Hydrogeochemical reactions and

groundwater compositions

S.N. Rai

Department of Earth Sciences

Indian Institute of Technology Roorkee
Roorkee 247 667
 Topics
• Key reactions of groundwater chemistry
• Oxidation-reduction reactions
• Ion exchange processes
• Micro-organism in groundwater
• Global and Indian standards
• Equilibrium and kinetics reaction
(Ref. book: Fundamentals of groundwater
By Franklin W. Schwartz/ Hubao Zhang
 Ion, anion, cations
• An ion is an atom or group of atoms in which the
number of electrons is not equal to the number
of protons, giving it a net positive or negative
charge.
• An anion is an ion that is negatively charged,
and is attracted to anode (positive electrode) in
the electrolysis)
• A cation has a positive charge and is attracted to
the cathode (negative electrode) during
electrolysis
 Groundwater Interaction with its surrounding
Generates various natural processes, products, and
conditions. Its moveability helps in self organizing the
effects of interaction within the flow system.

Three main types of interactions have been identified as

chemical, mechanical, and kinetic. Accordingly, the
processes of these interactions are classified as

 Chemical processes,
 Mechanical processes, and
 Kinetic or transport processes.
 Chemical processes

Chemical processes include

Dissolution,
Hydration,
Hydrolysis,
Oxidation/reduction,
Chemical precipitation, and
Base exchange.
 Dissolution
• Dissolution is the most effective processes
in groundwater chemistry and is considered
to be the first step in the chemical evolution
of water.

The degree of dissolution depends on

solubility of minerals, waters concentration,
and ambient pressure and temperature
conditions.
 Hydration

• Hydration is the process of water

penetration into the crystal lattice of
minerals or the attachment of water
molecules to the ions of dissolved
salts. It plays an important role in the
weathering of minerals such as
anhydrite to gypsum, or biotite to
vermiculite.
 Hydrolysis (or Acid-Base reactions)

• Hydrolysis is reaction of any substance with water

in which some of the produced ions are either
removed from the solution or added to it. The
hydrolysis of cations produces acidic solutions
whereas hydrolysis of anion results in basic
solutions.
• Acidic Water - pH<7; neutral- pH=7, basic- pH>7
• At low pH waters are capable of carrying a large
load of dissolved metals
• At high pH, the metals tends to precipitate as
solid.
 Oxidation/reduction
• Oxidation/reduction reactions are chemical reactions in
which electrons are transferred from one atom to another.
These reactions are important in controlling the geo-
chemistry of natural waters.
Oxidation is the result of a loss (or removal) of free
electrons by the substance being oxidized. For example
2
oxidation of Fe can be written as
2 3 
Fe  Fe e
Important oxidation processes include the oxidation of
sulfides, producing FeSO3, H2SO4 and CO2 with acids. The
attack by acids on rocks contributes to the chemical
evolution of groundwater.
 Reduction

Reduction is the gain of free electrons by

the reduced substance. For example
3 1 2
Fe  e  Fe
 Chemical precipitation
• Chemical precipitation of mineral matter dissolved
in water may occur because of:

