0
(hydroxide) portion of a water’s alkalinity. The methyl orange alkalinity, or M
alkalinity, measures both the strong and weak alkalinity (hydroxide, carbonate, Carbon dioxide CO2 44.0 22.0
and bicarbonate) present in the solution. The M alkalinity is often called the total
Ferric hydroxide Fe(OH)3 107 35.6
alkalinity because it also includes the P alkalinity. Alkalinity is not a measure of
pH, but alkalinity is a contributor to the pH of a solution. Magnesium
MgCO3 84.3 42.1
carbonate
Bacteria and Other Microorganisms Magnesium
Mg(OH) 58.3 29.1
Microorganisms are bacteria, viruses, and other simple organisms. They are living hydroxide 2
forms of matter that are not dissolved in water. Their unusual physiology allows Magnesium
them to grow and multiply in water containing only trace levels of nutrients. sulfate MgSO4 120 60.1
The amount of nutrients found in water usually correlates to the amount of
microorganisms, especially if the temperature is favorable for their growth. Sodium sulfate Na2SO4 142 71.0
Although microorganisms may be considered suspended solids, the treatment
required for their removal is different from treatments used to remove standard suspended solids.
Pyrogens are defined as any living or dead organism or fragment thereof that is capable of causing a fever response when introduced into
the body. Pathogenic organisms such as Legionella are considered pyrogens. Endotoxins, which are cell fragments derived from the walls of
gram-negative bacteria, are considered the most important and widely occurring group of pyrogens.
Other microorganisms include algae (a primitive form of plant life), fungi (plants lacking the chlorophyll required for photosynthesis),
and bacteria, which may exhibit both plant and animal characteristics. Bacteria are further subdivided into slime bacteria, which secrete slime;
iron bacteria, which thrive on iron; sulfate-reducing bacteria, which live by consuming sulfate and converting it to hydrogen sulfide gas; and
nitrifying bacteria, which use ammonia and whose by-product results in the formation of nitric acid.
Other Organisms
This term for biological life is applied to larger living things, such as clams, mussels, their larvae, and other forms of life. These larger organisms
are important because they tend to clog water inlets from bodies of salt and freshwater and also may find their way into the piping system of
a facility.
Calcium
Calcium is a silver-white, bivalent, metallic element of the alkaline-earth group. Calcium exists in several different naturally occurring forms
including calcium bicarbonate, calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate, and calcium silicate. The presence
of bicarbonate and carbonate contributes to the alkalinity of a water supply. Calcium and magnesium are the two most common elements when
speaking of “hard water.” Calcium is not a health concern, and in fact very hard water could provide important supplementary contributions
to the total calcium intake for humans.

Chlorides and Sulfates

The most common forms of chlorides and sulfates are dissolved salts of sodium, potassium, calcium, and magnesium. These impurities may
deposit scale on surfaces with which they come in contact if present beyond their maximum solubility in water. In high-purity water systems,
the presence of chlorides may disrupt the passive layer of stainless steel piping systems and accelerate corrosion.
Chlorine and Chloramine

Chlorine and chloramine are typically not present at significant levels in an untreated water supply, but are added by a municipality to the
public water supply prior to distribution and use in the community. Potable water supplies usually have chlorine or chloramine added for
microorganism control. Chlorine is typically used when the pH is controlled closer to neutral, whereas chloramine is typically used at elevated
pH levels where the municipality is concerned about metals leaching into the drinking water from older piping systems, some of which may
contain lead or pipes that were assembled using lead-based solder.
Dissolved Gases
The most common dissolved gases occurring in natural water supplies are oxygen, carbon dioxide, nitrogen, and hydrogen sulfide. Of increasing
concern is the presence of radon gas in many water supplies obtained from wells. Radon is a radioactive material, and its decomposition has
been linked to increased occurrences of lung cancer.
Corrosion in piping systems is accelerated by oxygen, acidic conditions, or increases in water temperature, and all of these factors can cause
corrosion in metallic piping systems. Removing oxygen from a water supply reduces the corrosiveness of the water. Plant steam systems typically
use additives to remove oxygen to reduce corrosion. Other gases including carbon dioxide, nitrogen oxides, sulfur oxides, and hydrogen sulfide
also contribute to corrosion of metallic piping systems by making the water more acidic.
Dissolved Organic Materials and Organic Carbon

Dissolved organic substances typically found in water include both man-made and natural substances.
Organic carbon molecules may be short in length (low molecular weight) or longer in length (medium to high molecular weight). Man-
made chemical compounds, some of which are harmful to the environment, include herbicides, pesticides, trihalomethanes, surfactants, and
detergents. Most of these are water soluble. Naturally occurring chemical compounds, which are typically not harmful in trace amounts, include
lignins, tannins, humic and fulvic acid, and other bio-decomposition products.
Naturally occurring materials may either be dissolved or exist as a colloidal suspension somewhere between dissolved and suspended. Organic
carbon is essential to life, and bacteria will grow in the presence of organic carbon. The removal and control of organic carbon is critical to the
control of bacteria and the success of many water purification systems.
Fluorides
Fluorides are typically not present at significant levels in a raw water supply, but are added by a municipality to the public water supply prior
to distribution and use in the community. Fluorides are added to a water supply to reduce the risk of tooth decay, but may be harmful if
added in excess.
Hardness
Hardness is a measure of the total calcium, magnesium, iron, and other metallic elements that contribute to the “hard” feel of water or the
difficulty in creating a lather using soap. Carbonate, sulfate, and chloride salts of these elements are responsible for most of the scaling deposited
on pipe and boiler walls. Generally accepted practice limits the term “hardness” to include only calcium and magnesium ions. Hardness usually
is expressed in terms of parts per million (ppm), milligrams per liter (mg/L), or grains per gallon (gpg) as CaCO3, with 1 gpg = 17.1 mg/L.
Because water has a specific gravity of 1, 1 ppm is equivalent to 1 mg/L, so they are typically converted to the same value.
Often, water is characterized in general terms by the amount of hardness as follows:
• Soft: 0–75 mg/L (or 0–75 ppm) (0–4.4 gpg) as CaCO3
• Moderate: 76–150 mg/L (or 76–150 ppm) (4.5–8.7 gpg) as CaCO3
• Hard: 151–300 mg/L (or 151–300 ppm) (8.8–17.5 gpg) as CaCO3
• Very hard: More than 300 mg/L (or more than 300 ppm) (17.5 gpg)
Iron
Iron in water is considered a nuisance substance as it causes staining on fixtures in residential applications when levels are above 0.3 mg/L. Iron
may exist as a dissolved mineral or as a suspended solid, depending on the valence of the iron atom. Iron is typically not a health concern, but
is considered a secondary aesthetic contaminant. It is often responsible for reddish stains on plumbing fixtures or reddish water discoloration.
A common form of iron is ferrous bicarbonate. Because this form of iron is soluble, it may be removed in the same way as hardness, but
there are limitations on how much iron can be removed in this manner. Soluble iron is called ferrous (Fe2+), while insoluble iron is called ferric
(Fe3+). The ferric form of iron is commonly referred to as rust. Iron in the ferrous form is predominant in groundwater sources when there
is no oxygen present. This form of iron will readily and easily oxidize when coming into contact with oxidizing agents such as oxygen and
chlorine. The presence of oxidizing agents in water causes soluble ferrous iron to be converted into insoluble ferric iron. This is the reason that
iron (rust) stains are common in fixtures when ferrous iron exists in an incoming water supply.

Iron creates challenges for almost any process intended to remove it. The ion-exchange processes (water softening) used to remove hardness
may be utilized to remove iron. However, iron is strongly attracted to water softening resins and often oxidizes from the ferrous to the insoluble
ferric state while captured on the resin. This makes it difficult to remove from the resin once it is attached, which creates permanent fouling of
the resin. Iron also creates challenges on the surface of separation membranes where iron may bind to the membrane and cause fouling. Iron
may also exhibit a catalytic effect on some membranes and accelerate the rate of degradation or attack on these membranes.
Lead and Copper
Lead and copper are found in drinking water largely due to leaching from piping and plumbing fixtures. Copper is restricted in municipal
drinking water to 1.3 mg/L, based on SDWA regulatory requirements. When excess copper is present, water has a metallic flavor (at 3 mg/L)
and can leave a blue to green discoloration on surfaces. In adults, water containing copper in excess of 3 mg/L can cause nausea, vomiting,
and abdominal pain. Lead is restricted in municipal drinking water by the SDWA to 15 parts per billion (ppb).
Lead in drinking water fails to leave a residue and generally cannot be tasted. The leaching of lead into plumbing systems can be greatly
reduced by introducing water-soluble orthophosphates into potable water distribution systems. Phosphates for potable water treatment perform
several functions that include iron and manganese control, scale inhibition and removal, corrosion control, and chlorine stabilization. At low
levels, the phosphates react with the lead and copper and hardness ions (calcium and/or magnesium) to form an insoluble coating on the
internal surfaces of the distribution system. Once this coating is formed, observed lead and copper levels in the drinking water drop rapidly.
This effect can be maintained by continued metering of phosphates into the system.
Magnesium
Magnesium is also a bivalent element of the alkaline earth group. The most common forms of magnesium are magnesium carbonate, magnesium
bicarbonate, and magnesium chloride. Together with calcium, these two elements form what are considered the water hardness minerals.
Magnesium is not a health concern, and in fact very hard water could provide important supplementary contributions to the total magnesium
intake for humans, sometimes up to 30 percent.
Manganese
Manganese behaves similarly to iron in that it may exist in either the reduced (soluble) or oxidized (insoluble) state. When manganese is in its
reduced state, it may be removed using an ion-exchange process (water softening) where it creates the same challenges as iron once attached
to the resin. Manganese causes dark-brown staining in fixtures when present at levels above 0.05 mg/L. Manganese may be oxidized to its
insoluble form and removed by mechanical filtration, but manganese is much more difficult to oxidize, requiring higher pH levels and more
contact time than iron.
Nitrates
The EPA has set drinking water limits for nitrates at 10 mg/L. Though water with a high nitrate level is treatable, similar limits are also placed
on the discharge nitrate concentration if neutralized ion-exchange regeneration waste or membrane-separation concentrate is discharged directly
into the environment or into a municipal wastewater treatment system. Thus, knowing the concentration of the supply and the local discharge
limits may be important in the selection of the appropriate treatment equipment and system design.
Per- and Polyfluoroalkyl Substances (PFAS)

The term PFAS is used to describe a group of hundreds of long-lasting, man-made substances that are being found more and more in public
water supplies. Health risks are being associated with many of these substances, but because there are so many variations of PFAS, their overall
levels are challenging to detect. As more negative health effects are attributed to these substances, lower acceptable limits are being adopted
for drinking water. PFAS may be removed by reverse osmosis or deionization in water purification systems.
Silica
The three common forms of silica are soluble, colloidal, and particulate. Soluble silica often is referred to as reactive silica, and colloidal silica
sometimes is called non-reactive or polymeric. The most common form in solution is silicon oxide, and in suspension it is found as a fine
colloid. These impurities tend to deposit a scale on the surfaces they come in contact with and form a gelatinous mass on many separation
membranes. Soluble silica may be removed by ion exchange in water purification systems.
Sodium and Potassium

Sodium and potassium form similar salts, with the most common being sodium or potassium chloride, sodium or potassium carbonate, and
sodium or potassium bicarbonate. Sodium and potassium salts are much more soluble in water than their calcium or magnesium counterparts,
and their solubility also increases with temperature. It is common practice to remove a calcium or magnesium salt and replace it with its
equivalent sodium or potassium salt through softening in boiler water treatment.
Suspended Solids, Turbidity, and Color

Turbidity is a general term used to describe any form of suspended solids in water. Turbidity is visually identified as cloudy or hazy water.
Color is a chemical phenomenon sometimes associated with turbidity and may be an indication of water containing decaying vegetation.
However, the term “turbidity” is often used when referring to mineral particulates because they are usually the most plentiful. Other commonly
occurring impurities that contribute to turbidity are liquids such as oil. Turbidity is commonly measured in formazin turbidity units (FTUs),

nephelometric turbidity units (NTUs), or Jackson turbidity units (JTUs). A nephelometer is a tool used to measure light scattered by particles
suspended in water. As more light is scattered, less light reaches the instrument’s detector, resulting in higher turbidity levels in the water.
Coarse particles that settle rapidly when water is standing are referred to as sediment, and fine particles that mostly remain in suspension
are called silt.
Trace Elements
Trace elements include metals, such as lead and iron; metalloids, such as arsenic; and radionclides (radioactive elements), such as radium and
radon. Trace elements in streams, rivers, and groundwater have natural and man-made sources. Rock weathering, soil erosion, and dissolution of
water-soluble salts are examples of natural sources of trace elements. Many human activities also contribute trace elements to the environment,
such as mining, urban runoff, industrial emissions, and nuclear reactions. Trace elements tend to concentrate in sediment, but also can dissolve
to some degree in water and present a risk to human and aquatic health.
Trace elements are present in very small quantities and are considered problematic only if the amount is above an accepted level for the
intended use of the water. Typically, drinking water standards require the removal of many of these impurities if they are present in the municipal
water supply. Examples are lead, cadmium, copper, barium, silver, lithium, zinc, chromium, mercury, arsenic, and selenium.
When a municipal water treatment system is designed, it may be important for the designer to consider any waste discharges that are
produced by the treatment system. Many publicly owned treatment works (POTW) sell the solids created by the wastewater treatment processes
to local farms as fertilizer, so discharge limits may be placed on certain substances. Though elements may be identified as trace by analysis of
the supply water, they may be concentrated by a particular water treatment process, and the discharge level may exceed local, state, or federal
discharge limits.
Volatile Organic Compounds

Volatile organic compounds (VOCs) are compounds that evaporate readily at ambient temperatures and pressures. Swamp gas is an example
of a naturally occurring VOC. If present in a water supply, VOCs are typically removed by the municipality prior to distribution to the
public. Many of these compounds are man-made, and strict discharge limits are placed on the discharge of such compounds to the POTW as
wastewater. The EPA lists dozens of regulated VOC compounds and dozens more unregulated VOC compounds.
Many of the VOCs of concern for users of high-purity water originate from the treatment process itself. VOCs may originate from the
following typical treatment components:
• Polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (CPVC) pipe
• Polypropylene (PP) and polyethylene (PE) pipe
• Unpolymerized materials used in the manufacture of cation and anion ion-exchange resins
• Solvents or preservatives used in the manufacture of reverse osmosis membranes
• Solvents or unpolymerized materials used in the manufacture of membrane filters
• Solvents or adhesives used to manufacture ultrafiltration and nanofiltration membranes
• Fiberglass-reinforced plastic (FRP)-, PP-, and PE-treated pressure vessels or water-storage tanks
• Filter and ion-exchange vessel linings
• Solvents, glues, adhesives, and dopes used to assemble piping systems
• Other plastic wetted materials used in the construction of a system
Material selection is typically dictated by the water quality requirements of a particular application. Many of the items listed above can be
treated or rinsed to remove VOCs. As manufacturing technologies advance, the contribution of VOCs by the majority of these materials has
been significantly reduced. To determine the best approach for avoiding serious contamination, contact the supplier of the treatment products
and consider the end-use requirements of the water. Because these organic compounds are volatile, they will dissipate dramatically with flushing
and use. Flushing solutions are available to rinse and sanitize high-purity water installations before they are brought online. These solutions
kill bacteria and rinse VOCs from the piping to ensure that the water is suitable for its intended purpose. Collaboration with the user will
determine the impact of VOCs on a process, and this collaboration can save considerable effort, time, and money.
TESTING THE INCOMING WATER SUPPLY FOR IMPURITY LEVELS

Prior to performing any testing of the source water, it is important to understand the end-use requirement for the water and to establish the
impurities that must be monitored, removed, and controlled. Feed water samples are collected and then analyzed to determine the quantities
of various impurities present. In some instances there may be seasonal variations in the quality of the incoming water, so multiple water tests
over the course of a year will determine the level of seasonal variations in impurity levels in the water supplies. This is one of the most important
reasons that pharmaceutical-grade water systems are tested for a full year during initial qualification and validation.
The most accurate analyses of water samples are done by laboratories specializing in this type of work, but the level of some impurities
changes after sampling and must be evaluated onsite. The attribute being measured will also determine the type of sample container selected. For
example, sterile containers must be used when sampling for bacteria, and glass containers should not be used when measuring for silica because
the container is made of silica. To determine seasonal variations, samples must be taken over a period of time to ensure that peak readings and
average values are obtained. Field testing of water samples using field test kits may not be as accurate as laboratory tests for some impurities,
but may provide accuracy levels acceptable to the user. Other impurities or attributes such as dissolved oxygen, pH, water temperature, and
silt density index (SDI) must be tested in the field since the readings will change as the sample is transported to the testing lab.
The results of an analysis may be expressed in several different ways. The most common method used to report the concentration of
materials present in a sample is the weight of an element or compound per liter of water, expressed as milligrams per liter of water. Another
FIGURE 11-2 TABLE 11-2

Typical Water Analysis Report Converting ppm of Impurities to ppm of Calcium
Carbonate
Cation Ionic ppm Multiplier
Hydrogen 50.00
Ammonium 2.78
Sodium 2.18
Potassium 1.28
Magnesium 4.10
Calcium 2.50
Ferrous iron 1.79
Ferric iron 2.69
Copper 1.57
Zinc 1.53
Aluminum 5.55
Chrome 2.89
Anion Ionic ppm Multiplier
Hydroxide 2.94
Chloride 1.41
Bicarbonate 0.82
Nitrate 0.81
Bisulfate 0.52
method is parts per million, which can be expressed either by the weight of an impurity
Carbonate 1.67
compared to the weight of water (abbreviated w/w [weight to weight]) or by the volume
of the impurity to the volume of water (abbreviated v/v). Other units also are used, such Sulfate 1.04
as grains per gallon and equivalents per million (epm). Other Ionic ppm Multiplier
Milligrams per liter is often considered interchangeable with parts per million, but the
former expresses values in w/v whereas the latter expresses values in w/w. This difference is Carbon dioxide 2.27
important in the analysis of highly saline waters, but for potable water supplies where the Silica 1.67
specific gravity of water is equal to 1, milligrams per liter and parts per million are equivalent.
Grains per gallon is often used when calculating ion-exchange equipment capacities, with 1 gpg being equivalent to 17.1 ppm.
Most mineral compounds separate into positively charged and negatively charged ions when dissolved in water, and water testing reveals
the levels of the dissolved ions present in the water solution.
To simplify reporting in water treatment, conditioning, or purification, it may be desirable to report the abundance of specific ions in solution
with reference to a common denominator. The water purification industry has established calcium carbonate as the common denominator, and
the amount of an ion may be expressed as its equivalent abundance to an amount of calcium carbonate. This is accomplished by comparing the
equivalent weight of the respective ions present and expressing them as the part-per-million equivalent of calcium carbonate. This method of
expression is a widely accepted standard for reporting a water analysis in the industry, but not all testing laboratories report results in this manner.
Table 11-2 presents the conversion factors used to convert the measured abundance of an impurity to its calcium carbonate “equivalent.”
Figure 11-2 illustrates a typical water analysis report indicating impurities expressed in parts per million and calcium carbonate equivalents,
which are useful in calculating equipment capacities for many water purification processes.
pH
pH has been called the “power of hydrogen” or “potential hydrogen,” but it really is a measurement of the hydrogen ion concentration in
water and, therefore, a measure of the water’s acidity. pH is calculated from the logarithmic reciprocal of the hydrogen ion concentration in
water according to Equation 11-1:
Equation 11-1
pH = -log [H+]
where
[H+] = Concentration of hydrogen ion, expressed in moles per liter
The pH scale ranges from 0 to 14, with values lower than 7 being acidic, values higher than 7 being basic, and 7 being neutral. When an
acid is added to water, the concentration of hydrogen ions increases, resulting in a lower pH. When a base is added to water, the hydrogen ion
decreases, resulting in a higher pH. Because the pH is determined using a logarithmic equation, a change of 1 pH unit represents a tenfold
change in the acid concentration, a change of 2 pH units represents a hundred-fold change in acid concentration, etc. pH is not a measure
of alkalinity.
One other important consideration with pH is that the accurate measurement of pH depends on the presence of ions (electrolytes) in
solution. As water is purified and these ions are removed, the measurement of pH becomes increasingly difficult. In practice, the measurement
of pH in high-purity water is not recommended as there are no ions present to measure and any attempt to measure pH will measure the pH
of the buffer solution in which the pH probe was last stored.
Specific Conductance or Resistance (Conductivity or Resistivity)
Specific conductance and specific resistance are two different
ways of expressing the same property: the amount of TABLE 11-3
electricity that will pass through a solution. They are related Water Quality Conversion Chart
through Equation 11-2: Conductivity Dissolved Solids (as
Resistivity Minimum
Equation 11-2 at 25°C, CaCO3) Maximum
at 25°C, Possible
microseimens Possible pH
ohms/cm3 ppm ppb gpg pH
Conductivity (μS/cm) x Resistivity (MΩ-cm) = micromhos/cm3
1,000.000
18,240,000 0.0548 0.000 0 7.00 7.00
Specific conductance (conductivity) and specific
18,000,000 0.056 0.028 28 7.11 6.89
resistance (resistivity) measurements do not tell the levels
of any specific minerals, but provide an estimate of the 16,000,000 0.063 0.031 31 7.12 6.88
combined levels of charged minerals (cations plus anions) 14,000,000 0.071 0.036 36 7.13 6.87
dissolved in a water supply. Only minerals that form ions
when dissolving into solution are detectable through 12,000,000 0.083 0.042 42 7.15 6.85
conductivity or resistivity measurements. Impurities that 10,000,000 0.100 0.050 50 7.18 6.82
dissolve but do not form ions will not be detected by the
8,000,000 0.125 0.063 63 7.21 6.79
measurement of conductivity/resistivity.
In general terms, the greater the abundance of dissolved 6,000,000 0.170 0.083 83 7.26 6.74
minerals in water, the more electricity the water will conduct 5,000,000 0.200 0.100 100 7.3 6.7
and the higher the conductivity. As water is purified, the
conductivity decreases. When producing pure or ultrapure 4,000,000 0.250 0.125 125 7.35 6.65
water, the conductivity of the water is usually less than 3,000,000 0.33 0.17 167 7.43 6.57
1 microsiemen per centimeter (μS/cm). At these levels it
2,000,000 0.5 0.25 250 7.54 6.46
becomes increasingly difficult to distinguish the water purity
when expressing the value as conductivity, so expressing 1,000,000 1 0.5 500 7.78 6.22
the inverse relationship (resistivity) becomes much more
500,000 2 1 1,000 8.01 5.99
meaningful and common.
This measurement varies with temperature, and 250,000 4 2 0.1 8.3 5.7
most instruments measure the temperature and display 166,667 6 3 0.2 8.5 5.5
a conductivity or resistivity value adjusted to a reference
temperature of 77°F (25°C). 125,000 8 4 0.2 8.6 5.4
The purest form of water has a resistivity of approximately 100,000 10 5 0.3 8.7 5.3
18.24 megohm-centimeter (MΩ-cm) at 77°F (25°C). This
50,000 20 10 0.6 9.0 5.0
resistivity value is based on the very small concentrations of
hydrogen and hydroxide ions present from the dissociation 25,000 40 20 1.2 9.3 4.7
of water. This dissociation yields concentrations of 1 x 20,000 50 25 1.5 9.4 4.6
10-7 moles per liter for each hydrogen and hydroxide ion,
corresponding to a pH of 7. Because of the temperature 10,000 100 50 2.5 9.7 4.3
sensitivity of resistivity and conductivity measurements, 5,000 200 100 5.0 10.0 4.0
instruments typically correct for temperature and report
4,000 250 125 7 10.1 3.9
conductivity or resistivity normalized to 77°F (25°C).
While the equation given above can be used to convert 2,500 400 200 12 10.3 3.7
resistivity to conductivity, other valuable conversions are also
2,000 500 250 15 10.4 3.6
provided in Table 11-3.
1,000 1,000 500 29 10.7 3.3
Total Suspended Solids and Turbidity
500 2,000 1,000 58 11.0 3.0
Total suspended solids is the sum of all suspended (not
dissolved) material found in a water sample and is commonly 250 4,000 2,000 100 11.3 2.7

expressed in milligrams per liter. Total suspended solids may be measured gravimetrically by passing a water sample through a filter and
weighing the filter after the water has been evaporated. An alternative method of measuring the suspended solids content of a water sample
is by measuring its turbidity.
Turbidity is a measure of the “cloudiness” of water and is measured by shining a beam of light through a sample and detecting how much
light passes through the sample and reaches a detector. Turbidity measurements are typically reported in nephelometric turbidity units (NTUs)
or Jackson turbidity units (JTUs), with higher values indicating cloudier water.
An often-used standard for potable water, turbidity testing is the method for the examination of water and wastewater developed by the
U.S. Public Health Service, which uses formazin to produce a known level of turbidity. The standard color scale to which it is compared is
derived from the platinum cobalt unit.
The most effective method of removing turbidity is by the use of mechanical filtration devices. The equipment chosen to accomplish this
task depends for the most part on the sizes and types of the solids to be retained. Other factors include the materials of construction, the nature
of the raw water, flow rate requirements, the particle removal target, initial and operating costs, and maintenance requirements.
Silt Density Index
The silt density index (SDI) is another tool to measure the suspended solids content of a water supply. This measurement must be done in the
field and cannot be performed on a water sample. It uses a submicron membrane filter and is commonly used to measure the fouling potential
of a feed water source. Since colloids and other fine suspended solids can be any size in the sub-micrometer range, there is no direct method to
measure their concentration in feed water. The silt density index is found by passing the feed water through a 0.4-micrometer filter at an inlet
pressure of 20 to 30 pounds per square inch (psi) (138 to 207 kPa). The silt density is determined using the following formula:
Equation 11-3
1 – (t1/t2) x
SDI =
T 100
where
t1 = Initial time needed to collect a 500-milliliter sample of water through a fresh 0.45-micrometer filter,
47 millimeters in diameter, seconds
t2 = Time to filter and collect a second 500-milliliter sample after exposing the same filter as above to the
flow of feed water for 15 minutes, seconds
T = Total test time, minutes (typically 15 minutes, but may be less for high SDI water)
To obtain an accurate test, at the end of the elapsed time the flow through the filter should never slow to the point of dripping. With higher
SDI water, it is usually good engineering practice to measure t2 at five, 10, and 15 minutes to ensure that an SDI result can be calculated if
the flow slows to drips.
Many manufacturers of reverse osmosis (RO) membranes recommend maximum allowable silt density index values for feed water to
establish membrane warranties. Typically, the maximum silt density index for reverse osmosis membranes is in the range of 3 to 5. In practice,
when water has a silt density index greater than 3 to 5, prefiltration to remove suspended solids is required. However, in some cases, the SDI
cannot be effectively reduced by prefiltration, and the flow of reject water of a reverse osmosis system must be increased to compensate for the
higher fouling potential of the water supply
Total Dissolved Solids

Often referred to as dissolved inorganics or mineral salts, total dissolved solids (TDS) is generally the sum of all dissolved cations and anions.
Dissolved solids may contribute to scale deposition or the corrosion of piping and equipment if not properly addressed.
Water analysis reports may show the abundance of an ion or may express the equivalent abundance as parts per million as CaCO3. For
example, sodium would be reported as Na+, and calcium would be reported as Ca2+. However, the water system designer typically converts
any reported values to the equivalent CaCO3 value (the common denominator). The conversion is done by considering the equivalent weight
of the ion or the atomic weight divided by the ion’s existing exchange valance. The equivalent weight then is converted to CaCO3 by dividing
the ion’s equivalent by itself and multiplying the product by the equivalent weight of CaCO3, or 50. See Table 11-2 for conversion factors for
other common inorganic or mineral salts.
Total Organic Carbon

Total organic carbon (TOC) is a measurement of the organic carbon compounds present in water. These compounds generally indicate the
abundance of “food” that bacteria have available to utilize for growth. TOC is one of the most important tests used to characterize a water
supply in a water purification system.
The measurement of TOC generally requires sophisticated instrumentation, and several different detection techniques are available. Many
companies have opted to measure product water TOC levels for process and quality control purposes.
Bacteria, Microorganisms, and Cell Fragments

The primary purpose of measuring for the presence of bacteria and microorganisms in the incoming water supply is to confirm that the water
meets EPA primary drinking water requirements. This usually involves measurement for total plate count (all bacteria) and also for coliform

(a measure of contamination with fecal matter). Additional bacteria and related testing are described in greater detail in the last section of this
chapter.
Deposit-Forming Materials
Many of the impurities present in a water supply will cause piping system fouling by depositing material on the walls of the pipe, thereby
reducing the efficiency of the system. One of the challenges of water treatment and conditioning is to achieve the correct balance so materials
do not deposit on surfaces.
Scale
Scale is a solid deposit on the walls of a pipe, boiler, or other surface resulting from the precipitation of dissolved mineral solids in the fluid
stream. Scale is less heat-conductive than the piping or boiler and its presence slows heat transfer and interferes with the flow of water by
restricting the inside diameter and increasing the friction of the fluid with the walls of the pipe. Boiler scale consists of calcium, magnesium,
iron, and silica deposits. It can be substantially minimized by pretreating water prior to it entering the boiler to remove much of the scale-
forming ingredients and adding effective chemicals to the feed water to adjust pH, minimize corrosion, and prevent deposits from occurring.
Condenser scale deposits consist of calcium carbonate, calcium sulfate, and silica minerals. They form when the minerals’ concentration in
water reaches a level where their solubility or the pH of saturation is exceeded and the minerals precipitate out of solution. This can be prevented
by controlling the pH, diluting the circulating water to prevent concentration, and adding chemicals to inhibit and prevent scale formation.
Sludge
Sludge is a sticky, adherent deposit resulting from the settling out of suspended matter from several sources. One source is an excess of iron
in the fluid, generally iron oxide (rust) and iron carbonate (a corrosion product). Other sources are mud, dirt, and clay that tend to collect
and adhere in areas of low flow. Sludge is prevented by filtering the incoming feed water and adding chemical dispersants to keep the solids in
suspension and in motion, which can then be removed during blowdown. Mud, dirt, and clay are much more prevalent when the feed water
is from surface sources.
Biological Fouling
Microbiological fouling is caused by the growth of bacteria, algae, fungi, and other organisms. Their growth is aided by favorable water
temperature, favorable pH, the presence of oxygen, and organic matter. The buildup of microbes and their waste products on surfaces, which
may also include dust and other suspended matter, is called slime or “biofilm.”
Microbial control is achieved by sterilization, disinfection, and sanitation. Sterilization is the lethal destruction of all bacteria, mold, and
yeast. It kills but may not remove biofilm and spores, and numerically it is defined as a 6-log reduction in bacteria. Disinfection is defined as
a 5-log reduction of microbials. Sanitation generally is considered a killing of vegetative organisms. It minimizes the presence of bacteria, and
numerically it is defined as a 3-log reduction in bacteria.
Chemicals, ultraviolet radiation, heat, filtering, and ozone are the methods most commonly used to control biofouling. The method selected
depends on the intended use of the treated water and the proposed materials for the system components.
Corrosive Properties of Water

Some impurities present in a water supply will reduce the thickness of the pipe wall through corrosion, which will eventually cause failure of
the piping system. Corrosion is the loss and eventual failure of metals and alloys from the chemical or electrochemical reaction between water
and the pipe material. It is separated into two basic types: general and localized. Conventional corrosion treatment of feed water for boilers,
chilled water, and cooling water systems consists of pH control and the use of chemical corrosion inhibitors.
General Corrosion
General corrosion is a breakdown of the pipe material at a uniform rate over its entire surface by direct chemical attack. It is caused by the loss
of the protective passive film that forms on the surface of a pipe coupled with a chemical reaction occurring between the pipe material and the
chemicals in the fluid. Particular types of general corrosion include the following:
• Galvanic corrosion occurs in a liquid medium (called an electrolyte) when a more active metal (anode) and a less active metal (cathode)
come in contact with one another and form an electrode potential. When this occurs, the more active (noble) metal tends to dissolve
in the electrolyte and dissolve into solution.
• Intergranular corrosion occurs in a pipe wall when material in the grain boundary of some alloys is less resistant to the corroding agent
than the grains themselves, and the bonds between the grains are destroyed.
• Erosion corrosion is caused by the wearing of a pipe wall, usually as a result of excessive fluid velocity or constant wearing by solids in
the water striking the walls of the pipe.
Localized Corrosion
Localized corrosion takes place on small areas of the surface, usually at higher rates than general corrosion. It takes the following forms:
• Stress corrosion cracking is a physical deterioration and cracking of a pipe wall caused by a combination of high operating temperature,
tensile stress on the pipe, and chemicals in the fluid stream.
• Pitting is characterized by deep penetration of the metal at small areas of the surface, concentrating in small cells without affecting the
entire surface.

