Classification of water

Based on its source, water can be divided into ground water and surface water. Both types of water can
be exposed to contamination risks from agricultural, industrial, and domestic activities, which may
include many types of pollutants such as heavy metals, pesticides, fertilizers, hazardous chemicals, and
oils.
Parameters of water quality
There are three types of water quality parameters physical, chemical, and biological. They are
summarized in Table 1.
Physical parameters of water quality
Turbidity
Turbidity is the cloudiness of water. It is a measure of the ability of light to pass through water. It is
caused by suspended material such as clay, silt, organic material, plankton, and other particulate
materials in water.
Turbidity in drinking water is esthetically unacceptable, which makes the water look unappetizing. The
impact of turbidity can be summarized in the following points:
It can increase the cost of water treatment for various uses.
The particulates can provide hiding places for harmful microorganisms and thereby shield them from
the disinfection process.
Suspended materials can clog or damage fish gills, decreasing its resistance to diseases, reducing its
growth rates, affecting egg and larval maturing, and affecting the efficiency of fish catching method.
Suspended particles provide adsorption media for heavy metals such as mercury, chromium, lead,
cadmium, and many hazardous organic pollutants such as polychlorinated biphenyls (PCBs), polycyclic
aromatic hydrocarbons (PAHs), and many pesticides.
The amount of available food is reduced because higher turbidity raises water temperatures in light of
the fact that suspended particles absorb more sun heat. Consequently, the concentration of the dissolved
oxygen (DO) can be decreased since warm water carries less dissolved oxygen than cold water.
Turbidity is measured by an instrument called nephelometric turbidimeter, which expresses turbidity in
terms of NTU or TU. A TU is equivalent to 1 mg/L of silica in suspension.
Turbidity more than 5 NTU can be visible to the average person while turbidity in muddy water, it
exceeds 100 NTU. Groundwater normally has very low turbidity because of the natural filtration that
occurs as the water penetrates through the soil.
Solids
Solids occur in water either in solution or in suspension. These two types of solids can be identified by
using a glass fiber filter that the water sample passes through. By definition, the suspended solids are
retained on the top of the filter and the dissolved solids pass through the filter with the water.
If the filtered portion of the water sample is placed in a small dish and then evaporated, the solids as a
residue. This material is usually called total dissolved solids or TDS.
Total solid(TS)=Total dissolved solid(TDS)+Total suspended solid(TSS)E2
Water can be classified by the amount of TDS per liter as follows:
freshwater: <1500 mg/L TDS;
brackish water: 1500–5000 mg/L TDS;
saline water: >5000 mg/L TDS.
The residue of TSS and TDS after heating to dryness for a defined period of time and at a specific
temperature is defined as fixed solids. Volatile solids are those solids lost on ignition (heating to 550°C).
These measures are helpful to the operators of the wastewater treatment plant because they roughly
approximate the amount of organic matter existing in the total solids of wastewater, activated sludge,
and industrial wastes.
Alkalinity
The alkalinity of water is its acid-neutralizing capacity comprised of the total of all titratable bases. The
measurement of alkalinity of water is necessary to determine the amount of lime and soda needed for
water softening (e.g., for corrosion control in conditioning the boiler feed water). Alkalinity of water is
mainly caused by the presence of hydroxide ions (OH−), bicarbonate ions (HCO3−), and carbonate ions
(CO32−), or a mixture of two of these ions in water. As stated in the following equation, the possibility
of OH− and HCO3− ions together are not possible because they react together to produce CO32− ions:

OH−+HCO3−→CO32−+H2OOH−+HCO3−→CO32−+H2O

Alkalinity is determined by titration with a standard acid solution (H2SO4 of 0.02 N) using selective
indicators (methyl orange or phenolphthalein).
The high levels of either acidity or alkalinity in water may be an indication of industrial or chemical
pollution. Alkalinity or acidity can also occur from natural sources such as volcanoes. The acidity and
alkalinity in natural waters provide a buffering action that protects fish and other aquatic organisms
from sudden changes in pH. For instance, if an acidic chemical has somehow contaminated a lake that
had natural alkalinity, a neutralization reaction occurs between the acid and alkaline substances; the pH
of the lake water remains unchanged. For the protection of aquatic life, the buffering capacity should
be at least 20 mg/L as calcium carbonate.

