LU 4 CHEMICAL WEATHERING

◊WEATHERING

Rocks of every sort and shape are worn away over time.

Weathering is the process that breaks rocks into smaller

bits/decomposes rocks.

TYPES OF WEATHERING

There are three main types of weathering:

1. Physical weathering:

This is physical action which breaks up rocks:

An example of this is called freeze-thaw weathering when water

gets into tiny cracks in rocks.
When the water freezes it expands, if this is repeated the crack
grows and bits eventually break off.

2. Chemical weathering:

This happens when the rock is chemically attacked:

An example of this is the breakdown of limestone by acid rain.

3. Biological weathering:

This happens when rocks are weakened and broken down by animals
and plants.

An example would be a tree root system slowly splitting rocks.

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 Weathering feedbacks: chemical and physical
• Physical weathering and
chemical weathering
generally proceed in parallel
in most environments.
• Physical and chemical
weathering promote one
another:
– Formation of cracks by
physical weathering allows
solutions to enter the rock
and increases reactive
surface area; this promotes
chemical weathering.
– Chemical weathering
replaces strong, intact
interlocking minerals with
weak clays or void space,
making the rock easier to
physically disaggregate, thus
promoting physical
weathering

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◊ FACTORS CONTROLLING RATES OF WEATHERING

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◊CHEMICAL WEATHERING

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This is the action of water, oxygen, CO2, acids etc. on rock.

Water is the main agent of weathering both by itself and by promoting

the action of other chemicals dissolved in it.

• the decomposition of rock by chemical reactions

• occurs in water, especially soil water and groundwater are rich in

dissolved carbon dioxide produced during the decomposition of
plants

Types of Reaction Mechanisms:

1. Carbonation:

Dissolving of calcium carbonate (limestone) in acidic groundwater

o all the products are ionic and there is no residue

o bicarbonate (HCO3-) is a product of carbonation and a major part

of the dissolved load of most rivers

2. Hydrolysis:

Mineral cations (e.g., Ca+, Fe+, Na+, K+, Al+) are replaced by
hydrogen ions (H+) from acidic water

o the most common weathering process

3. Oxidation:

Loss of an electron to dissolved oxygen

o iron is the most commonly oxidized mineral element Fe2+

(ferrous iron)

o other readily oxidized mineral elements include Mg, S, Al and

chromium.

Examples of the main types of chemical weathering

(Some available at www. Ul.ie/~ces/chemical_ weathering.htm):

1. Hydration/dehydration

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 (Binding of water molecules):

e.g. CaSO4(s) + 2H2O CaSO4.2H2O(s)

5Fe2O3 + 9H2O → Fe10O15 • 9H2O

Hematite Ferrihydrite

2. Dissolution

(Solution of soluble minerals):

e.g. