Water Quality - Total Alkalinity and

Hardness
More confusion exists between hardness and alkalinity than any of the other water quality parameters. This is
because most hardness and alkalinity comes from limestone or dolomite sources in nature. Limestone is
calcium carbonate, and dolomite is a combination of calcium carbonate and magnesium carbonate. Water passes
through the rocks in the ground as it makes it way to rivers and lakes, and picks up minerals on the way. When
limestone and dolomite dissolve in water, one half of the molecule is calcium or magnesium (the "hardness")
and the other half is the carbonate (the "alkalinity"), so most of the times they are equal. However, they are
very separate measurements, and have very different importance for the aquarium.
Total Alkalinity: Total alkalinity is the measurement of all bases in the water and can be thought of as the buffering
capacity of water, or its ability to resist change in pH. The most common and important base is carbonate. Total
alkalinity is expressed as milligrams per liter (mg/L) or parts per million (ppm) of calcium carbonate (CaCO3).

Total Hardness: Total hardness is the measurement of divalent cations (+2 ions) in the water and, like total alkalinity,
is expressed as milligrams per liter (mg/L) or parts per million (ppm) of calcium carbonate (CaCO3).

What is the difference between hardness and alkalinity?

Answer
Hardness is the sum of the multivalent metal ions in solution, whereas alkalinity
is a measure of the solution’s ability to neutralize acids (sum of hydroxide,
carbonate, and bicarbonates). In natural water systems calcium carbonate is
usually present and responsible for different characteristics of the water. Both
hardness and alkalinity are expressed as a concentration of CaCO3 for
convenience of reporting a single number to represent multiple chemicals and
for ease in calculating a solution’s carbonate and non-carbonate hardness.

Monitoring alkalinity and hardness

Alkalinity refers to the total amount of bases in water expressed in mg/l of equivalent calcium carbonate. A
base is a substance that releases hydroxyl ions (OH-) when dissolved in water. In most waters these bases
are principally bicarbonate (HCO3) ions and carbonate ions (CO32-). These ions are the buffers in water; that is
they buffer the water against sudden changes in pH. They can do this by absorbing hydrogen ions when the
water is acid and releasing them when the water becomes basic. Waters of low alkalinity (<20 mg/l) are
poorly buffered, and the removal of carbon dioxide (CO2) during photosynthesis results in rapidly rising pH.
Waters, with greater than 20 mg/l alkalinity have greater buffering capacity and prevent large fluctuations in
pH during photosynthesis (Fig. 1).
Fig. 1. The effect of buffering on pH at low and high alkalinities
 Hardness is the concentration of metal ions (primarily calcium and magnesium) expressed in mg/l of
equivalent calcium carbonate. Alkalinity and hardness values are normally similar to magnitude because
calcium, magnesium, bicarbonate, and carbonate ions in water are derived in equivalent quantities from the
solution of limestone in geological deposits. However, in some waters alkalinity may exceed its hardness and
vice versa. If alkalinity is high and hardness low, pH may rise to very high levels (greater than 10.5) during
periods of rapid photosynthesis.
Waters are often categorised according to degrees of hardness as follows:

 0-75 mg/l - soft

 75-150 mg/l - moderately hard
 150-300 mg/l - hard
 over 300 mg/l - very hard

Alkalinity and hardness are not greatly affected by biological activity or aquacultural operations, and the initial
concentrations in ponds are determined by their level in the water supply; any changes are largely the result
of rainfall and evaporation. Desirable levels for fish culture generally fall within the range of 20-300 mg/l. If
total alkalinity and total hardness are too low, they may be raised by liming. However, there is no practical
way of decreasing alkalinity and hardness when they are above desirable levels.
As a general rule, the most productive waters for fish culture have a hardness and alkalinity of approximately
the same magnitude. For example, a water with an alkalinity of 100 mg/l and hardness of 10 mg/l is not as
good for fish culture as water in which the alkalinity is 100 mg/l and the hardness is 100 mg/l. Greater
production does not result directly from higher levels of hardness and alkalinity per se, but from the higher
concentrations of phosphorus and other essential elements that increase along with hardness and alkalinity.

Hardness

If water consumes excessive soap to produce lather, it is said to be hard. Hardness is

caused by divalent metallic cations. The principal hardness causing cations are calcium,
magnesium, strontium, ferrous and manganese ions. The major anions associated with
these cations are sulphates, carbonates, bicarbonates, chlorides and nitrates.

The total hardness of water is defined as the sum of calcium and magnesium
concentrations, both expressed as calcium carbonate, in mg/L. Hardness are of two
types, temporary or carbonate hardness and permanent or non carbonate hardness.
Temporary hardness is one in which bicarbonate and carbonate ion can be precipitated
by prolonged boiling. Non-carbonate ions cannot be precipitated or removed by boiling,
hence the term permanent hardness. IS value for drinking water is 300 mg/L as
CaCO3.