Hardness
Hardness is a term used to express the properties of highly mineralized waters [10]. The dissolved
minerals in water cause problems such as scale deposits in hot water pipes and difficulty in producing
lather with soap.
Calcium (Ca2+) and magnesium (Mg2+) ions cause the greatest portion of hardness in naturally
occurring waters. They enter water mainly from contact with soil and rock, particularly limestone
deposits.
These ions are present as bicarbonates, sulfates, and sometimes as chlorides and nitrates. Generally,
groundwater is harder than surface water. There are two types of hardness:
Temporary hardness which is due to carbonates and bicarbonates can be removed by boiling, and
Permanent hardness which is remaining after boiling is caused mainly by sulfates and chlorides.
Water with more than 300 mg/L of hardness is generally considered to be hard, and more than 150 mg/L
of hardness is noticed by most people, and water with less than 75 mg/L is considered to be soft.
From health viewpoint, hardness up to 500 mg/L is safe, but more than that may cause a laxative effect.
Hardness is normally determined by titration with ethylene diamine tetra acidic acid or (EDTA) and
Eriochrome Black and Blue indicators. It is usually expressed in terms of mg/L of CaCO3.

Total hardness mg/L as CaCO3 = calcium hardness mg/L as CaCO3 + magnesium hardness mg/L
as CaCO3
Table 1.
Parameters of water quality.
Types of water quality parameters
No.
Physical parameters Chemical parameters Biological parameters
1 Turbidity pH Bacteria
2 Temperature Acidity Algae
3 Color Alkalinity Viruses
4 Taste and odor Chloride Protozoa
5 Solids Chlorine residual
6 Electrical conductivity (EC) Sulfate
7 Nitrogen
8 Fluoride
9 Iron and manganese
10 Copper and zinc
11 Hardness
12 Dissolved oxygen
13 Biochemical oxygen demand (BOD)
14 Chemical oxygen demand (COD)
15 Toxic inorganic substances
16 Toxic organic substances
17 Radioactive substances

Dissolved oxygen
Dissolved oxygen (DO) is considered to be one of the most important parameters of water quality in
streams, rivers, and lakes. It is a key test of water pollution. The higher the concentration of dissolved
oxygen, the better the water quality.
Oxygen is slightly soluble in water and very sensitive to temperature. For example, the saturation
concentration at 20°C is about 9 mg/L and at 0°C is 14.6 mg/L.
The actual amount of dissolved oxygen varies depending on pressure, temperature, and salinity of the
water. Dissolved oxygen has no direct effect on public health, but drinking water with very little or no
oxygen tastes unpalatable to some people.
There are three main methods used for measuring dissolved oxygen concentrations: the colorimetric
method—quick and inexpensive, the Winkler titration method—traditional method, and the
electrometric method.
Biochemical oxygen demand (BOD)
Bacteria and other microorganisms use organic substances for food. As they metabolize organic
material, they consume oxygen. The organics are broken down into simpler compounds, such as CO2
and H2O, and the microbes use the energy released for growth and reproduction.
When this process occurs in water, the oxygen consumed is the DO in the water. If oxygen is not
continuously replaced by natural or artificial means in the water, the DO concentration will reduce as
the microbes decompose the organic materials. This need for oxygen is called the biochemical oxygen
demand (BOD). The more organic material there is in the water, the higher the BOD used by the
microbes will be. BOD is used as a measure of the power of sewage; strong sewage has a high BOD
and weak sewage has low BOD.
The complete decomposition of organic material by microorganisms takes time, usually 20 d or more
under ordinary circumstances. The quantity of oxygen used in a specified volume of water to fully
decompose or stabilize all biodegradable organic substances is called the ultimate BOD or BODL.
BOD is a function of time. At time = 0, no oxygen will have been consumed and the BOD = 0. As each
day goes by, oxygen is used by the microbes and the BOD increases. Ultimately, the BODL is reached
and the organic materials are completely decomposed.
A graph of the BOD versus time is illustrated as in Figure 3. This is called the BOD curve, which can
be expressed mathematically by the following equation:

Figure 3. BOD curve.