(1) reaction with ions from the solid framework to

form insoluble precipitates, and

(2) change in pressure and temperature affecting

the solubility of certain chemical constituents in
water, etc. and oxidation of dissolved matter
exposed to air resulting in components having
decreased solubility.
 Ion exchange or Base exchange
• Ion exchange is the process in which ions and molecules
absorbed loosely on the surface of solid substances by
physical or chemical forces are exchanged for ions in the
water. This kind of exchange can result in dramatic change
in the chemistry of water. The most important substances
capable of ion exchange are clay minerals.
• Relatively high concentrations of Ca+Mg make the ground
hard. An example of ion exchange is the natural water
softening reactions that exchange Ca and Mg ions in the
water with Na ions sorbed on to clay mineral. The
exchange process effectively replaces Ca+Mg with Ca
which soften the water. These reactions are written as
Ca 2  Na  clay  2 Na  Ca  clay
Mg 2  Na  clay  2 Na  Mg  clay
 Physical Processes
• Pore-pressure change is the most important
physical processes affecting many
geological phenomena. Reductions or
increases in pore pressures affect the
magnitude and direction of groundwater
velocity, which ultimately affect the type,
rate, and direction of chemical reactions, the
solubility of minerals, etc.
 Kinetic Processes
• A wide variety of matter in many different
forms such as aqueous solutions of organic
and inorganic ions, matter in colloidal form
or larger-sized suspended grains, gases,
molecules of liquid hydrocarbons, viruses
and bacteria are transported by
groundwater movement.
 Equilibrium and Kinetic Reaction
It’s concept provide a basis for treating chemical reaction.
The law of Mass action
Consider the following reaction where ions C and D react to
produce ions Y and Z
cC + dD = yY + zZ
with c, d, y and z representing the number of moles of these
constituents.
The mole is widely used in chemistry instead of units of mass or
volume as a convenient way to express amounts of reactants or
of products of chemical reactions. For example, the chemical
equation 2 H2 + O2 → 2 H2O implies that 2 mol of dihydrogen
(H2) and 1 mol of dioxygen (O2) react to form 2 mol of water
(H2O).
 Law of Mass action
For a dilute solution, the law of mass action describes the
equilibrium distribution of mass between reactant and produce
as (Y ) y ( Z ) z
K 
(C ) c ( D) d
where K is the equilibrium constant and (Y),(Z),(C), and (D)
are the molal (or molar) concentrations for reactants and
products.
Molar concentration represents the number of moles of a species
per liter of solution (mol/L).
A mole is the formula weight of a substance expressed in gram.
For example, a one liter solution containing 1.42 g of Na2 SO4
has a Na2 SO4  molarity of 1.42/(2x22.99+32.06+4x16), or
0.010M. Because Na 2 SO4 dissociates completely in water as
2
Na2 SO4  2 Na   SO4 . In this reaction one mole of Na2 SO4
 2
Dissolve to produce two mole of Na and one mole of SO4 .
 Law of Equilibrium

• When a reaction is at equilibrium in closed

system, there is no chemical energy
available to alter the relative distribution of
mass between the reactants and products
in a reaction. Away from equilibrium,
energy is available to spontaneously drive
a system towards equilibrium by allowing
the reaction to progress.
WHO RECOMMENDED GUIDELINES FOR PHYSICAL AND CHEMICAL PARAMETERS OF
DRINKING WATER IN INDIA
Characteristics Acceptable

pH 7.0 to 8.5

Total dissolved solids mg/l) 500

Total hardness (as CaC03) (mg/l) 200

Chlorides (as CI) (mg/l) 200

Sulphates (as S04) (mg/l) 200

Fluorides (as F)mq/l 1.0

Nitrates (as NO2 (mg/l) 45

Calcium (as Ca) mg/l 75

Magnesium (as Mg) (mg/l) 30

Iron (as Fe) (mg/l) 0.1

Manqanese (as Mn) (mg/l) 0.05

Copper (Cu) (mg/l) 0.05

Aluminium (as AI) (mg/l) 0.03

Alkalinity (mg/l) 200

Residual Chlorine (mg/l) 0.2

Zinc (as Zn) (mg/l) 5.0

Phenolic compounds (as Phenol)(mg/l) 0.001

Anionic detergents (mg/l) (As MBAS) 0.2

Mineral Oil (mg/l) 0.01

 TOXIC MATERIALS

Arsenic (as As) (mg/l) 0.01

cadmimum (as Cd) (mg/l) 0.01

Chromium (as hexavalent Cr) (mg/l) 0.05

Cyanides (as CN) mg/l) 0.05

Lead (as Pb) (mg/l) 0.05

Selenium (as Se) (mg/l) 0.01

Mercury (total as Hq) (mg/l) 0.001

 Mole
Mole is a unit of measurement used in chemistry to express amounts of a chemical
substance, that contains as many elementary entities
(e.g., atoms, molecules, ions, electrons) as there are atoms in 12 grams of
pure carbon-12 (12C), the isotope of carbon with relative atomic mass of exactly 12
by definition. This corresponds to the Avogadro constant, which has a value
of 6.02214129(27)×1023 elementary entities of the substance. It is one of the base
units in theInternational System of Units; it has the unit symbol mol and corresponds
with the dimension symbol N. The mole is widely used in chemistry instead of units of
mass or volume as a convenient way to express amounts of reactants or of products
of chemical reactions. For example, the chemical equation 2 H2 + O2 → 2 H2O
implies that 2 mol of dihydrogen (H2) and 1 mol of dioxygen (O2) react to form 2 mol
of water (H2O). The mole may also be used to express the number of atoms, ions, or
other elementary entities in a given sample of any substance. The concentration of a
solution is commonly expressed by its molarity, defined as the number of moles of
the dissolved substance per litre of solution.
• The number of molecules in a mole (known as Avogadro's constant) is defined such
that the mass of one mole of a substance, expressed in grams, is exactly equal to
the substance's mean molecular mass. For example, the mean molecular mass of
natural water is about 18.015, so one mole of water is about 18.015 grams. Making
use of this equation considerably simplifies many chemical and physical
computations.