• Crevice attack corrosion occurs at junctions between surfaces (often called crud
traps) where a crack exists that allows the accumulation of a corroding agent. TABLE 11-4
Prediction of Water Tendencies by the Langelier Index
Predicting Scale Formation and Corrosion Tendencies Langelier
A common and costly water-caused problem is the formation and deposit of mineral Saturation Tendency of Water
scale. Although scale deposits may contain a complex mixture of mineral salts, sludge, Index
and biological fouling, the primary constituent is usually calcium carbonate.
Scale forming and for practical purposes
Most salts are more soluble in hot water than in cold water. Calcium and 2.0 noncorrosive
magnesium salts, on the other hand, follow this general rule up to about 100°F, but
as the temperature increases above 100°F, the solubility of calcium and magnesium 0.5 Slightly corrosive and scale forming
salts decreases. As a result, they tend to deposit on surfaces when a rise in temperature 0.0 Balanced, but pitting corrosion possible
occurs. As the temperature rises, the tendency of dissolved solids to precipitate out of
solution increases because of their property of inverse solubility. This is particularly -0.5 Slightly corrosive and non-scale forming
true of calcium carbonate. -2.0 Serious corrosion
Alkalinity and pH are other factors that contribute to mineral
scale formation. The pH value reflects the concentration of TABLE 11-5
hydrogen ions (H+) or hydroxyl ions (OH-) in aqueous solutions. Numerical Values for Substitution in Equation 11-3 to Find the pHs of
The level of this concentration, as indicated by pH, defines the Saturation for Water
ratio of bicarbonate to carbonate alkalinity. The measure of Maximum
pH is made on a logarithmic scale. One end of the scale is the Total Solids, ppm Ca as CaCO3,
A C Alkalinity, D
ppm
hydrogen proton, and the other end is the hydroxyl ion. When ppm
the pH is 7, the amount of hydrogen protons and hydroxyl 50–330 0.1 10–11 0.6 10–11 1.0
ions in the water is exactly balanced. A pH below 7 indicates
an acid or a predominance of hydrogen protons. A pH above 400–1,000 0.2 12–13 0.7 12–13 1.1
7 indicates a basic solution or a predominance of hydroxyl 14–17 0.8 14–17 1.2
ions. A pH below 5 indicates 100 percent carbonic and other Temperature, °F (°C) B 18–22 0.9 18–22 1.3
mineral acids. A pH between 5.3 and 8.2 indicates a bicarbonate/
carbonate relationship in the water. A pH above 8.2 indicates 32–34 (0–1.1) 2.6 23–27 1.0 23–27 1.4
carbonate and hydroxyl alkalinity (refer to Figure 11-1). As 36–42 (2.2–5.6) 2.5 28–34 1.1 28–35 1.5
the pH proceeds upward from acidic to basic, the increase in 44–48 (6.7–8.9) 2.4 35–43 1.2 36–44 1.6
carbonates increases the tendency for calcium and magnesium
carbonates to precipitate out of solution. 50–56 (10–13.3) 2.3 44–55 1.3 45–55 1.7
58–62 (14.4–16.7) 2.2 56–69 1.4 56–69 1.8
Langelier Saturation Index 64–70 (17.8–21.1) 2.1 70–87 1.5 70–88 1.9
In the 1930s, W. F. Langelier studied the primary factors that
affect the tendency of water to form deposits of mineral scale on 72–80 (22.2–26.7) 2.0 88–110 1.6 89–110 2.0
heat-transfer equipment. As a result of this work, the Langelier 82–88 (27.8–31.1) 1.9 111–138 1.7 111–139 2.1
Saturation Index (LSI) was created. This index is based on 90–98 (32.2–36.7) 1.8 139–174 1.8 140–176 2.2
numerical values given to the factors that affect deposits.
The index is actually a calcium carbonate saturation index. 100–110 (37.8–43.3) 1.7 175–220 1.9 177–220 2.3
It is based on the assumption that water with a scaling tendency 112–122 (44.4–50) 1.6 230–270 2.0 230–270 2.4
will deposit a corrosion-inhibiting and protective film of calcium 124–132 (51.1–55.6) 1.5 280–340 2.1 280–340 2.5
carbonate on a surface and thus be less corrosive. Water with a
non-scaling tendency will dissolve protective films and thus be 134–146 (56.7–63.3) 1.4 350–430 2.2 350–440 2.6
more corrosive. The interpretation of the LSI is based on the 148–160 (64.4–71.1) 1.3 440–550 2.3 450–550 2.7
numerical values given in Table 11-4. 162–178 (72.2–81.1) 1.2 560–690 2.4 560–690 2.8
The LSI is calculated as follows:
178–194 (81.1–90) 1.1 700–870 2.5 700–880 2.9
Equation 11-4
194–210 (90–98.9) 1.0 880–1,000 2.6 890–1,000 3.0
LSI = pH – pHs
where
LSI = Langelier Saturation Index number
pH = pH value obtained from testing the water in question
pHs = Calculated pH of saturation for the calcium carbonate present in the water in question
The most accurate method is to use the following formula to calculate pHs:
Equation 11-5
pHs = (9.3 + A + B) – (C + D)

The numerical values of A, B, C, and D for substitution into FIGURE 11-3

Equation 11-5 are found in Table 11-5. A more empirical method pH of Saturation for Water
to find pHs is to use Figure 11-3.
Ryzner Stability Index
The Ryzner Stability Index (RI), often referred to as the stability
index, is an empirical method used to predict the scale-forming
tendencies of water. The RI is calculated from the following formula,
applying the same definitions used for the LSI.
Equation 11-6
RI = 2 pHs – pH
The RI is always positive. When it falls below 6, scale formation
is possible. Lower numbers of the index indicate more probable
scale formation. For an interpretation of the RI, refer to Table 11-6.
Aggressiveness Index
Developed by the EPA, the Aggressiveness Index (AI) is used as a
guideline parameter to find the corrosive tendency of potable water.
This index is calculated as follows:
Equation 11-7
AI = pH + Log10 (Alkalinity× Hardness)
Both alkalinity and hardness in this equation are expressed in
mg/L. AI values lower than 10 indicate aggressive water; values between 10 and 12 indicate
moderately aggressive water; and a value higher than 12 indicates nonaggressive water. TABLE 11-6
Prediction of Water Tendencies by the Ryzner
TECHNOLOGIES AVAILABLE TO THE PLUMBING ENGINEER Index
This section describes the various technologies available to the plumbing engineer to treat, Ryzner Index Tendency of Water
condition, or purify a water supply based on a specific purpose, specification, or requirement.
Following this section is a discussion of the applications of these technologies to solve the 4.0–5.0 Heavy scale
water treatment, conditioning, or purification requirements of various industrial, laboratory, 5.0–6.0 Light scale
and high-technology applications. Technologies are presented in alphabetical order and not in
6.0–7.0 Little scale or corrosion
the order in which they may be employed in a treatment, conditioning, or purification system.
7.0–7.5 Significant corrosion
Aeration
Aeration is a gas-transfer process in which water is brought into contact with air for the purpose 7.5–9.0 Heavy corrosion
of transferring volatile substances either into or out of the feed water. It is used most often to 9.0 and higher Intolerable corrosion
remove undesirable gases such as carbon dioxide, hydrogen sulfide, and methane. Aeration, by
introducing oxygen, also is used to oxidize iron and manganese into removable particles and
to lower the amount of VOCs that may be contained in groundwater. Following are criteria for its use.
• Reduction of carbon dioxide by 90 percent is obtained by near saturation with oxygen. Carbon dioxide dissolved in groundwater will
reduce the pH of the water (refer to Figure 11-1).
• Aeration will partially remove VOCs from raw water either by oxidation, making them insoluble, or by evaporation, where the air
introduced causes the VOCs to be transferred to the air stream.
• Aeration alone could be used for the removal of hydrogen sulfide in concentrations of 2 mg/L or less. Above this level, it could be used
in conjunction with chlorination, which oxidizes hydrogen sulfide.
• Iron and manganese may be removed by aeration if this will not be done by other methods. These metals are oxidized to form insoluble
oxides, which precipitate out at the proper pH levels. They then can be removed by settlement or filtered out of the water stream. This
process is sensitive to pH, and iron is easier to remove than manganese.
• Aeration is also an effective technology for removing radioactive radon from groundwater supplies and venting radon gas to the
atmosphere.
The types of aerators commonly used are waterfall, diffusion (or bubble), and mechanical. Waterfall is used most commonly in utility
water treatment.
Waterfall aerators are made in several types: cascade, spray nozzle, and multiple tray. Raw water enters the unit from the top and falls by
gravity to the bottom, and various methods are used to evenly distribute and disperse the water throughout the unit. The type of waterfall
aerator most commonly used is the naturally ventilated, multiple-tray type. This unit consists of a series of trays, one above the other, with
perforated, slot, or mesh bottoms. The trays are filled with 2 to 6 inches (40 to 140 mm) of a medium, such as coke, stone, or ceramic balls,
to improve water distribution and gas transfer as well as to provide catalytic oxidation in the medium. The vertical opening between trays
ranges between 12 and 30 inches (305 and 762 mm), depending on the number of trays required. Water loading on the trays is usually in the

range of 10 to 20 gpm per square foot (379 to 757 L/min/m2). Efficiency can be improved by the use of enclosures and forced air blowers to
provide counter-flow ventilation.
The simplest aerator is the diffusion type, which bubbles compressed air up through a water tank. Although commonly used in municipal
wastewater treatment processes, the large volume of air required limits this to low flows of water. Air requirements vary from 0.1 to 0.2 standard
cubic feet per minute (scfm) per gallon (0.003 to 0.006 m3/min/L) of water aerated. A detention time, which ranges from 10 to 30 minutes, is
necessary but also depends on the pH of the water. Advantages of this type of aerator are the freedom from cold-weather operating problems,
very low head loss, and the possibility of using this process for chemical mixing.
Mechanical aerators consist of an open impeller operating on the water surface of a tank. They are not as efficient as the waterfall or diffusion
types, so longer retention times are necessary.
Carbon Filtration
Carbon filtration using activated carbon may be used to remove residual chlorine, chloramine disinfectants, ozone, dissolved organics such as
trihalomethanes, and some naturally occurring dissolved organic material from municipal water supplies. The removal of disinfectants from
a water supply may be required as part of a water purification system as these disinfectants are oxidizing agents that are detrimental to many
processes such as reverse osmosis. The presence of chlorine speeds up the destruction of the passive layer of stainless steel and other metallic
piping systems, greatly accelerating corrosion rates.
Some system designers are reluctant to use activated carbon filters in the generation of pure water because of the development of significant
levels of bacteria in the unit itself. Depending on the
application, this may or may not be a concern. Bacteria FIGURE 11-4
levels in activated carbon beds may be controlled in several Schematic Detail of Large-Scale, Granular-Activated Carbon Filter
ways depending on the size of the system:
• By periodically (every three to six months) removing
the carbon and replacing it with fresh carbon
• By frequent backwashing and monitoring, with
replacement every six to 12 months based on
bacteria levels
• By periodically sanitizing the unit with hot water at
a temperature between 150°F and 180°F (65°C and
80°C). The need for sanitizing can be determined
only by testing the water. Because of this need for
sterilization, the interior of the filter housing should
be lined or coated.
A typical detail of a packed-bed, backwashing activated
carbon unit is illustrated in Figure 11-4.
Another important consideration for the removal of
materials by activated carbon filtration is contact time, which
should be optimized based on application requirements.
As an example, the contact time required for carbon to
effectively remove chlorine is about two minutes, but
chloramine removal is much more difficult, requiring
approximately five times the amount of contact time
compared to chlorine.
Clarification
Clarification reduces or removes turbidity, silt, and sediment in the raw water supply through gravity settling, and it is typically reserved for
high water volumes and wastewater treatment. The water could be treated with chemicals, filtered, or some combination of both depending
on the amount of impurities present and the volume of water to be treated. If treated with chemicals, time is required for the solids to settle
out of suspension.
Colloidal materials normally range in size from less than 0.001 micrometer (micron) to about 1 micron. Colloidal materials tend to be
uniformly dispersed because negatively charged ionized matter is absorbed on their surfaces, and they tend to repel each other. A measure of
the charge surrounding the colloid is known as the zeta potential. These negative charges are reduced by the use of positively charged chemicals
called cationic polymers, which, because of their attraction to the colloidal materials, reduce the zeta potential and allow the colloids to cluster
to form a larger, jelly-like mass that can be settle by gravity or be filtered. In a process called flocculation, colloidal particles, bacteria, and
organic matter are mechanically brought together into larger and heavier particles, which will settle out of the water. This process is called
clarification or sedimentation.
Large volumes of water are typically clarified in large, conical-bottom basins. First, the coagulant must be introduced with a strong action
to completely disperse and mix the chemicals with the incoming water. Often, some of the sludge produced by this process is mixed with
the coagulant. After coagulation is accomplished, the mixture is gently mixed to allow these larger particles to collect and subsequently settle
rapidly to the bottom of the basins. The particles and chemicals that settle out are called sludge, which must be removed from the bottom of
the basin and disposed of.

The most frequently used chemical coagulant is aluminum sulfate, FIGURE 11-5
also referred to as alum or filter alum. Other frequently used coagulants Six-Station Jar Testing Apparatus Used to Optimize Chemical Dosages for
are sodium aluminate and potash alum. Iron coagulants include ferric Coagulation and Flocculation
Photo courtesy of Phipps & Bird, Inc., Richmond, VA. ©2018.
sulfate and ferric chloride. Organic polyelectrolytes, which are polymers
of high molecular weight, also are employed in low dosages to increase
the effectiveness of treatment. These polymers can be cationic, anionic,
or nonionic in nature depending on the solids being settled.
It is usually a matter of trial and error to find the correct amount of
any chemical additive, and testing is usually done by a jar test, shown
in Figure 11-5. This is because the type of chemicals used and their
dosage depend on the size and quantity of the suspended solids in the
raw water, retention time prior to flocculation, water temperature,
and amount of mixing.
When the demand for water is low, one alternative flocculation
method is to produce a finer floc, which can be removed by an
appropriate filter system. By eliminating a large settling basin, high-
quality water can be produced more quickly with smaller equipment.
Deaeration or Degasification
Dissolved gases in the water supply, such as oxygen, carbon dioxide, hydrogen sulfide, and ammonia, may cause corrosion and pitting or
may create other issues based on the application. Depending on the use of the water, removal of these gases may be important. Although
carbon dioxide and hydrogen sulfide can be removed by aeration, in many cases it is easier and less expensive to remove them by deaeration
or degasification. In a heat-based deaerator, the water temperature is raised, and the gas of concern is allowed to evaporate from the water.
The three types of heat-based deaerators utilize steam, vacuum, or a membrane. When heated water is needed, such as for boilers, the steam
type is preferred. When cold water is required, the vacuum type is typically used.
Steam deaerators break up water into a spray or thin film and then sweep steam across and through it to force out the dissolved gases.
With this method, oxygen can be reduced to near the limit of detection. Steam deaerators are available as spray, tray, or combination units.
Typical deaerators have a heating and deaeration section and a storage section for hot, deaerated water. Often, a separate tank is provided to
hold an additional supply of deaerated water. The direction of steam may be crossflow, downflow, or countercurrent. The majority of the steam
condenses in the first section of the unit. The remaining mixture of noncondensable gases is discharged to atmosphere through a vent condenser.
Vacuum deaerators use a steam jet or mechanical vacuum pump to develop the vacuum required to draw off and evaporate or literally pull
the unwanted gases from the water. The vessel has a packing material inside, and the inlet water is introduced to the top of the unit and passed
down through this packing. Deaerated water is stored at the bottom of the vessel. The vacuum is located at the top of the unit and discharges
the removed gases. The vacuum unit is less efficient than the steam unit, and it most often is used in demineralizer systems to reduce the
chemical operating cost and the demineralizer size and to prolong the life of anion-exchange resins.
Membrane deaerators/degasifiers use a hydrophobic hollow fiber membrane filter in conjunction with a sweep gas (typically nitrogen) and/
or vacuum to remove dissolved gases from a water supply. Membranes may be easily clogged with particles, so the water should be filtered
prior to a membrane-based degasifier.
Dealkalizing
Dealkalizing is a process that reduces the alkalinity of feed water. This can be done either with or without the use of acid regenerant. Without
the use of acid, the regenerant used is salt, and the process often is called salt splitting. The salt-splitting process exchanges all bicarbonate,
sulfate, and nitrate anions for chloride anions. Where hard, alkaline, and low-sodium water is available, the use of a weak acid cation exchange
resin may be considered.
The entire regeneration cycle is similar to water softening (described later in this chapter). It is not uncommon to use the same salt and
regenerant piping to accommodate both the softener and the dealkalizer. Some caustic soda may be added (one part caustic soda to nine parts
salt) to reduce the leakage of alkalinity and carbon dioxide. Since this can cause hardness leakage from the dealkalizer, a filter downstream of
the processed water may be utilized.
A weak acid cation exchange resin may also be used. The process transfers the alkaline salts of calcium and magnesium to the weak acid
resin and should include degasification if required by the product water. The weak acid process operates at a very high utilization factor, near
the theoretically required amount. Hydrochloric acid, rather than sulfuric acid, is preferred for regeneration. This process is very sensitive to
the flow rate, temperature, and contaminant level of the feed water. These changing conditions must be considered in the design of the process.
The entire regeneration cycle is similar to that of a cation ion-exchange column (described later).
Decarbonation or Carbon Dioxide Removal

Decarbonation may be accomplished in small systems by the use of filtered air flowing through the water stream and stripping out the carbon
dioxide. Carbon dioxide removal may also be accomplished by raising the pH to approximately 8.2 to convert any carbon dioxide into
bicarbonate ion, which may be removed by other technologies.

Distillation
In its basic form, distillation is the process of boiling feed water, condensing the vapor produced from the feed water, and collecting the
vapor as it condenses, which yields product water theoretically free from nonvolatile impurities, minerals, organics, and bacteria. Distillation
is the only technology that is universally accepted throughout the world for producing water for injection (WFI) grades of water used in the
manufacture of pharmaceutical products.
Three methods are commonly used to produce distilled water: single-effect distillation, multi-effect distillation, and vapor compression
distillation. All of these technologies involve boiling the water to remove the water from its impurities, so all technologies are energy-intensive
processes.
Single-Stage Distillation
The still used for single-stage distillation is the simplest type of still. Feed water enters the still and is evaporated and condensed in a single
stage. Cooling water is required to condense the steam produced. This type of still produces water of approximately 0.25 to 1 megohm-cm
resistivity, with higher purity possible with additional equipment that removes dissolved gaseous impurities. This method has a small footprint,
is less labor-intensive than the other methods, and tolerates feed water with some level of impurity.
Multi-Effect Distillation
Multi-effect distillation units use staged evaporation and condensation steps to generate distilled water. Each stage is called an effect. Distilled
water is produced in each effect when the steam generated by the evaporation of high-purity feed water in the previous stage is condensed. The
initial driving force for the evaporation is plant steam applied to the shell side of the first effect vessel. The multi-effect method has a higher
initial cost than a single-effect still, but it has the lowest operating cost of the three distillation methods. However, it requires the highest quality
feed water. Multi-effect distillation is typically used when the water volumes required are between 0.1 and about 10 gpm.
The feed water enters the unit, and its pressure is boosted by the feed pump (see Figure 11-6). The feed water flows through a coil in the
condenser, which allows it to pick up heat from the condensing steam. This preheated feed water flows through the feed control valve and
into the tube side of the first effect. The first effect level controller senses the feed water level and signals the feed control valve to maintain the
desired level. Plant steam is introduced into the unit and flows through the steam control valve and into the shell side of the first effect. Plant
steam is utilized as the energy source for only the first effect of a multi-effect system.
Temperature sensors sense the temperature on the tube side of the first effect and signal the steam control valve to maintain the required
temperature. Plant steam condenses on the outside of the tubes of the first effect, giving up its latent heat of vaporization to the feed water
inside the tubes, causing the pure feed water to boil and generate pure steam.
The pure steam generated in the first effect is introduced into the shell side of the second effect. This pure steam condenses on the outside
of the tubes in the second effect, simultaneously producing distilled water while giving up its latent heat to the high-purity feed water inside
FIGURE 11-6
Detail of Multi-Effect Still

the second effect tubes, causing this feed water to boil and generate pure steam. The pure steam generated by the second effect then becomes
the steam feeding the shell side of the third effect, and so on. Each effect operates at a slightly lower pressure compared to the previous effect
to provide the temperature difference allowing efficient heat transfer and pure steam generation in each effect. The pure steam generated in
the tube side of each effect passes through the mist eliminator to remove any entrained water droplets as well as an orifice before proceeding
to the shell side of the following effect.
At the last effect in the multi-effect unit, the pure steam generated passes through the mist eliminator and enters the condenser and condenses
on the outside of the condenser coils. This condensed distilled water from the last effect mixes with the condensed distilled water from the
previous effects and may be used to heat the feed water or may be cooled by the cooling water of the condenser if lower temperatures are desired.
The distilled water exits the condenser and enters the distillate pump. The distillate is pumped through the distillate control valve and through
the storage/dump valve. The condenser level controller senses the distillate level and signals the control valve to maintain the desired level.
Non-condensable gases in the condenser are vented to the atmosphere. The condenser temperature is maintained at a predetermined level
by the cooling water flow. The unit is typically protected by pressure-relief valves along with high- and low-level alarms and other controls.
Vapor Compression Distillation
Also called thermocompression distillation, vapor compression is a method of producing distilled water in which a liquid is boiled inside a
bank of tubes at a lower pressure when compared to multi-effect distillation. The vapor generated then passes through a mist eliminator that
removes any water droplets. The pure vapor is withdrawn by a compressor in which the energy imparted results in a compressed steam with
increased pressure and temperature. The higher-energy compressed steam is discharged into an evaporator (see Figure 11-7). At this point, the
steam gives up most of its energy (latent heat) to the water inside the tubes. More pure steam is generated, and the process is repeated. The
condensate (distilled water) is withdrawn by the distillate pump and is discharged through a heat exchanger.
The excess feed water that did not evaporate also is pumped through a heat exchanger, where the distillate and the blowdown are cooled
and the feed water is preheated prior to its entering the evaporator. These exchangers minimize the energy consumption of the system and
eliminate the need for additional cooling water. Additional makeup heat, usually supplied by steam, is required for continuous operation.
FIGURE 11-7
Detail of Vapor Compression Still
Vapor compression generally is considered more economical for large quantities of water and does not require high-quality feed water for
proper operation. It has moderate capital and operating costs.
Deionization or Demineralization
See the section on ion exchange.
Filtration (also see Membrane Filtration, Reverse Osmosis, and Ultrafiltration/Nanofiltration)

Filtration refers to the removal of suspended solids or particles through mechanical means. Common devices used for this purpose are strainers,
permanent media filters, and disposable media filters.

Strainers
Strainers are typically used to protect pumps, valves, and other devices from particles and suspended solids, with openings appropriate for the
application and ranging in size from ½ inch down to about 50 microns.
Permanent Media Filters

Permanent media filters include deep bed sand filters and multimedia filters, both of which are effective at removing particles down to about
10 to 20 microns in size. Permanent media filters are typically used for higher flow rates when the cost of replacement filter elements becomes
prohibitive and the cost of a permanent media filter can be justified.
Deep-Bed Sand Filtration and Multimedia Filtration

Deep-bed sand filters and multimedia filters are designed to remove coarse suspended particulates larger than 10 to 20 microns in size. The
media is contained in pressure vessels utilizing either a single layer of sand or multiple layers of media as the filter medium. Particulate removal
in the range of 80 to 90 percent should be expected. Particles removed by these filters are periodically backwashed to drain to refresh the media.
The media installed in these filters typically has a useful life of about 10 years. The pressure vessels used to hold the media are similar to those
used for the carbon filter described earlier (refer to Figure 11-4).
Single-media sand filters contain a single layer of sand installed over a few layers of underbedding, FIGURE 11-8
which keeps the media inside the vessel. These filters generally operate at a velocity of about 2 to 4 Layers of Graded Density Media in a
gpm per square foot of cross-sectional bed area. In general, lower flow rates allow for greater contact Multimedia Filter
Image courtesy of Bluewater Bio Limited.
time and more efficient particle removal. Because of the uniformity of the media in the bed, the vast All rights reserved
majority of particulate removal occurs in the upper few inches of sand.
Multimedia filters contain several layers of filter media starting with a coarse layer at the top
followed by gradually finer layers through the depth of the filter (see Figure 11-8). The media is
selected based on a graded density, with the density of the media increasing from top to bottom to
ensure that the media orientation is preserved after backwashing.
Because multimedia filters contain several layers of media with varying pore sizes, particles will be
captured throughout the filter bed, with larger particles being captured in the upper layers and smaller
particles being captured in the lower layers. This more uniform particle loading gives multimedia
filters extra particle-holding capacity, which translates to higher capacities to hold contaminants and
less frequent backwashes. Multimedia filters also operate at higher flow rates, with rates ranging from
6 to 15 gpm per square foot of bed area. This means a smaller footprint and lower capital investment.
With any permanent media filter (sand, multimedia, carbon, greensand, etc.), backwashing is
required to remove the captured materials from the filter, with the effluent discharged to an appropriate
drain per local code. Backwashing involves reversing the flow through the filter (from top down to
bottom up), which causes the filter media to expand as captured materials are rinsed to drain. It is
important to have a high enough backwash rate to remove captured materials, but a backwash rate
that is too high can lift the filter bed and cause media to be rinsed to drain and lost. This is the reason
that permanent media filter are never (with rare exceptions) completely filled with media. The space
between the media and the top of the vessel is called freeboard, which varies by filter type and is
present to allow for bed expansion during backwashing while preventing media loss. For multimedia
filters, a backwash flow rate of 10 to 15 gpm per square foot is required for effective cleaning.
Disposable Media Filters

Disposable filters include cartridge filters, bag filters, and similar devices. These types of filters are typically used in lower-flow applications or
when initial costs, spatial constraints, or backwash requirements preclude the use of a permanent filter (or for other factors).
Typically, the disposable media is installed in a pressure vessel (housing), and the removal rating of the system is determined by the rating
of the element installed. Cartridge and bag-type filters usually have removal ratings ranging from 200 microns down to 1 micron. These types
of filters usually use fibrous strands of media that are bonded or mechanically assembled into a filter matrix to create the desired porosity of
the end product. The filter elements are rated for nominal removal efficiencies between 75 and 95 percent at their respective micron rating.
(There may be significant performance variations among manufacturers and product types.) Cartridge filters are usually either depth or pleated
filters. Depth filters are typically string-wound or melt-blown, and particles are removed throughout the “depth” of the media, whereas pleated
filters are characterized by a few layers of high surface area material that is glued or welded to end caps. Regardless of the type, the filter is
typically sealed to the housing using a compression or knife-edge seal, which is effective for filter elements with removal ratings down to about
1 micron. Below this rating, a cartridge with an O-ring seal is typically recommended so the sealing mechanism does not allow particles to pass.
As the pore size of filters decreases, the flow per unit area also decreases, while both the pressure drop and cost increase. The engineer should
pay attention to the pressure and flow restrictions introduced by these products.
Ion Exchange for Deionization

Ion exchange is the basic process in which specific ions in a feed water stream are transferred into an exchange medium called resin. In this
process, the removed ions are “exchanged” for different ions with a similar charge. When the ion-exchange process is used to treat water only

for the removal of hardness, it uses one type of resin and is called water softening (see the section on water softening for more information).
When the ion-exchange process is used to treat water for the removal of ions to produce pure water, two types of resins are required, and it
is referred to as deionization (DI) or demineralization. Ion-exchange media include natural inorganic aluminum silicates (sometimes called
zeolites or greensands) and bentonite clay, as well as synthetic resins. The vast majority of ion-exchange media in use today is from the synthetic
resin category, and the following discussion focuses on these synthetic resins.
The deionization/demineralization process uses two different types of resins: one to exchange positively
charged cations and one to exchange negatively charged anions, resulting in the removal of nearly all ions TABLE 11-7
from feed water when the process is carried to completion. When all of the ionic components involved Typical Cations and Anions Found
in water are removed by ion exchange, the water is said to be deionized or demineralized. in Water
Table 11-7 lists the common cations and anions typically found in water that are removed by typical Cations Anions
ion-exchange resins. Ion exchange does not remove significant amounts of organics, bacteria, particles,
Calcium Carbonates
colloids, or turbidity, but may capture some of these materials.
Thousands of different types of synthetic resins are available, but this discussion only focuses on a few Magnesium Bicarbonates
for simplicity. Resins designed to removed cations are called cation-exchange resins, and resins designed Sodium Sulfates
to remove anions are called anion-exchange resins. Cation resins are further separated into strong acid
and weak acid cation-exchange resins. Anion resins are also separated into strong base and weak base Potassium Chlorides
anion resins. The key difference between the strong and weak forms of a resin is that the strong form will Iron Nitrates
remove all ionic species, whereas the weak form will remove most but not all ionic species. Weak forms
generally have higher capacities, whereas strong forms produce greater purity. In the production of high- Manganese Silica
purity water, the strong forms of resins are most commonly used, with the cation-exchange resin used in
the hydrogen form and the anion resin used in the hydroxide form. Cation-exchange resins have a useful life of up to 10 years, whereas anion
resins are more fragile and may only last two to five years.
Ion-exchange resins are manufactured by polymerizing styrene and cross-linking the polymerized polystyrene with divinyl benzene (think
of it as lots of rungs on lots of ladders). Resins are polymerized and crosslinked until they become insoluble and achieve a certain size, and
then the reaction is stopped. Most resins range in size from 0.3 to 1.4 millimeter in diameter, but sizes may vary. Resins are then activated by
chemically adding exchange sites to each type of resin to yield its final functionality.
Traditional deionization utilizes cation- and anion-exchange resins working in tandem. Cation resins remove cations (sodium, potassium,
iron, etc.), replacing them with hydrogen (H+) ions. Anion resins remove anions (chloride, sulfate, etc.), replacing them with hydroxyl (OH-)
ions. Working together, these two exchange processes remove the majority of cations and anions from water, with the displaced H+ and OH-
ions combining to form water. When the ionized impurities are removed, the water is said to be deionized or demineralized. The degree of
purity is measured using a conductivity/resistivity analyzer.
Ion-exchange resins have a finite capacity and are only able to process water until the exchange sites have become filled with trapped cations
and anions, at which time the resistivity begins to decline, indicating that the resin is exhausted. At the end of their operating cycle, the resins
must either be replaced or regenerated to restore their performance. Because of the dangerous nature of the chemicals required to regenerate
these resins, many companies elect to utilize portable exchange or service deionizers, where a vendor is called to replace an exhausted tank with
a fresh tank containing regenerated resin. The exhausted resin is taken back to the vendor’s facility, where it is regenerated using concentrated
solutions of acid and base to return it to the active form.
The key to a successful ion-exchange process is that it can be reversed reliably under controlled conditions so that the resin may be used
over and over again. When used for water purification, resins operate in the H+ and OH- forms until they become exhausted. At that point,
the exchange process must be reversed, and the captured cations and anions must be removed from the resin to return it to its original (H+
and OH-) forms so the resin can be used again. This process is called regeneration.
Ion-exchange resins are designed to remove cations and anions from a water supply. Different ions have different levels of attraction for a
resin, with the H+ and OH- forms of the resins being the most weakly held ions by the resin. During service, other ions with greater attraction
to the resin displace the H+ and OH- ions from the resin. Regeneration reverses this process, but for the regeneration process to be effective,
cation resins must be treated with high concentrations of strong acids, and anion resins must be treated with high concentrations of strong
bases to overcome the stronger attraction of removed ions for the resins.
Cation resins are typically regenerated with a 4- to 8-percent hydrochloric acid (HCl) solution having a pH below 0, whereas anion resins
are typically regenerated with a 4- to 8-percent sodium hydroxide (NaOH) solution having a pH above 14. Occasionally, sulfuric acid or
potassium hydroxide are substituted as regenerant acids and bases respectively, but this is relatively rare. With additional backwash, flush, and
rinse cycles, the regeneration process generates large volumes of wastewater requiring neutralization prior to discharge.
With these regeneration constraints in mind, it is also easy to conclude that the simplest form of deionizer would be a two-bed, or dual-
bed, deionizer. In a dual-bed deionizer, one vessel contains the cation-exchange resin, and a second vessel contains the anion-exchange resin.
Dual-bed deionizers are easier to regenerate because the resins are contained in separate vessels. A dual-bed deionizer will remove 90 to 95
percent of the ions from a water supply and will produce an effluent water quality ranging from 0.5 to 2 megohm-cm resistivity.
To achieve higher water quality, a second dual-bed deionizer could be installed after the first unit, but to achieve the highest levels of water
quality, the cation resin and anion resin must be mixed and placed into the same vessel, and the resulting unit is called a mixed-bed deionizer.
The challenge with regenerating a mixed-bed deionizer onsite is to separate the cation and anion resins effectively while they are contained in
the same vessel in order to regenerate them. Piping, valving, and manifolds become much more complicated in a mixed-bed deionizer, but
these units are capable of producing 18-megohm water. A typical mixed-bed deionizer contains a ratio of 40 percent cation to 60 percent