BODt=BODL×(1−10 ) −kt

where BODt = BOD at any time t, mg/L; BODL = ultimate BOD, mg/L; k = a
constant representing the rate of the BOD reaction; t = time, d.

The value of the constant rate k depends on the temperature, the type of organic materials, and the type
of microbes exerting the BOD.
Chemical oxygen demand (COD)
The chemical oxygen demand (COD) is a parameter that measures all organics: the biodegradable and
the non-biodegradable substance. It is a chemical test using strong oxidizing chemicals (potassium
dichromate), sulfuric acid, and heat, and the result can be available in just 2 h. COD values are always
higher than BOD values for the same sample.
Table 2.
Classification of water according to its hardness.

Total hardness concentration as mg/L as

Water classification
CaCO3
Soft water <50 mg/L as CaCO3
Moderately hard 50–150 mg/L as CaCO3
Hard water 150–300 mg/L as CaCO3
Very hard >300 mg/L as CaCO3

Industrial water should fulfil the following quality requirement (requisites) :

✓ pH between 6.5-8.5
✓ dissolved oxygen 6mg/l or more.
✓ Biochemical oxygen demand 5 days 20 C, 2mg/l or less.
o

Major application of industrial water use includes thermoelectric power plants, manufacturing plants,
ore and oil refineries, and hydroelectric dams. Water in these processes can play the roles of cooling,
solvent, and chemical reagents.

Water treatment is any process that improves the quality of water to make it appropriate for a specific
end-use. The end-use may be drinking, industrial water supply, irrigation, etc. Water treatment removes
contaminants and undesirable components, or reduces their concentration so that the water becomes fit
for its end-use.

Water treatment steps

Coagulation
Coagulation is often the first step in water treatment. During coagulation, chemicals with a
positive charge are added to the water. The positive charge neutralizes the negative charge of
dirt and other dissolved particles in the water. When this occurs, the particles bind with the
chemicals to form slightly larger particles. Common chemicals used in this step include specific
types of salts, aluminum, or iron.

Flocculation
Flocculation follows the coagulation step. Flocculation is the gentle mixing of the water to
form larger, heavier particles called flocs. Often, water treatment plants will add additional
chemicals during this step to help the flocs form.
Sedimentation
Sedimentation is one of the steps water treatment plants use to separate out solids from the
water. During sedimentation, flocs settle to the bottom of the water because they are heavier
than water.

Filtration
Once the flocs have settled to the bottom of the water, the clear water on top is filtered to
separate additional solids from the water. During filtration, the clear water passes through
filters that have different pore sizes and are made of different materials (such as sand, gravel,
and charcoal). These filters remove dissolved particles and germs, such as dust, chemicals,
parasites, bacteria, and viruses. Activated carbon filters also remove any bad odors.

Water treatment plants can use a process called ultrafiltration in addition to or instead of
traditional filtration. During ultrafiltration, the water goes through a filter membrane with very
small pores. This filter only lets through water and other small molecules (such as salts and
tiny, charged molecules).

Ion exchange
Ion exchange involves removing the hardness ions calcium and magnesium and replacing
them with non-hardness ions, typically sodium supplied by dissolved sodium chloride salt, or
brine. The softener contains a microporous exchange resin, usually sulfonated polystyrene
beads that are supersaturated with sodium to cover the bead surfaces. As water passes through
this resin bed, calcium and magnesium ions attach to the resin beads and the loosely held
sodium is released from the resin into the water. The softening process is illustrated in Fig. 1.
After softening a large quantity of hard water the beads become saturated with calcium and
magnesium ions. When this occurs, the exchange resin must be regenerated, or recharged. To
regenerate, the ion exchange resin is flushed with a salt brine solution (Figure 1). The sodium
ions in the salt brine solution are exchanged with the calcium and magnesium ions on the resin
and excess calcium and magnesium is flushed out with wastewater.