Carbonate Hardness and Non-carbonate Hardness

Classification of hardness can be classified based anion that has association with metal ion namely carbonate hardness
and non-carbonate hardness. In the carbonate hardness, calcium and magnesium ions associated with CO 32-and HCO3-.
In the non-carbonate hardness, calcium and magnesium ions associated with SO 42-, Cl-and NO3-. Carbonate hardness
very sensitive to heat and easy to make sediment at high temperatures such as the following reaction:

Ca(HCO3)2 → CaCO3 sediment + CO2 + H2O

Mg(HCO3)2 → Mg(OH)2 sediment + 2CO2

Therefore, carbonate hardness can be called as temporary hardness. Non-carbonate hardness can be called as
permanent hardness because calcium and magnesium that bind with sulfate and chloride, does not make sediment and
hardness values does not change despite in high temperature.

Part of the total hardness is equivalent to bicarbonate that participates in the presence of carbonate alkalinity in
accordance with carbonate hardness. Since the alkalinity and hardness are determined in CaCO 3, carbonate hardness
can be calculated by following formula:

If the total alkalinity < total hardness so carbonate hardness = total alkalinity.

If the total alkalinity ≥ total hardness so carbonate hardness = total hardness.

Non-carbonate hardness = total hardness - carbonate hardness.

If total alkalinity exceeds total hardness so some of anion constituent of alkalinity (bicarbonate and carbonate)
associated with single valence cations (monovalent), for example, potassium (K +) and natrium (Na +) that are not
detected in determination of hardness. Conversely, if total hardness exceeds total alkalinity so some of cation
constituent of hardness (calcium and magnesium) bind to sulfate (SO 42-), chloride (Cl-), silicate (SiO32-) or nitrate (NO3-)
that are not detected in determination of alkalinity. Therefore the relationship between hardness and alkalinity is not
always positive; or greater hardness is not always accompanied with higher alkalinity and vice versa.

Classification of Hardness
Classification of hardness can be categorized based on some parameters such as based on metal ions, based on anion
that has association with metal ion and based on CaCO3 content.

Classification of hardness based on metal ion can be divided as follow:

1. Calcium hardness
2. Magnesium hardness
Classification of hardness based on anion that has association with metal ion can be divided as follow:

1. Carbonate hardness
2. Non-carbonate hardness

Classification of hardness based on CaCO3 content can be divided as follow:

1. Soft hardness if contains 0-75 mg/l CaCO3 content.

2. Semi hardness if contains 75-150 mg/l CaCO3 content.
3. Hardness if contains 150-300 mg/l CaCO3 content.
4. Very hardness if contains more than 300 mg/l CaCO3 content.

Calcium and Magnesium Hardness

Water hardness can be classified based on metal ion namely calcium hardness and magnesium hardness. Most of natural
water has calcium and magnesium hardness due to calcium and magnesium ions. Calcium and magnesium hardness
often need to be known to determine amount of lime and soda ash which is needed in the process of water softening
(lime-soda ash softening). If the calcium hardness value is known so magnesium hardness can be determined through
the following equation:

Magnesium hardness = Total Hardness - Calcium hardness

In determining hardness value of total hardness, calcium hardness and magnesium hardness, the presence of iron and
manganese are considered as nuisance because it can react with the reagent which is used. Therefore, calcium
hardness is assumed greater than the level of calcium ions, and vice versa. The following equation can be used to get
the level of calcium ions and magnesium ions of hardness value:

Levels of Ca2+ (mg/liter) = 0.4 x calcium hardness

Levels of Mg2+ (mg /liter) = 0.243 x magnesium hardness

Carbonate Hardness and Non-carbonate Hardness

Classification of hardness can be classified based anion that has association with metal ion namely carbonate hardness
and non-carbonate hardness. In the carbonate hardness, calcium and magnesium ions associated with CO 32-and HCO3-.
In the non-carbonate hardness, calcium and magnesium ions associated with SO 42-, Cl-and NO3-. Carbonate hardness
very sensitive to heat and easy to make sediment at high temperatures such as the following reaction:

Ca(HCO3)2 → CaCO3 sediment + CO2 + H2O

Mg(HCO3)2 → Mg(OH)2 sediment + 2CO2
Therefore, carbonate hardness can be called as temporary hardness. Non-carbonate hardness can be called as
permanent hardness because calcium and magnesium that bind with sulfate and chloride, does not make sediment and
hardness values does not change despite in high temperature.