anion resin because anion resins have lower exchange capacities on a per-unit volume basis. It is not uncommon for facility owners to utilize
portable exchange mixed-bed deionizers so they do not have to worry about separating and regenerating resins (and the chemicals associated
with the processes).
Figures 11-9 and 11-10 illustrate a typical dual-bed ion-exchange unit and a typical mixed-bed ion-exchange unit respectively. The piping
and valve arrangements of manufacturers may differ from those shown.
FIGURE 11-9
Typical Dual-Bed Ion Exchanger
To consistently produce the highest quality of deionized water (18 megohms), two mixed-bed deionizers are typically installed in series.
The first unit is called the worker unit and is used for the initial removal of the vast majority of ions from the feed water. The second unit is
called the polisher and is used to “polish” the water up to its final water quality.
Electrically Regenerated Mixed-Bed Deionizers
One alternative to chemically regenerated resins is the use of resins that are regenerated using electricity. These units go by various trade names
including continuous deionization, electro-deionization, continuous electro-deionization, and others. These units represent a continuous
water-purification process using direct current, an alternating arrangement of cation and anion permeable membranes, and mixed-bed ion-
exchange resin. The cation and anion permeable membranes form parallel, thin flow compartments, alternating between concentrating and
diluting compartments. The diluting compartments contain a thin layer of ion-exchange resin. Some manufacturers also use ion-exchange resin
in the concentrating compartments. A single set of these components is called a cell pair. Many sets of these cell pairs can be placed between
sets of electrodes in a plate-and-frame device to achieve the desired flow output. More cell pairs allow higher flow rates to be achieved. This
arrangement is schematically illustrated in Figure 11-11.
Feed water enters at the top of all of the compartments. Under the influence of a direct-current electrical field, ions move from the water
in the dilute stream, through the ion-exchange resin, and toward the electrode with the opposite charge. Cations move toward the cathode,
through the cation permeable membrane, and into the adjacent concentrate stream. Anions move toward the anode, through the anion
permeable membrane, and into the adjacent concentrate stream. Deionized water exits from the bottom of the dilute stream. The alternating
cation and anion permeable membranes trap and concentrate ions in the concentrate channels, and a small flow of water continuously rinses
the concentrated ions to drain. The ion-exchange resin bed serves as a highly conductive medium through which ions flow because of the
electric field. The various flow streams are hydraulically independent, allowing a high volume of high-purity water (product) to be produced
with a very low volume of concentrate (waste), typically 95 to 97 percent product and 3 to 5 percent waste, which can be recycled.
The electricity supplied to the units continuously regenerates the resins, and this process results in a steady supply of high-purity water. This
technology presents some advantages over conventional ion exchange, including no handling and disposal of hazardous regeneration chemicals
and no interruptions due to exhaustion of the resins’ ion-exchange capacity.

FIGURE 11-10
Typical Mixed-Bed Ion Exchanger
Continuous deionization does have some

limitations. It is sensitive to feed water impurities; it FIGURE 11-11
Schematic Operation of a Continuous Deionization Unit
will not reliably produce 18-megohm-cm resistivity
water without a polishing mixed-bed deionizer; and
the units are not compatible with most sanitizing
agents. Very few natural potable feed water supplies
can meet the required feed water specifications without
softening and additional pretreatment. Because of
this limitation, most systems utilize continuous
deionization following a reverse osmosis pretreatment
process. The use of reverse osmosis and continuous
deionization results in a complimentary combination
of purification technologies, with the reverse osmosis
removing the bulk of the contaminants and the
continuous deionization polishing the water to purity
levels between 1 and 15 megohms.
Leakage
Leakage is the presence of undesired ions in the final
treated water and is a limitation of any ion-exchange
process where resins are regenerated. One of the
major decisions that must be made when selecting
an ion-exchange system is the allowable amount of
leakage. The amount of leakage is a function of the
completeness of resin regeneration. Cation resin
regeneration typically is 85 to 90 percent effective at

restoring the exchange sites back to the hydrogen (H+) form, whereas anion resin regenerations are typically only 65 to 75 percent effective at
restoring the exchange sites back to the hydroxide (OH-) form. Because sodium ions are the most weakly held cations, sodium tends to be the
first cation to leak from cation exchangers, and for the same reason, silica tends to be the first anion to leak from anion exchangers. Mixed-bed
units typically have lower leakage. In critical applications where the highest water quality is desired, it is not uncommon to utilize “virgin,”
or never-used-before, resin as the final deionization step and to have ion-specific sodium and silica analyzers present to measure for these ions
eluting from an ion-exchange resin to indicate resin exhaustion.
Manganese Greensand and Other Oxidizing Filter Media
Manganese greensand is one of several oxidizing filter media that may be utilized for specific water treatment applications. Other oxidizing
filter media include birm and several proprietary blends of materials designed for specific purposes. Manganese greensand is most effective as
a combination oxidizing agent and filtration device and is commonly used to remove dissolved iron and manganese from a water supply, with
manganese requiring more aggressive conditions for effective removal. The oxidizing media is chemically regenerated with an oxidizing agent
such as chlorine or potassium permanganate. Collected particulates are backwashed to drain periodically.
Membrane Filtration
Membrane filtration is a general term for a filtration process that removes suspended solids and other contaminants from feed water by means
of a thin, cast membrane. These filters are typically utilized to remove bacteria from a water supply or to protect a process that requires the
removal of bacteria and fine particulates. Filters in this category range in removal ratings from 1 micron down to 0.1 micron, although some
manufacturers claim 0.05- or 0.03-micron ratings. Because these membranes are almost exclusively manufactured by a casting process, the filter
media is much more consistent and the pore size is much more closely controlled, which also increases the cost. Hence, removal efficiencies are
typically a minimum of 99.99 percent or better. These filters are typically described as “absolute filters,” and nondestructive testing methods
allow users to verify the performance of these filters prior to installation and after use if desired.
Membrane filters may be purchased as flat stock for laboratory applications, but are usually assembled into cartridges or capsules. Cartridges
are installed into housings and sealed using O-ring seals. Capsule configurations are used for smaller-scale applications. These filters are used
in many industries as one of the final purification steps used to remove bacteria from a pure water supply prior to use. The pharmaceutical
industry typically uses a double layer of membrane in a filter to “sterile filter” some products when they cannot be heat sterilized.
Microbial Control Using Chemicals and Heat (also see Ultraviolet Treatment)
The most often-used disinfection method in chilled water and cooling tower systems is the addition of oxidizing or non-oxidizing chemicals.
Chemicals can be either biocides, which are substances that kill microbes, or biostats, which prevent the further growth of microbes. Commonly
used chemicals are chlorine and chlorine compounds, hydrogen peroxide, and acid compounds.
To be effective, the chemical must have a minimum contact time in the water. In addition, a residual amount of the chemical must be
present to maintain its effectiveness against organisms.
Chemicals add impurities to the water and generally are not suitable for use in a water purification system. In the case of water purification
systems, chemicals are typically used to disinfect a system during startup or periodic maintenance and then rinsed to drain before the system is
put back online. In potable and process water systems, chemicals may be injected directly into the fluid stream by means of a metering pump.
When added to the feed water of a water purification system, they must be removed.
Heating pure water to 175°F (80°C) for one hour effectively sanitizes a pure water piping system, equipment, and storage tanks. Heating
can be accomplished by using steam, electric, or other types of heat exchangers, but it is an energy-intensive process. Because of its effectiveness,
it is the most common practice used in the pharmaceutical industry to ensure sterility. Many pharmaceutical water systems are operated at
elevated temperatures continuously. In these cases, it is common FIGURE 11-12
practice to circulate purified water at this temperature and use Principle of Corona Discharge Ozone Generator
heat exchangers to lower the water temperature for safety or other
reasons prior to use. Heating pure water may only be done when
all components are stable to the heat generated by this process.
With a few exceptions, the majority of heat-sanitizable systems
are constructed entirely of stainless steel.
Ozone
Ozone (O3) is an oxidizing gas typically generated from gaseous
oxygen or catalytically from water. Ozone is an incredibly reactive
compound that cannot be effectively stored for any length of
time. At room temperature, ozone has a half-life of about 15
minutes, so it must be generated onsite and immediately used or
it will decompose back into oxygen. Ozone is used for bacteria
and organics control as well as to remove biofilm from a water
system.
The most commonly used method of producing ozone is by the corona-discharge process (see Figure 11-12), which uses high voltages to
convert oxygen gas into ozone gas. The air is passed between two electrodes, and an electrostatic discharge across the gap converts oxygen to

ozone. A complete ozone-generating system consists of a feed-gas treatment unit, an ozone generator, a water/ozone contact mechanism, and
a destruction unit to eliminate any ozone that off-gases from the water.
The feed gas reaching the generator may be either pure oxygen or dry compressed air. When using pure oxygen, no further treatment is
typically required prior to use. When using compressed air as the source, the air should be filtered to remove particulates. Compressed air is
typically passed through an oxygen concentrator to increase the oxygen content, and moisture must be removed or acids will be formed and
ozone output will be reduced.
Ozone may be injected into a water stream by the use of static or mechanical mixers, injectors, bubblers, or columns that optimize the
dissolution of the gas. Ozone may be injected into a storage tank, or it may be injected into a pressurized water line. When injected into a storage
tank, some of the ozone will off-gas and not actually dissolve into the water. The mechanism for ozone oxidation is through the generation of
highly reactive hydroxyl radicals as ozone decomposes to oxygen.
Because ozone is harmful to humans, ozone should not be allowed to escape to the atmosphere without being reduced to a level below 0.05
to 0.1 ppm. Ozone destruction can be effectively accomplished using a combination of a catalyst and high temperature. These ozone destruct
units operate at a temperature up to 572°F (300°C) and generally require a short contact time to destroy the ozone.
Ozone is widely used in industries such as semiconductor and bottled water, but its acceptance by other industries has been slower.
Ozone is not without its limitations. When oxidizing large organic molecules, it will take time to convert a large 50,000-MWCO (molecular
weight cutoff) organic molecule completely to carbon dioxide, but this process can be accelerated if some of the intermediate compounds are
removed from the water. Because of ozone’s reactivity, if too much ozone is added to a water system, any residual ozone will attack the system’s
components, which may cause premature degradation of elastomers, gaskets, pump seals, coatings in pressure vessels, etc. With ozone’s use in
various industries increasing, improved guidelines are being established to govern its effective use.
Reverse Osmosis permeate or product water, and the contaminant-containing water is called reject or concen
shown in Figure 11-13. The pressure required to force water through a reverse osmosis mem
Reverse osmosis (RO) is a pressure-driven water-purifying process involving a combination of osmosis
dictated by the osmotic pressureand ionic
of the water,repulsion. Typical
a term that loosely reverse
describes the concentratio
osmosis membranes have a removal rating of about 200–300 molecular weight dissolved
(MW),minerals
so theyor salts
are in a water supply.
capable More dissolved
of removing mineralscolloids,
particles, yield higher osmotic pr
requiring higher pressure pumps to drive the process. For example, water from a lake or rive
and bacteria from a water supply. Additionally, because of the hydrogen bonding properties of the pressure
have a lower osmotic water molecule with
compared with dissolved
water taken fromions, reverse
the ocean , and RO systems
osmosis membranes are capable of removing many dissolved minerals with surprisingly
produce high efficiency.
pure water This
would vary makes
greatly basedreverse osmosis
on the feed one of the
water characteristics.
most powerful water purification processes available to the engineer. Figure 11-13 Schematic DiagramFIGURE 11-13
of a Reverse Osmosis (RO) Membrane with the Membrane
With reverse osmosis, feed water is forced through the membrane with pressure,Represented bySchematic
the Diagonal Line
Diagram of an RO Membrane
leaving behind the bulk of the contaminants. The concentrated contaminantsFeed water is purified by passing through the membrane, which creates product water. The
Membrane is represented by the diagonal line. Feed water is purified
contaminants removed by the RO membrane are concentrated in reject or concentrate stre
remaining on the feed side of the membrane are flushed to drain continuously andindicated.by passing through the membrane, which creates product water. The
contaminants removed by the RO membrane are concentrated in the reject
thereby removed from the system. The purified water is called “permeate” or product or concentrate stream as indicated.
water, and the contaminant-containing water is called reject or “concentrate.” This
is shown in Figure 11-13. The pressure required to force water through a reverse
osmosis membrane is dictated by the osmotic pressure of the water, a term that
loosely describes the concentration of dissolved minerals or salts in a water supply.
More dissolved minerals yield higher osmotic pressures, requiring higher-pressure
pumps to drive the process. For example, water from a lake or river would have
a lower osmotic pressure compared with water taken from the ocean, and RO
systems designed to produce pure water would vary greatly based on the feed water
characteristics.
The performance characteristics of a particular membrane determine the system’s
size. RO membranes are rated to produce a specified flow rate, which is usually expressed in gallons
The performance per day under
characteristics standard
of a particular conditions
membrane determineof the system’s si
temperature, pressure, and mineral content, which may not be representative ofmembranesthe conditions
are rated to encountered
produce a specifiedin the field.
flow rate RO
which membranes
is usually expressed in gallons p
under standard conditions of temperature, pressure, and mineral content, which may not be
are installed into pressure vessels and may be installed in series, parallel, or some combination
representative of both encountered
of the conditions to achievein the desired
the field. output are
RO membranes and installed into p
performance. In some instances, product water from one set of membranes is passed through
vessels and may be a second
installed inset of membranes.
series, parallel, or someA system designed
combination of both to achieve the d
output and performance. In some instances, product water from one set of membranes is pa
with this membrane configuration is called product-staged, two-pass, or double-pass RO.
through a second set of membranes. A system designed with this membrane configuration is
The percent of feed water that is converted into product water is called the “percent
productrecovery.”
staged or doublePercent recoveries vary based on system size,
pass RO.
with larger systems typically engineered to have higher recovery rates. Recovery rates vary from of
The percent a low of about
feed water that is 25 percent
converted (or even
into product lower
water in the percent r
is called
Percent recoveries vary based on system size, with larger systems typically engineered to hav
some lab applications) to about 80 percent. Recovery rates may vary based on feed waterrates.
recovery characteristics
Recovery rates varysuchfrom as amineral
low of aboutcontent
25% (evenand fouling
lower in some lab applica
potential. It is important to remember that a reject stream must always be present aboutwhen using rates
80%. Recovery reverse osmosis,
may vary based onorfeed
thewater
membranes will
characteristics suchbeas mineral con
irreversibly fouled. Percent rejection describes the percentage of salts removed fouling potential. It is important to consider that a reject stream must always be present or th
membranes will be irreversibly fouled. Percent rejection describes the percentage of salts rem
from the feed water and is measured with a two-probe conductivity meter. the feed water and is measuredFIGURE with a two11-14
probe conductivity meter.
Two major types of membrane module configurations are used for Two major types of Hollow-Fiber
membrane module RO Configuration
configurations are used for reverse osmosis applica
hollow fiber and spiral wound, although other configurations may be used in small scale appl
reverse osmosis applications—hollow fiber and spiral wound—although Spiral wound RO membranes are by far the most commonly used configuration. In each conf
other configurations may be used in small-scale applications. Spiral-wound
RO membranes are by far the most commonly used configuration. In each
configuration, turbulence is necessary to prevent membrane fouling from
sediment or the precipitation of solids on the membrane surface.
The hollow-fiber configuration, illustrated in Figure 11-14, consists of a
perforated hollow fiber manufactured from a synthetic polymer with small
inside diameters. The hollow fiber must be robust enough to withstand the