Frequency of the regeneration or recharge cycle depends on the hardness of the water, the
amount of water used, size of the softener, and capacity of the resins. Sixty to 120 minutes
generally are required for the brine to pass through the unit and flush the tank before soft water
is available again.

Ion exchange systems are used for efficient removal of dissolved ions from water.

Ion exchangers exchange one ion for another, hold it temporarily, and then release it to a
regenerant solution. In an ion exchange system, undesirable ions in the water supply are
replaced with more acceptable ions. For example, in a sodium zeolite softener, scale-forming
calcium and magnesium ions are replaced with sodium ions.

All natural waters contain, in various concentrations, dissolved salts which dissociate in water
to form charged ions. Positively charged ions are called cations; negatively charged ions are
called anions. Ionic impurities can seriously affect the reliability and operating efficiency of a
boiler or process system. Overheating caused by the buildup of scale or deposits formed by
these impurities can lead to catastrophic tube failures, costly production losses, and
unscheduled downtime. Hardness ions, such as calcium and magnesium, must be removed from
the water supply before it can be used as boiler feedwater. For high-pressure boiler feedwater
systems and many process systems, nearly complete removal of all ions, including carbon
dioxide and silica, is required. Ion exchange systems are used for efficient removal of dissolved
ions from water.

Ion exchangers exchange one ion for another, hold it temporarily, and then release it to a
regenerant solution. In an ion exchange system, undesirable ions in the water supply are
replaced with more acceptable ions. For example, in a sodium zeolite softener, scale-forming
calcium and magnesium ions are replaced with sodium ions.
SODIUM ZEOLITE SOFTENING

Sodium zeolite softening is the most widely applied use of ion exchange. In zeolite softening,
water containing scale-forming ions, such as calcium and magnesium, passes through a resin
bed containing SAC resin in the sodium form. In the resin, the hardness ions are exchanged
with the sodium, and the sodium diffuses into the bulk water solution. The hardness-free water,
termed soft water, can then be used for low to medium pressure boiler feedwater, reverse
osmosis system makeup, some chemical processes, and commercial applications, such as
laundries.

Principles of Zeolite Softening

The removal of hardness from water by a zeolite softening process is described by the following
reaction:

As illustrated by the softening reactions, SAC resin readily accepts calcium and magnesium
ions in exchange for sodium ions. When exhausted resin is regenerated, a high concentration
of sodium ions is applied to the resin to replace calcium and magnesium. The resin is treated
with a 10% sodium chloride solution, and regeneration proceeds according to the following
equation:

During regeneration, a large excess of regenerant (approximately 3 times the amount of

calcium and magnesium in the resin) is used. The eluted hardness is removed from the softening
unit in the waste brine and by rinsing.

DEMINERALIZATION

Softening alone is insufficient for most high-pressure boiler feedwaters and for many process
streams, especially those used in the manufacture of electronics equipment. In addition to the
removal of hardness, these processes require removal of all dissolved solids, such as sodium,
silica, alkalinity, and the mineral anions (Cl¯, SO4²¯, NO3¯).
Demineralization of water is the removal of essentially all inorganic salts by ion exchange. In
this process, strong acid cation resin in the hydrogen form converts dissolved salts into their
corresponding acids, and strong base anion resin in the hydroxide form removes these acids.
Demineralization produces water similar in quality to distillation at a lower cost for most fresh
waters.

Principles of Demineralization

A demineralizer system consists of one or more ion exchange resin columns, which include a
strong acid cation unit and a strong base anion unit. The cation resin exchanges hydrogen for
the raw water cations as shown by the following reactions:

To complete the demineralization process, water from the cation unit is passed through a strong
base anion exchange resin in the hydroxide form. The resin exchanges hydrogen ions for both
highly ionized mineral ions and the more weakly ionized carbonic and silicic acids, as shown
below:

The above reactions indicate that demineralization completely removes the cations and anions
from the water. In reality, because ion exchange reactions are equilibrium reactions, some
leakage occurs. Most leakage from cation units is sodium. This sodium leakage is converted to
sodium hydroxide in the anion units. There-fore, the effluent pH of a two bed cation-anion
demineralizer system is slightly alkaline. The caustic produced in the anions causes a small
amount of silica leakage. The extent of leakage from the anions depends on the chemistry of
the water being processed and the regenerant dosage being used.