Part of the total hardness is equivalent to bicarbonate that participates in the presence of carbonate alkalinity in
accordance with carbonate hardness. Since the alkalinity and hardness are determined in CaCO 3, carbonate hardness
can be calculated by following formula:

If the total alkalinity < total hardness so carbonate hardness = total alkalinity.

If the total alkalinity ≥ total hardness so carbonate hardness = total hardness.

Non-carbonate hardness = total hardness - carbonate hardness.

If total alkalinity exceeds total hardness so some of anion constituent of alkalinity (bicarbonate and carbonate)
associated with single valence cations (monovalent), for example, potassium (K +) and natrium (Na +) that are not
detected in determination of hardness. Conversely, if total hardness exceeds total alkalinity so some of cation
constituent of hardness (calcium and magnesium) bind to sulfate (SO42-), chloride (Cl-), silicate (SiO32-) or nitrate (NO3-)
that are not detected in determination of alkalinity. Therefore the relationship between hardness and alkalinity is not
always positive; or greater hardness is not always accompanied with higher alkalinity and vice versa.

Total Hardness
Definition - What does Total Hardness mean?
Total hardness is a measurement of the mineral content in a water sample that is irreversible by
boiling. Therefore, total hardness can be equivalent to the total calcium and magnesium hardness.
Total hardness is determined by the multivalent cations' concentrations present in water. These
cations have a positive charge that is higher than 1+. Typically, cations have a charge of 2+. The
most common cations present in hard water are Mg2+ and Ca+.
Hard water is not seriously harmful to human health. However, water with a high level of hardness
could cause serious problems in industrial settings wherein water hardness is typically monitored to
prevent costly failures in components like cooling towers, boilers and other equipment that contains or
processes water.

Corrosionpedia explains Total Hardness

Various measures and kits can be used to measure the magnesium and calcium present in the hard
water. These two essential minerals are the main cause of water hardness.
To reduce the total hardness of water, certain processes such as water softening can help. With
softening, the adverse effects of hard water can be reduced significantly.
High total hardness can result in abnormal cloudiness and the formation of scale. However, levels of
hardness that are too low could make the water corrosive and more aggressive. Thus, industries that
utilize equipment and machinery that handle water should ensure that the total hardness levels are
maintained at appropriate levels to prevent the water from becoming corrosive.

What do you mean by hardness of water?

(Classifications and removal)
Hardness of water (Classifications and removal)
Water which cannot form lather easily with soap is known as hard water and this
characteristic is called hardness.

On the other hand, water which forms lather with soap is called soft water.

The hardness which can be removed easily just by boiling is temporary hardness,
otherwise, it is called permanent hardness. Permanent hardness can be removed
through some appropriate physical or chemical methods.

The principle ions responsible for hardness are calcium (Ca2+) and magnesium
(Mg2+). Smaller quantities of other ions which cause hardness of water are iron
(Fe2+), manganese (Mn2+), strontium (Sr2) and aluminum (Al3+).
Hardness of water causes many problems. The reaction between hard water with
soap produces sticky, gummy deposit known as ‘soap curd’, a dirty ring around
the bathtub. Hard water, thus consumes lot of soap unnecessarily.

When hard water is heated, calcium carbonate (CaC03) and magnesium

hydroxide [Mg (OH) 2] precipitate out of the solution, forming rock like scale.
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The scale, in turn clogs hot water pipes and the efficiency of water-heaters,
boilers is reduced day by day, with increased amount of deposit. The cleaning of
such equipments is also costly.

Due to reduced efficiency, the heat transmission goes down increasing energy
consumption and also the equipment cannot last long. The unnecessary
consumption of such soap, along with formation of scaling, makes hard water
unsuitable for washing of clothes at home and in laundry.

Groundwater generally is harder (~ 300 mg/1) compared to surface water (~ 200

mg/1) and is termed as ‘soft’ water. Hardness is measured in mg/1 as CaC03. The
total hardness is taken as the sum of Ca2* and Mg2+ as they are the main
components causing hardness.
Hardness can be classified into two groups:
(i) Carbonate hardness:
In this case, the captions Ca2+ and Mg2 are associated with two anions C03 2” and
HC03~
(ii) Non carbonate hardness:
The captions Ca2+ and Mg2+ are associated with CP and S04 2“, P04 3“, etc.
The carbonate hardness is temporary hardness and it can be removed easily by
just boiling the water and is very important in the sense that the boiling leads to
formation of carbonate causing scaling.

Bicarbonate Carbonate:
For the removal of hardness two processes can be adopted (1) Lime soda process
(2) Ion exchange process.

Lime Soda Process:

In this process, quick lime (CaO) or hydrated lime (Ca [OH]2) is added to hard
water. The soluble bicarbonate of (Ca2+) is precipitated out as insoluble carbonate
and that of Mg2* as hydroxide.