high feed pressures of RO systems without collapsing. Feed water could be FIGURE 11-15
introduced into either the center or the outside of the fiber, depending on Spiral-Wound RO Configuration Showing Three Membranes
the manufacturer of the module. Fouling resistance is relatively low with this Installed in a Pressure Vessel
membrane configuration, and the incoming water supply should be highly
filtered prior to introduction to the membrane.
The more commonly used spiral-wound membrane configuration, illus-
trated in Figure 11-15, typically achieves a large surface area per unit volume.
In this design, the membrane is built like a plastic bag (open on one side and
closed on three sides), with the open side terminating at the perforated product
water collection tube located in the center of the module. Alternating layers
of spacer material are placed inside the RO membrane and between adjacent
layers of RO membrane, and several of these “plastic bags” with spacer materials
are installed and spiral-wrapped to make a finished RO membrane. Looking
at the membrane from an end, it looks like a roll of paper towels. An external
layer of high-pressure tape or fiberglass is wrapped around the outside of the
membrane, and a brine seal is installed to complete the construction of a
membrane module, although some membranes are built without a brine seal
for specialty applications. The assembled membrane is placed inside a pressure
vessel. Feed water is forced through the membrane and flows radially inside
the enclosure toward the product tube.
Reverse osmosis technology has evolved rapidly over the past several decades.
The original RO membranes were constructed from cellulose acetate and were
characterized by low flux rates, susceptibility to bacterial attack, and degradation
if the pH increased above 8. Cellulose acetate or triacetate membrane systems
require a chlorine feed to prevent bacteria from consuming the membrane.
These limitations led to the development of synthetic membranes that were
resistant to bacterial attack. These include polyamide, polysulfone, and
eventually thin-film composite membranes, which dominate the market today. Polyamide and thin-film composite membranes are stable
under a wider pH range, they produce more product water per unit area of membrane, and the water quality produced by these membranes
is generally superior to the cellulose-based membranes. However, these synthetic membranes are not without their limitations, most notably a
very low tolerance to chlorine and other oxidizing agents. As such, waters purified by systems using these membranes must be dechlorinated
before the water is introduced to the RO membrane, or permanent degradation will occur.
Membrane selection is determined by considering the following factors, which influence the capacity of the individual membranes selected:
• Operating pH range
• Chlorine tolerance
• Temperature of the feed water (flow decreases as temperature decreases)
• Feed water fouling characteristics, usually measured as silt density index
• Types of impurities and prior feed water treatment
• Percent rejection characteristics
• Ability to heat-sanitize a system
A comparison of the performance
characteristics of various membranes is shown TABLE 11-8
in Table 11-8. Comparison of RO Membrane Polymer Types
Some RO membranes have been developed Thin-Film Cellulose Cellulose
Polyamide
to withstand heat sanitization at 180°F (82°C), Composite Acetate Triacetate
and their use has increased in the pharmaceutical pH stability 2–12 4–11 2–8 4–7.5
and other high-technology industries. Other
high-flux membranes have been developed that Chlorine tolerance Fair–poor Poor Good Fair–good
produce more water at lower pressures without Bacteria removal Excellent Excellent Good Good
sacrificing performance.
Biological resistance Good Good Poor Fair–good
Membranes typically must be protected
from large particles and free chlorine in the raw Temperature limit for continuous 122 (45) 95 (35) 95 (35) 86 (30)
water stream to extend their life and improve operation, °F (°C)
permeate production efficiency. Activated Typical ionic removal, % >97 >95 90 92
carbon filters and chemicals such as sodium
bisulfite are common methods of removing Flux High Low Low–medium Low–medium
free chlorine in feed water to RO membranes Heat-sanitizable Some No No No
to protect from oxidation.
Frequency of use in commercial and
Dominant Minor Little Little
industrial applications

In large-scale systems or wastewater systems utilizing RO, the dissolved air flotation process, or DAF, may be utilized. In DAF, particles
that would damage and oxidize an RO membrane are separated out of the water by floating them to the surface. The process introduces
micron-sized air bubbles through diffusers located at the bottom of a tank or reservoir where they mix with the coagulated solids and float the
particles to the water surface. The air bubbles are produced by recycling a portion of the effluent through a tank where 80-psi (5.5-bar) air is
introduced, causing the water to become saturated, and then reduced to ambient pressure at the nozzles in the header of the reaction zone of
the DAF cell, thus creating the pressurized flow. The floated particles are removed from the top of the basin by mechanical or hydraulic means,
and clean water is collected from the bottom of the tank or reservoir. Mechanical desludging will provide a floated sludge with 2 to 5 percent
solids content, resulting in significantly less sludge volume to process in the solids-handling portion of the treatment plant.
Softening
Water softening is a process that reduces or removes dissolved impurities that cause hardness in water. This is done by one of two methods:
adding lime and soda ash to the raw water for very large volumes or passing the raw water through an ion-exchange process.
The lime and soda ash method uses either hydrated lime or quicklime along with soda ash. When added to water, these chemicals react
with the dissolved calcium and magnesium carbonate to form insoluble compounds. These compounds precipitate out of solution, are passed
through a filter to be removed, and then are discharged to drain. This process usually is carried out during the clarification process rather than
separately and is reserved for large volumes of water.
The ion-exchange method of water softening is a cation-exchange process (refer to the ion-exchange section) used to remove dissolved
calcium, magnesium, iron, and other multivalent cations, which are the primary contributors to hardness, and to replace them with sodium
ions. Unlike the cation-based deionizer described previously, which removes all minerals and replaces them with hydrogen ions (H+), a water
softener uses the same type of resin, but this resin replaces removed minerals with sodium (Na+). Water softening provides great benefits when
water is about to be heated.
The resin is installed in a permanent bed filter with similar design constraints to the permanent bed filters described earlier. Because the resin
is an ion-exchange resin, it has a finite capacity to remove hardness minerals, and it must be periodically regenerated to restore its performance.
With a water softener, regeneration is not accomplished with acid
(HCl), but with salt (NaCl), which removes attached minerals and FIGURE 11-16
replaces them with sodium ions. Water softeners are regenerated Typical Single-Bed Ion Exchanger or Water Softener Schematic
with a 4- to 6-percent brine solution to restore the exchange sites
back to the sodium form. A schematic showing the operation of a
water softener is illustrated in Figure 11-16.
Leakage in a water softener is the presence of hardness minerals
in the final treated water. One of the major decisions that must be
made when selecting an ion-exchange system is allowable leakage. As
with all ion-exchange systems, the amount of leakage is a function of
the completeness of regeneration of the resin. For water softening,
generally accepted leakage amounts range between 0.1 and 1 ppm.
Since a complete regeneration of the resin bed is inefficient, costly,
and impractical in the field, most water softeners are operated at
about 75 percent of their theoretical capacity to minimize leakage.
Ultrafiltration and Nanofiltration

Ultrafiltration (UF) and nanofiltration (NF) are two different terms
used to describe the removal of impurities smaller than a submicron
membrane filter will remove but larger than what a reverse osmosis
membrane will remove. Like reverse osmosis, both ultrafiltration
and nanofiltration have reject streams and are considered cross-flow
or tangential-flow processes where water in the feed/reject stream
flows tangentially across a membrane, removing impurities before
they can deposit on the surface of the membrane.
Ultrafiltration and nanofiltration membranes are categorized by
their pore size, with ultrafiltration membranes having larger pores
and nanofiltration membranes having smaller pores. Ultrafiltration membrane pore sizes are smaller than that of a 0.1-micron membrane
filter. Typically, the characteristics of an ultrafilter are described by its molecular weight cutoff (MWCO) rather than by a micron rating. This
rating may also be expressed as daltons, which is equivalent to MWCO. These units describe the size of a typical molecule that they are capable
of removing. Ultrafilter membranes typically have ratings ranging from 250,000 MWCO down to about 5,000 MWCO. Nanofiltration
membranes have smaller pore sizes from about 5,000 MWCO down to about 500 MWCO. Nanofilters on the finer end of the spectrum may
be used to remove hardness minerals from a water supply while allowing sodium ions to pass through.
Ultrafilters are available in hollow-fiber or spiral-wound configurations, with hollow fiber being most commonly used. Ultrafilters are typically
used to remove colloidal materials, bacteria, and bacterial cell fragments, which may sometimes be referred to as “endotoxins.” Nanofilters are
available in the same configurations, but spiral-wound configurations are the most common. Nanofilters are generally considered a coarser
version of an RO membrane.

With its larger pore sizes, the amount of water sent FIGURE 11-17
to drain with ultrafilters is lower than either nanofilters UV Wavelength Spectrum
or reverse osmosis membranes. Typical recovery rates for
ultrafilters range from 50 to 98 percent, and for nanofilters
recovery rates range from about 30 to 90 percent.
Ultraviolet Treatment
Ultraviolet (UV) treatment is an in-line process commonly
used to control bacteria and/or total organic carbon (TOC),
where water flows through a chamber and is exposed to UV
radiation generated by the unit.
The most common type of UV unit is classified as a
low-pressure UV unit. In these units, UV light is generated
using mercury vapor lamps. Two specific wavelengths are
produced by these lamps, and the intensity and energy
output are determined by the manufacturer for the intended
germicidal treatment requirements. (The UV spectrum
is illustrated in Figure 11-17.) The 254-nanometer (nm)
wavelength is effective because it permanently binds DNA
molecules together, thereby making it impossible for
bacteria, yeasts, molds, and other organisms to replicate. It
is important to remember that although the organisms have
been inactivated, they must be removed from the system or
they will eventually break down and create a food source for other organisms. The 254-nm wavelength is commonly used in pure water systems
because it significantly reduces bacterial populations. The other wavelength generated by mercury vapor lamps is a 185-nm wavelength. This
shorter wavelength is also a higher-energy wavelength and is capable of breaking chemical bonds and oxidizing organic materials. The additional
energy available can break down organic molecules and compounds first to carboxylic acids and eventually to carbon dioxide and water.
Medium- and high-pressure UV units generate UV radiation over a broader UV wavelength spectrum and are more effective at oxidizing
organics compared with low-pressure units. Regardless of the type of unit used, the oxidation of organics will increase the conductivity of the
water and create water quality problems if the unit is installed in the incorrect location in a water purification system. If decreases in resistivity
are a major concern, the recommended location for the UV unit is prior to the deionization equipment. UV units producing only 254-nm
radiation will not change the resistivity of the water and may be installed following the deionization equipment.
UV lamps have a finite life and should be replaced approximately every six to 12 months to ensure continued performance. UV systems
utilize quartz sleeves to isolate the UV lamp from the water being treated, and these sleeves require periodic replacement because extended
exposure to UV radiation will reduce the amount of UV energy transmitted into the water being treated.
UV units are used to control bacteria, oxidize organics, remove chlorine, or decompose ozone. Consult manufacturers of these units for
proper sizing for each application. Unit sizing is also influenced by the cleanliness of the water being treated, with dirtier water being more
difficult to effectively treat. When used for bacterial control purposes, UV units typically reduce bacteria levels by approximately 99 percent.
As such, they should not be considered sanitizers (99.9 percent reduction), disinfectors (99.999 percent reduction), or sterilizers (99.9999
percent reduction), although manufacturers commonly refer to their units in this manner.
APPLICATIONS REQUIRING WATER TREATMENT, CONDITIONING, OR PURIFICATION

The section discusses the various uses of water and the requirements of each specific application, outlining the tools the engineer can utilize
to produce the specific level of purity required by the application.
Utility Water
Water from wells, rivers, lakes, and streams commonly is used for cooling, washing, and other purposes. Clarifying and treating such water to
meet the purity requirements of the specific end use require regular monitoring of the raw water for fluctuations to ensure the reliable supply of
a consistent treated water profile. With the general tendency toward water conservation, less water is being used in once-through applications,
and more water is being recirculated and reused. If the water is going to be recirculated, the treatment methods are more stringent than if it
is not going to be recirculated. If the water will be discharged into the environment, local codes must be followed to ensure compliance with
local wastewater discharge permit requirements to avoid the need for waste treatment.
Some considerations for the preparation of utility water include the following.
Initial Filtering
If the supply is from surface water, a coarse or fine screen usually is placed at the intake to exclude fish and other large debris. Coarse screens
are usually ½-inch (1.27-cm) diameter bars with a clear opening of 1 to 3 inches (2.54 to 7.62 cm). Fine screens could have openings of
approximately 3/8-inch (0.95-cm) square, with the water velocity through the screen limited to about 2 feet per second (fps) (0.6 m/s). If the
water quantity is small, basket strainers can be used. In climates where freezing may occur, the inlet should be placed far enough below the
low water level to prevent freezing.

Clarification
After initial filtering, clarification may be utilized to obtain water that meets the standards for the proposed use. The chemistries added and
the clarifier selected are based on the volume of water to be treated and the final quality desired. If the volume of water is small and the raw
water is not very turbid, permanent media or disposable filters may be used.
Biological Control
To control fouling by microorganisms and biofilm, microorganisms must be treated to keep them from reproducing and removed from the water
stream. This usually is accomplished by chlorination, filtration, ultraviolet radiation, ozone generation, special adsorbents, or a combination
of these technologies.
Chlorination is the least costly and most often-used method. The action of chlorine requires a specified contact time and the establishment
of a residual chlorine amount. A range of 0.5 to 1 ppm generally is accepted for typical waters. Chlorination is not universally used because
of its corrosive properties.
Water Softening
Water softening should be considered to reduce the hardness in the utility water system when the system is used for recirculated purposes or
where the water is heated.
Boiler Feed Water