DEALKALIZATION
Often, boiler or process operating conditions require the removal of hardness and the reduction
of alkalinity but not the removal of the other solids. Zeolite softening does not reduce alkalinity,
and demineralization is too costly. For these situations, a dealkalization process is used.
Sodium zeolite/hydrogen zeolite (split stream) dealkalization, chloride-anion dealkalization,
and weak acid cation dealkalization are the most frequently used processes.

Sodium Zeolite/Hydrogen Zeolite (Split Stream) Dealkalization

In a split stream dealkalizer, a portion of the raw water flows through a sodium zeolite softener.
The remainder flows through a hydrogen-form strong acid cation unit (hydrogen zeolite). The
effluent from the sodium zeolite is combined with the hydrogen zeolite effluent. The effluent
from the hydrogen zeolite unit contains carbonic acid, produced from the raw water alkalinity,
and free mineral acids. When the two streams are combined, free mineral acidity in the
hydrogen zeolite effluent converts sodium carbonate and bicarbonate alkalinity in the sodium
zeolite effluent to carbonic acid as shown below:

Carbonic acid is unstable in water. It forms carbon dioxide gas and water. The blended effluents
are sent to a decarbonator or degasser, where the carbon dioxide is stripped from the water by
a countercurrent stream of air.

Carbonic acid is unstable in water. It forms carbon dioxide gas and water. The blended effluents
are sent to a decarbonator or degasser, where the carbon dioxide is stripped from the water by
a countercurrent stream of air.

Sodium Zeolite/Chloride Anion Dealkalization

Strong base anion resin in the chloride form can be used to reduce the alkalinity of a water.
Water flows through a zeolite softener and then an anion unit, which replaces the carbonate,
bicarbonate, sulfate, and nitrate ions with chloride ions as shown in these reactions:

The chloride anion dealkalizer reduces alkalinity by approximately 90% but does not reduce
total solids. When the resin nears exhaustion, treated water alkalinity increases rapidly,
signaling the need for regeneration.

The zeolite softener is regenerated as previously described. In addition, the anion resin is also
regenerated with a sodium chloride brine that returns the resin to the chloride form. Frequently,
a small amount of caustic soda is added to the regenerant brine to enhance alkalinity removal.

CLASSIFICATIONS OF ION EXCHANGE RESINS

Ionizable groups attached to the resin bead determine the functional capability of the resin.
Industrial water treatment resins are classified into four basic categories:
• Strong Acid Cation (SAC)
• Weak Acid Cation (WAC)
• Strong Base Anion (SBA)
• Weak Base Anion (WBA)
SAC resins can neutralize strong bases and convert neutral salts into their corresponding acids.
SBA resins can neutralize strong acids and convert neutral salts into their corresponding bases.
These resins are utilized in most softening and full demineralization applications. WAC and
WBA resins are able to neutralize strong bases and acids, respectively. These resins are used
for dealkalization, partial demineralization, or (in combination with strong resins) full
demineralization.
Ion exchange (IX) resin technology has been used extensively as a practical and effective form
of water treatment for many years. IX is often used with water softening, which is its most
common application. However, IX resins have many other applications. Water contamination
is an important issue globally, and new drinking water quality regulations have been introduced
for contaminants such as disinfectant byproducts, arsenic, nitrate, perchlorate and uranium.
Specialized IX resins address these challenges.
The IX process removes soluble ionized contaminants such as hardness and alkalinity from
water via a reversible ionic interchange between a solid phase (resin beads) and liquid phase
(water). IX resins’ two main categories are cation and anion. Cation IX resins include
strong/weak cation, (H+ and Na+). Anion IX resins include a strong/weak anion, such as OH-
and Cl-. Acting together or alone, these types remove many ionic contaminants from water.
Neither type removes non-ionic contaminants such as benzene.