In a boiler, energy in the form of heat is transferred across a heat-transfer surface from a fuel source to the water used for generating steam.
When subject to elevated temperature and pressure, the composition of the raw boiler water supply undergoes radical changes. The effects of
dissolved gases are magnified, particularly the corrosive effects of oxygen and carbon dioxide. The dissolved minerals may deposit scale on the
heat-transfer surface that impedes and retards the heat-transfer process. The result is a reduction in the heat-transfer rate, a reduction in the
rate of steam produced, and increased damage by overheating of the boiler tubes.
A wide range of treatment methods is available, depending primarily on the impurities found in the raw water, the operating pressure of
the boiler, and the water makeup rate. These methods could be mechanical or chemical (the addition of chemicals to prevent deposits, inhibit
corrosion, or neutralize impurities detrimental to the proposed end use of the water and the use of dispersants to keep particulates in suspension).
The treatment starts with an accurate feed water analysis, which is compared to the final treatment objectives established by the user and
the boiler manufacturer. The degree of removal is determined by the difference between the two analyses. Recommended standards for boiler
feed water and steam quality are given in Table 11-9.
Dissolved gases may be initially removed using a deaerator, which is usually followed by adding an oxygen scavenger and elevating the pH.
Many oxygen scavengers are available, but the most frequently used scavengers are sulfites (for boilers operating at pressures up to 1,000 psig)
and compounds of hydrazine. Hydrazine is being replaced by diethylhydroxylamine (DEHA), carbohydrazide, hydroquinone, and isoascorbic
TABLE 11-9 Recommended Boiler Feed Water Limits and Steam Purity
Range TDSa Boiler Range Total Alkalinityb Suspended Solids Boiler Range TDSc Steam, ppm
Drum Pressure, psig (kPa)
Water, ppm max. Boiler Water Water, ppm max. (max. expected value)
Drum-Type Boilersa
0–300 (0–2,068) 700–3,500 140–700 15 0.2–1.0
301–450 (2,075–3,103) 600–3,000 120–600 10 0.2–1.0
451–600 (3,110–4,137) 500–2,500 100–500 8 0.2–1.0
601–750 (4,144–5,171) 200–1,000 40–200 3 0.1–0.5
751–900 (5,178–6,205) 150–700 30–150 2 0.1–0.5
901–1,000 (6,212–6,895) 125–625 25–125 1 0.1–0.5
1,001–1,800 (6,902–12,411) 100 1 0.1
1,801–2,350 (12,418–16,203) 50 n/a 0.1
2,351–2,600 (16,210–17,926) 25 n/a 0.05
2,601–2,900 (17,933–19,995) 15 n/a 0.05
Once-Through Boilers
1,400 and above 0.05 n/a n/a 0.05
a. Actual values within the range reflect the total dissolved solids (TDS) in the feed water. Higher values are for high solids, and lower values are for low solids in the feed water.
b. Actual values within the range are directly proportional to the actual value of TDS of boiler water. Higher values are for the high solids, and lower values are for low solids in the boiler water.
c. These values are exclusive of silica.
Source: American Boiler Manufacturers Association

acid. The oxygen is consumed by the scavenger, and the elevated pH converts all corrosive carbon dioxide to bicarbonate and carbonate (refer
to Figure 11-1). Because calcium and magnesium carbonate are less soluble in hot water and it is desirable to prevent scale formation on boiler
tubes, boiler feed water is typically softened to remove the calcium and magnesium ions, replacing them with sodium ions and creating sodium
carbonate, which is much more soluble in water and will minimize scale. Chemistries may be added to maintain alkalinity levels and to keep
suspended solids from settling so they may be removed during boiler blowdown.
Other chemicals can be added to the boiler feed water for two purposes. One is to keep the salts in solution so they will not cause scaling.
The second is to precipitate salts out of solution to allow the particulates to be disposed of during blowdown. There are many effective materials,
generally blends of component chemicals. Those most-often used are polymers, phosphates, and carbonates that are designed to optimize the
precipitation of calcium, magnesium, and iron. Modern treatment has made hardness deposits much less common, but iron deposits have
become more problematic because of the return of condensate to the boiler.
Boiler blowdown is the bleeding off of some water from the boiler. When steam is generated, impurities are left behind as the feed water
is converted to steam, and these impurities accumulate over time. When the level of impurities becomes too high, a portion of the water is
discharged to drain during blowdown. Blowdown may be intermittent or continuous, and this water is typically exempt from wastewater
treatment and may be discharged directly to the sewer without any additional treatment.
Cooling Tower Water
Simply stated, successfully treating cooling tower water is a balancing act between keeping bacteria under control and making sure the water
is not too corrosive or too scale-forming. This balance needs to be maintained while water is constantly evaporating from the system, while
fresh water is periodically added, and while water is periodically discharged from the system to drain during blowdown.
Cooling tower water is used for cooling purposes inside a facility, and water is continuously being lost to evaporation on rooftops. The
basic reason for treatment is to keep any dissolved solids from depositing onto piping or equipment by preventing the dissolved solids from
reaching their saturation point. It is beneficial to keep the water in the tower for as long as possible, so minerals present in the feed water are
concentrated during their time in the cooling tower. This is usually expressed as the cycle of concentration of the water, which compares the
dissolved solids in the feed water with the dissolved solids of the circulating water. As an example, if the feed water has a total dissolved solids
of 100 ppm and the circulating water has a total dissolved solids of 300 ppm, a cycle of concentration of 3 has been reached. The cycle of
concentration is reduced by bleed-off (blowdown) from the system.
Scale
The basic treatment for scale in cooling water systems is to add inhibitors that keep the scale from depositing on the walls of the pipe. The
inhibitors are similar to those used for boiler water treatment, but with the addition of surfactants, which change the surface characteristics of
the pipe to prevent deposit formation and aid in removal if deposits occur.
Corrosion
Broadly defined as an electrochemical process, corrosion takes place when an electrical potential is possible between two surfaces common to
an electrolyte (the cooling tower water). The factors impacting corrosion in cooling towers include dissolved oxygen, total dissolved solids,
alkalinity and pH, total hardness, temperature, flow velocity, types of metal used in the process, condition of the interior surface of the plumbing
system, extraneous electrical current, and bacteria.
Simple tools used to predict the propensity of an aqueous solution to be corrosive are the Langelier, Stiff and Davis, and Ryzner indices.
Corrosion treatment may consist of one or more of the following:
• pH control
• Chemical inhibitors
• Oxygen scavengers such as hydrazine, sodium bisulfite, or bisulfate
• Ensuring proper flow rates by correctly sizing metal pipe
• Sacrificial anodes
• Polishing and passivation of interior surfaces
• Biocide treatment
These shall be recommended by the manufacturer of both the chemicals and the equipment to ensure compatibility. The pH of the
circulating water usually is controlled to a point near 7.5 to decrease its scale-forming tendency. The addition of a dilute acid or base is the
most often-used method of pH control. A corrosion inhibitor often adds compounds that increase the tendency of scale to occur; therefore,
a balance must be reached.
Biological Fouling
Microbial control is achieved with the addition of biocides, either oxidizing or non-oxidizing depending on their chemistry and killing action.
Ozone may also be used.
Biocide treatment initially shocks microbes with a heavy dose, and then the concentration of the compounds is allowed to dissipate to a
level of about 25 percent of the initial dose. This is a generally accepted lower limit below which the biocide is not considered effective. Often,
because of the presence of several different strains of microbes, more than one biocide may be alternated to ensure that resistance does not
develop. A contact time approved by the chemical manufacturer is required.
These chemicals are added by means of a chemical feed pump discharging directly into the piping system. The levels must be closely
monitored with alarms established by performance indicators based on operating experience.

Suspended Solids
With side-stream filtration, a small portion (3 to 20 percent) of the cooling water may be continuously filtered and returned to the system to
remove suspended solids from cooling tower systems. The main technologies used are pressure sand filtration and gravity continuous-backwash
filtration. The latter is particularly suitable for cases where large capacities are involved and the system could be easily coupled with the cooling
water reservoir. Centrifugal or other similar filter types are also commonly used.
Potable Water Treatment (Small Scale)

Water used for human consumption or intended to be part of food products must be treated to comply with the Safe Drinking Water Act,
the Surface Water Treatment Rules (part of the Safe Drinking Water Act), EPA Primary Drinking Water standards, and local regulations.
Substances that affect the quality of potable water are classified in four major headings.
TABLE 11-10
Water Treatment Technologies for Small Potable Water Systems
Technology Advantages Disadvantages
Filtration
Operational simplicity and reliability, low cost, ability to Not suitable for water with high turbidity, requires large
Slow sand
achieve greater than 99.9% Giardia cyst removal land areas
Most suitable for raw water with low bacterial counts
and low turbidity (<10 NTU), requires coagulant and
Diatomaceous earth Compact size, simplicity of operation, excellent cyst and
filter aids for effective virus removal, potential difficulty
(septum filter) turbidity removal
in maintaining complete and uniform thickness of
diatomaceous earth on filter septum
Most suitable for raw water with turbidity <1 NTU, usually
Reverse osmosis Compact, automated, complete removal of nearly any must be preceded by high levels of pretreatment, easily
membranes impurity clogged with colloids and silt if not properly designed,
upwards of 25–35% of water lost in concentrate stream
Rapid sand/direct filtration Compact, treat a wide range of water quality parameters and Chemical pretreatment may be complex and time-
package plants variable levels consuming, cost
Effective removal of dissolved iron and manganese from
Manganese greensand filter Takes up a lot of space
water supplies, chlorination regenerates media
Disinfection
Very effective, has a proven history of protection against
waterborne disease, widely used, variety of possible Potential for harmful trihalomethane (THM) by-products
Chlorine
application points, inexpensive, appropriate as both primary under certain conditions
and secondary disinfectant
Relatively high cost, more complex operation because it
Ozone Very effective, no trihalomethanes (THMs) formed must be generated onsite, dissipates quickly and requires
a secondary residual disinfectant
Very effective for viruses and bacteria, readily available,
Water must be highly filtered for effective use, no residual
Ultraviolet radiation no known harmful residuals, simple operation and
beyond the unit, requires a secondary residual disinfectant
maintenance for high-quality waters
Organic Contaminant Removal
Granular-activated carbon Effective for a broad spectrum of organics Spent carbon disposal, bacterial growth on media
Packed tower aeration Effective for volatile compounds Potential for air emissions issues
Diffused aeration Effective for volatile compounds and radionuclides Clogging, air emissions, variable removal efficiencies
Advanced oxidation Very effective By-products
Reverse osmosis Broad spectrum removal, disposal Variable removal efficiencies, wastewater
Inorganic Contaminant Removal
Large volumes of reject water generated, may remove too
Reverse osmosis Highly effective
many minerals
Expensive waste treatment, uses strong acids and bases,
Ion exchange Highly effective requires neutralization prior to discharge, may remove too
many minerals
Activated alumina Highly effective Expensive waste removal

• Physical: Physical characteristics, such as color, turbidity, taste, and odor, often are related to the appearance of the water. Physical
quality is corrected through the use of various types of permanent filtration devices.
• Chemical: The chemical characteristics of water are related to dissolved minerals (iron, hardness, sodium, etc.), gases, and organics. The
chemical quality of water is adjusted by the use of water softeners, manganese greensand filters, ion exchange, reverse osmosis units,
and activated charcoal units to remove organic impurities.
• Biological: These characteristics are concerned with microorganisms that may adversely impact the health of the consumer. Biological
treatment requires the use of biocides and biostats, ultraviolet treatment, or ozone to eliminate and reduce the number of microorganisms
present in the water and to create a residual amount of the chemical to maintain the required level of action required by code. Chlorine
and chloramine are the most common residual materials added to a potable water system prior to distribution.
• Radiological: This category is concerned primarily with radon in areas where the water may have come in contact with radioactive
substances. Retention and aeration lower the radon count to acceptable limits in approximately eight hours.
A synopsis of general treatment methods for small potable water systems, including a discussion of general advantages and disadvantages,
is given in Table 11-10.
WATER PURIFICATION
Water purification is the selective removal of impurities from source water, making it suitable for use for a specific purpose. There are a multitude
of uses for pure water, and the degree of purification required varies based on the ultimate use of the water. An integrated water purification
system designed to produce pure water used for any application generally consists of four interconnected steps: pretreatment, primary treatment,
storage, and finally polishing and distribution. Purification methods include any of the processes mentioned earlier in this chapter and are
selected based on the specific end-use requirements for the water.
Laboratory Systems
For laboratory work, all applications do not require the same quality of water. ASTM International, the Clinical and Laboratory Standards
Institute (CLSI), and other organizations have developed standards for water used in laboratories depending on the intended use. These
standards are summarized in Table 11-11.
To assist with decoding the various pure water categories, TABLE 11-11
CLSI classifies the three types of water as follows: CLSI and ASTM Reagent-Grade Water Specifications
• Type I, called reagent-grade water, is used for the CLSI Type ASTM Type
analysis of trace matter and other critical applications. Characteristic
It is the purest water covered by any laboratory I II III I II III IV
standard. This water is free from organic and inorganic Specific conductance,
0.1 0.2 0.5 0.056 1.0 0.25 5.0
impurities, suspended solids, and microorganisms. µmhos/cm
• Type II, called analytical-grade water, is suitable for all Specific resistance, MW
but the most critical procedures. 10 2.0 1.0 18 1.0 4 0.2
· cm
• Type III, called general laboratory-grade water, is
suitable for most qualitative analysis and equipment Silicate, µg/L 50 100 1,000 3 3 500 —
rinsing and as a supply for generating Type I water. Total organic carbon,
— — — 100 50 200 —
The four basic applications where high-purity water is µg/L
needed in a biological laboratory are: Sodium, µg/L — — — 1 5 10 50
• Water for media used in growing tissue cultures
• Water used in media formulations for growing bacteria Chlorides, µg/L — — — 1 5 10 50
and other prokaryotes Bacterial growth, cfu/mL <10 10 — a a a a
• Water used to make buffer solutions used for various
5.0–
purposes pH — — — — — —
8.0
• Water used to make analytical standards
With increases in sophistication and continuous demands a.classified
Microbiological contamination: When bacterial levels need to be controlled, reagent-grade types should be further
as follows: Maximum heterotropic bacteria count: Type A: 10/1,000 mL; Type B: 100/1,000 mL; Type C:
for higher-purity water, end-point polishing units are widely 10,000/1,000 mL
used to further purify feed water meeting the requirements for
Type I, II, or III water to remove some or all of the following trace impurities:
• Organics to a level below 5 ppb
• Bacteria and cell fragments to a non-detectable level
• Nucleases such as RNAse and DNAse
Hemodialysis Water
Water may be purified for use in hemodialysis applications where a membrane process or filter is used in place of a patient’s non-working
kidney to eliminate waste products from the patient’s bloodstream. The membrane used for hemodialysis is approximately the size and porosity
of an absolute membrane filter. During hemodialysis, a patient’s blood is introduced on one side of the dialysis membrane, and hemodialysis-
grade water is introduced on the other side of the membrane. Waste products are allowed to diffuse from the bloodstream across the dialysis

membrane and are thereby removed from the patient’s bloodstream. The water used for dialysis
purposes is blended to approximately the salinity of the bloodstream to ensure that minerals are TABLE 11-12
AAMI/ANSI Water Quality Standards
not lost during the dialysis process.
The criticality of the water used for hemodialysis is easy to understand—any impurities present Suggested Maximum
Contaminant
in hemodialysis-grade water may pass directly from the water through the dialysis membrane Level, mg/L
and into the patient’s blood. However, different organizations and regulators have established Calcium 2.0
different guidelines for the purity of this water. These organizations include the Association for
Magnesium 4.0
the Advancement of Medical Instrumentation (AAMI), ASTM, U.S. Pharmacopoeia, ISO,
Centers for Medicare and Medicaid Services (CMS), and others. While efforts are underway Sodium 70
to standardize and harmonize these requirements, significant discrepancies remain among the Potassium 8.0
various groups. In the U.S., the requirements of AAMI are generally followed in dialysis clinics,
and these requirements are listed in Table 11-12. Fluoride 0.2
As more knowledge is developed and the industry advances, standards for hemodialysis- Free chlorine 0.5
grade water are being tightened and harmonized. At some point, there should be harmonization
Chloramines 0.1
between AAMI and the U.S. Pharmacopoeia, which creates legally enforceable standards for
pharmaceutical-grade water. Nitrate (N) 2.0
Pharmaceutical Water Sulfate 100
The two major types of pharmaceutical grade water are purified water (USP-PW) and water
Antimony 0.006
for injection (USP-WFI). Purified water is typically used for products that are applied to the
skin or ingested by mouth. Water for injection is required for any pharmaceutical product that Copper, barium, zinc 0.1 each
is introduced or injected directly into the body or bloodstream. Companies representing that Arsenic, lead, silver 0.005 each
they are producing water meeting the requirements for purified water or WFI-grade water must
demonstrate compliance with established requirements by going through a qualification or Beryllium 0.0004
validation process that typically takes at least one year to complete. Chromium 0.014
The purity requirements for each are given in Table 11-13. These standards are legally
Cadmium 0.001
enforceable, and while the U.S. Pharmacopoeia creates the enforceable water purity requirements,
USP is not responsible for the enforcement of these requirements. Enforcement of these standards Selenium 0.09
is done by the U.S. Food and Drug Administration (FDA). Aluminum 0.01
The pharmaceutical industry is a global industry, and it is a common occurrence for a
pharmaceutical product to be manufactured in the U.S. and sold in other countries. Under Mercury 0.0002
these circumstances, pharmaceutical companies must comply not only with the requirements Thallium 0.002
established by USP, but also with requirements established by other pharmacopoeias where the
drug product is sold. The three largest and most well-established pharmacopoeias are the United Bacteria <100 (cfu/mL)
States, Europe, and Japan, although similar groups are present or are being established in other Endotoxin 0.25 EU/mL
countries throughout the world, most notably China and India.
Each pharmacopoeia establishes its own legally enforceable Table 11-13
requirements for purified water and WFI, and these legally USP 40 Purified Water and WFI Water Purity Standards
enforceable requirements vary from one pharmacopoeia to
Attribute/Impurity Purified Water Water for Injection
the next. There are currently more than 140 pharmacopoeias
in the world. Conductivitya <1.3 @ 25°C <1.3 @ 25°C
From the perspective of the pharmaceutical manufacturer, Total organic carbon ( g/L) 500 500
the variations in the water quality requirements between
different pharmacopoeias means that a manufacturer must None given, but None given, but
Bacteria recommended to be no recommended to be no
demonstrate that they meet or exceed all of the requirements
more than 100 cfu/mL more than 10 cfu/100 mL
established by each pharmacopoeia in countries in which
they want to do business. There are efforts underway through Endotoxin ---- <0.25 EU/mL
the International Conference on Harmonization (ICH) to a. There are three stages for conductivity measurement established USP <645>. This table lists only the first stage
harmonize the requirements that vary between one country and requirement.
the next. Progress is being made, but there is still considerable

work to be done.
Generally speaking, each pharmacopoeia does not seek to dictate how a company is allowed to produce a particular grade of water. What
they insist on is that the process that is selected is reliable, repeatable, and well documented. Pharmaceutical companies must demonstrate
compliance during drug submission as well as continued compliance during regular audits that are performed by enforcement authorities and
agencies. However, because of the critical purity requirements for WFI-grade water, regulatory groups tend to be more specific about acceptable
technologies, but there are some variations between groups. For example, every regulatory body agrees that distillation is a universally accepted
method for producing WFI-grade water. In fact, until just recently, the European Pharmacopoeia stated that distillation was the only method
they would accept for producing WFI-grade water. The USP, JP, and now EP (along with others) have allowed other technologies to be used
to produce WFI-grade water, provided that these processes are proven to be repeatable, robust, reliable, and consistent and can demonstrate
through testing, maintenance, etc., that these systems are operating in a continuous state of control. The challenge is that there are variations

between groups. Until these differences are worked out, pharmaceutical manufacturers will likely continue using the universally accepted
approach (distillation) for producing WFI unless there is a compelling reason for considering an alternative. As of the date of this publication,
China continues to only accept distillation as a method to product WFI-grade water.
It is generally accepted that the starting water quality for producing pharmaceutical-grade water is potable water. If the incoming water
does not meet potable water requirements in the country where the system is being constructed, the water must first be treated to make it
potable, and then it can be further purified into pharmaceutical-grade water.
As an example, to produce WFI-grade water by distillation, two types of distillation units may be used: multi-effect and vapor compression.
Each has different feed water requirements, so the water purification systems for each type of unit would vary significantly. Vapor compression
stills require softened water with low silica content. Multi-effect stills require water to be free of minerals, chlorides, silica, and more, and the
resulting water purification system used as a feed to a multi-effect still may be quite elaborate.
There is much more flexibility with technologies that may be utilized for the production of purified water. Many different designs have been
installed and are operating effectively. Because feed water characteristics vary widely across the U.S. and around the world, it is not uncommon
to see variations in purification methods.
A full discussion of equipment selection is beyond the scope of this handbook. For a complete discussion of pharmaceutical water systems,
the reader is encouraged to consult the ISPE’s Baseline Guide Volume 4: Water & Steam Systems.
Once purified or WFI water has been generated, it must be distributed to users without any degradation in water quality. Purified water and
WFI may be conveyed to use points through plastic or stainless steel piping systems, but stainless steel piping systems are dominant with WFI
water. Many WFI systems are maintained at elevated temperature (150 to 180°F [66 to 82°C]). These systems are considered self-sterilizing
at these temperatures, but WFI water may need to be cooled prior to use or to protect or ensure worker safety or for other reasons. Purified
water may be delivered to use points at ambient or elevated temperatures. Similar to WFI systems, hot purified water systems are considered
self-sterilizing. Many ambient temperature systems are periodically heat-sanitized, and stainless steel is usually the piping of choice if a system
is to be heat-sanitized.
Many purified water systems are constructed entirely from plastic piping and are operated at ambient temperature. In these cases, companies
must establish sanitization frequencies and protocols to demonstrate consistent compliance with established guidelines.
There are some special considerations for piping systems installed in pharmaceutical applications. Because of the importance of keeping
bacteria levels at a minimum, distribution systems are typically designed with the following in mind:
• Piping systems are fully drainable: All distribution piping systems should slope to drain so that, if shut down, all of the water contained
in them may be drained.
• Flow through the piping system all the time: Water should flow at all times through all parts of a distribution system. Even during
peak water usage, there should always be flow in the return leg of the system. Engineers have generally used a flow velocity of 5 fps for
purified water systems and 5 to 10 fps for WFI systems. Consideration is usually given for maintaining a lower velocity in the system
return during peak usage.
• No threads are allowed in a distribution system: This applies to purified water and WFI. Once the water leaves the final treatment step,
threads are not allowed, and the cleanest of assembly techniques is strongly recommended (orbital welding or similar for plastic piping
systems). Piping with a smooth internal surface finish is highly recommended.
• Minimize dead legs at tees and use points: It is generally understood that bacteria will come to rest and attach to piping and components
in low flow areas. To minimize these, pharmaceutical water distribution piping systems should be designed and installed with no dead
legs or dead spots where there is no flow. Manufacturers have developed an array of what are referred to as “zero dead leg valves” to
meet the strict requirements imposed by this industry.
Electronics and Semiconductor Water
While the pharmaceutical industry has favored the widespread use of stainless steel equipment and piping systems for maintaining the bacterial
purity of a water system through heat sanitization, the microelectronics and semiconductor industries have taken an alternative approach and
have favored the use of high-purity plastics such as polyvinylidene fluoride (PVDF) and perfluoroalkoxy (PFA) because of their smoothness,
purity, and chemical compatibility with high-purity water. In the semiconductor industry, trace levels of metallic impurities may be introduced
by water coming into contact with stainless steel, introducing impurities that negatively impact product quality and yield, so every effort is
made to reduce or eliminate stainless steel from these systems.
The microelectronics and semiconductor industries are concerned with living bacteria, but they are also concerned with non-viable or
dead bacteria, cell fragments, particles, large organic molecules, colloids, and any other impurity or contaminant that would interfere with the
products they are manufacturing. Table 11-14 contains a partial listing of the purity requirements that have been established for semiconductor
manufacturers.
The microelectronics and semiconductor industries have the most stringent requirements for water purity of any industry, and they are
continuously looking to improve the detection limits of instrumentation and other monitoring technologies. All other industries producing
pure water benefit from the guidance provided by these industries.
High-purity water systems designed to meet the needs of semiconductor water users typically incorporate pretreatment, reverse osmosis
(single or double pass), several steps of deionization, TOC control using ozone and/or UV, and filtration down to the submicron, ultrafilter,
nanofilter, or even RO level prior to use. Most microelectronics high-purity water systems generate hundreds, if not thousands, of gallons
per minute of ultrapure water. These water systems also reclaim and reprocess a significant portion of the water they generate to maintain the
cleanliness of piping and equipment while conserving water where possible.

TABLE 11-14
ASTM D5127-13/SEMI F63-0701 Electronics-Grade Water Standards (Partial)
Grade
Parameter
E-1 E-1.1 E-1.2 E-1.3 E-2 E-3 E-4
Resistivity at 25°C 18.1 18.2 18.2 18.2 16.5 12 0.5
Total organic carbon, TOC, max. (µg/L) 5 2 1 1 50 300 1,000
SiO2 (total), max. (µg/L) 5 3 1 0.5 10 50 1,000
Viable bacteria, max. 5/100 mL 3/100 mL 1/100 mL 1/10 L 10/100 mL 50/100 mL 100/100 mL
Copper, max. (µg/L) 0.05 0.02 0.002 0.0001 1 2 500
Zinc, max. (µg/L) 0.05 0.02 0.002 0.001 1 5 500
Nickel, max (µg/L) 0.05 0.02 0.002 0.0001 1 2 500
Sodium, max. (µg/L) 0.05 0.02 0.005 0.001 1 5 1,000
Potassium, max. (µg/L) 0.005 0.02 0.005 0.001 2 5 500
Chloride, max. (µg/L) 0.1 0.05 0.02 0.005 1 10 1,000
Nitrate, max. (µg/L) 0.1 0.05 0.02 0.005 1 5 500
Phosphate, max. (µg/L) 0.1 0.05 0.02 0.005 1 5 500
Sulfate, max. (µg/L) 0.1 0.05 0.02 0.005 1 5 500
TESTING TO CONFIRM THE SUITABILITY OF WATER PRODUCED BY A TREATMENT, CONDITIONING,

OR PURIFICATION SYSTEM
Testing must be performed periodically to ensure compliance with the established water quality requirements for each specific application. For
utility water, boiler water, soft water, and monitoring in the pretreatment portion of a high-purity water system, a proper sampling technique is
less critical and introduces fewer variables. However, when water is more highly purified, it becomes more challenging to remove a sample from
a system without introducing contamination from the sample valve, container, air, operator technique, or other extrinsic factors. For this reason,
it is desirable to monitor as many parameters as possible using an inline or online instrument rather than collecting samples from the system.
The types of impurities to be tested can be generally divided into chemical impurities and biological impurities. Chemical impurities such
as minerals, TOC, ions, and conductivity/resistivity are relatively uniformly distributed throughout a distribution system, meaning that a
measurement taken in several different locations will generate identical results. Once this equivalence has been established and documented,
these impurities are excellent candidates for continuous monitoring in a single location. Unfortunately, biological impurities such as bacteria
and endotoxins are not uniformly distributed in a water system, and samples must be collected to document the water quality at various
different use points if these impurities require monitoring.
Several methods to measure for the presence of bacteria can be used, including plate or viable-count assays, direct-count epifluorescence
microscopy, scanning electron microscopy, and direct culturing techniques. The most common means is the plate or viable-count method.
This is done by passing the water through a filter containing a sterile nutrient medium and counting the number of colonies appearing on the
medium after a period of time is allowed for growth. The resulting bacterial colonies are called colony forming units (cfu).
Because of the delays introduced by the direct culturing method (three to seven days), there is a high level of interest in methods to more
rapidly detect the presence of bacteria, particularly in water produced for pharmaceutical purposes. Rapid microbiological monitoring (RMM)
techniques utilizing online water bioburden analyzers (OBWAs) are rapidly evolving as of the writing of this handbook. Several instrument
manufacturers are developing analyzers based on a variety of analytical techniques to assist with the rapid detection of bacteria. While there is
great promise, widespread acceptance will require months if not years of comparative testing to establish correlations and to ultimately accept
an RMM technique over an established technique, particularly for product release purposes. In the pharmaceutical industry in particular, this
technique offers great promise as a process control tool, but point-of-use sampling will likely continue as the method of choice to document
the continued compliance of water with established quality requirements.
Endotoxins are measured in endotoxin units per milliliter (EU/mL). The most common measurement method for endotoxins is the
limulus amoebocyte lysate (LAL) test, wherein a blood extract of the horseshoe crab clots or solidifies in the presence of bacterial endotoxins.
Instrumentation has been developed to allow detection of endotoxins within about 20 to 30 minutes, with further advances bringing this
technology closer to being instantaneous.
For a more complete discussion of sampling best practices, the reader is encouraged to consult the ISPE’s Good Practice Guide: Sampling
for Pharmaceutical Water, Steam, and Process Gases. Although this guide was written specifically for pharmaceutical water systems, it discusses
best practices that apply to all industries.

ASPE Read, Learn, Earn Continuing Education

In order to receive CEU credit, please complete the below quiz online. If you score 90 percent or higher on the test, you will be notified that you have earned
0.1 CEU, which can be applied toward CPD or CPDT recertification or numerous regulatory-agency CE programs. (Please note that it is your responsibility to
determine the acceptance policy of a particular agency.)
Expiration date: Continuing education credit will be given for this examination through April 30, 2024.
Thank you to J. Francisco DeHoyos, CPD, FASPE for authoring this month’s quiz.
Water Treatment, Condition, and Purification (CEU 318)
1. In turbidity water, the particals that mostly remain in suspension are 7. What is called a measure of the “cloudiness” of water that is
called: measured by shining a beam of light through a sample and detecting
A) Sediment how much light passes through the sample and reaches a detector.
B) Silt A) Turbidity
C) Turbidity units B) Acidity
D) Calsification C) Resistance
D) Specific conductance
2. What is the consequence of accelerating oxygen, or by increasing
water temperature in a metalic piping system? 8. This measurement must be done in the field and is another tool to
A) Flow-Static measure the suspended solids content of a water supply:
B) Calsification A) PH Level
C) Changing a fluid stage from liquid into gas B) Jackson turbidity units (JTUs)
D) Corrosion C) Total Dissolved Solids (TDS)
D) Silt density index (SDI)
3. Municipalites normally add this to the public water supply prior to
distribution and use in the community for microorganism control. 9. This is a gas-transfer process in which water is brought into contact
A) Sand Filtration with air for the purpose of transferring volatile substances either into
B) Friendly Bacteria or out of the raw water:
C) Chlorine and chloramine A) Changing a fluid stage from liquid into gas
D) Nitrogen B) Areation
C) Carbon filtration
4. What is the range used to meassure the hydrogen concentration in D) Deaeration
water?
A) 0 to 14 10. What are the two types of heat-based deaerators?
B) 0 to 100 A) Filtration and Chemical Sanitation
C) -10 to 10 B) Ph balance an Vacuum
D) -14 to 14 C) De-scaling and Steam
D) Steam and Vacuum
5. Mineral scale deposits in water piping may contain a complex
mixture of mineral salts, sludge, and biological fouling. What is 11. In a Reverse Osmosis System; what process is referd as the removal of
usually the it’s primary constituent? suspended solids or particles through mechanical means.
A) Magnesium A) Back-Wash
B) Fluoride B) Filtration
C) Calcium carbonate C) Areation
D) Bacteria D) Distillation
6. When the concentration of hydrogen ions per Liter in water has a 12. At what temperature the Revese Osmosis RO membranes have been
value of 5; the wate is being? developed to withstand heat?
A) Basic A) 180° F
B) Neutral B) 160° F
C) Acid C) 220° F
D) Turbid D) 140° F

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Water Treatment,

Continuing Education from the

Water Treatment, Conditioning,

Water treatment, conditioning, and purification are generally considered to be as follows:

REGULATIONS, CODES, AND CONSENSUS STANDARDS

BASIC WATER CHEMISTRY

maximum solubility is reached, excess amounts of these compounds will not

3 Read, Learn, Earn April 2023

as it meets the ground, surface, or mineral formations as it percolates through the

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Chlorides and Sulfates

Chlorine and Chloramine

Dissolved Organic Materials and Organic Carbon

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Per- and Polyfluoroalkyl Substances (PFAS)

Sodium and Potassium

Suspended Solids, Turbidity, and Color

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Volatile Organic Compounds

TESTING THE INCOMING WATER SUPPLY FOR IMPURITY LEVELS

FIGURE 11-2 TABLE 11-2

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Total Dissolved Solids

Total Organic Carbon

Bacteria, Microorganisms, and Cell Fragments

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Corrosive Properties of Water

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The numerical values of A, B, C, and D for substitution into FIGURE 11-3

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Decarbonation or Carbon Dioxide Removal

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Filtration (also see Membrane Filtration, Reverse Osmosis, and Ultrafiltration/Nanofiltration)

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Permanent Media Filters

Deep-Bed Sand Filtration and Multimedia Filtration

Disposable Media Filters

Ion Exchange for Deionization

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Continuous deionization does have some

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Ultrafiltration and Nanofiltration

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APPLICATIONS REQUIRING WATER TREATMENT, CONDITIONING, OR PURIFICATION

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Boiler Feed Water

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Potable Water Treatment (Small Scale)

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the next. Progress is being made, but there is still considerable

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TESTING TO CONFIRM THE SUITABILITY OF WATER PRODUCED BY A TREATMENT, CONDITIONING,