Cation resins
Positively charged cation resins remove positively charged ionic water contaminants. Included
in this category of resins are strong acid/strong cation (SAC) and weak acid/weak cation
(WAC) resins.

Hardness removal
SAC resin is effective for water softening, which removes hardness ions. It has been used in
residential, commercial and industrial applications for more than 100 years. Like tiny magnets,
SAC resin beads remove scale-forming calcium (Ca2+) and magnesium (Mg2+) ions by
exchanging them for sodium ions. Hardness levels are reduced and sodium levels are increased.
All resin has a finite exchange capacity. Individual exchange sites on the resin beads will
eventually become full and incapable of exchanging further hardness, so the resin must be
recharged. Since SAC resin beads have a higher affinity for calcium/magnesium ions than
sodium ions, a concentrated solution of sodium chloride brine (typically 8 to 12 percent) is
used to force accumulated hardness ions off the resin beads.

Softening and dealkalization

Weak acid cation (WAC) resin can remove hardness and alkalinity simultaneously. It also
provides some degree of total dissolved solids (TDS) removal. Generally, WAC resin removes
about 80 percent of the temporary hardness (hardness associated with dissolved bicarbonate
minerals). TDS are reduced by about 17.1 parts per million (ppm) for each grain of hardness
removed. Since WAC resin exchanges hardness and alkalinity ions for hydrogen ions, the
treated water will be acidic (or lower pH). The degree to which TDS are reduced and pH
lowered largely depends on the incoming hardness levels.
Barium and radium removal
Barium and radium, two divalent cations, are regulated by the U.S. Environmental Protection
Agency (EPA) for National Primary Drinking Water Standards and can be removed by
standard SAC resin. However, when regenerating the resin, efficiency is reduced because of
the slow diffusion of their larger atomic mass deep into the resin matrix. Special types of SAC
resin with properties that enhance barium and radium reduction are commercially available and
tested/certified by the National Science Foundation (NSF).
Anion resins
Negatively charged anion resins remove negatively charged ionic contaminants in water.
Included in this category of resins are strong base/strong anion (SBA) and weak base/weak
anion (WBA) resins. These anion resins can be used to remove the contaminants described in
this section.
NO3–
SBA resin can remove nitrate (NO3-). If the ratio of sulfate to NO3– concentration in the water
is high, the resin must be regenerated early to avoid the sulfate anion acting as a regenerant and
discharging NO3-. In situations with elevated sulfate concentrations, a selective SBA resin can
be used as well.
ClO4–
SBA resins exist that selectively remove perchlorate (ClO4-). These resins can be single-use
and/or regenerable.
Arsenic
In water, arsenic is related to arsenate, As(V) and arsenite, As(III). Only negatively charged
arsenate (HAsO42-) anions can be removed using SBA resins. Arsenite (H3AsO3) is normally
neutral in aqueous solution. Therefore, pre-oxidation is needed to convert As(III) to As(V)
anion. Once this oxidation is complete, the residual must be removed before contacting the
SBA resin.
TOC
Total organic carbon (TOC) or naturally occurring organic matter can be oxidized by secondary
chlorine disinfection and create DBPs, such as THMs and HAAs. These DBPs are suspect
carcinogens and regulated by the EPA in drinking water. Municipal treatment plants sometimes
remove TOC to limit the formation of DBPs. TOC is typically negatively charged and removed
using SBA resin.
Uranium
SBA resin can be used to remove uranium, which typically exists as anionic uranyl
carbonate/sulfate complexes.
Demineralization/deionization
SAC and SBA resins employed in combination either individually or mixed together can be
used to reduce minerals and TDS in water. Minerals in the water are exchanged with hydrogen
cations (H+) and hydroxide anions (OH–) from the resin beads to form highly purified water
(H2O).
Disinfection
SBA resin is used to ionically bind halogens as an antimicrobial disinfectant and is
commercially available for use in different treatment applications.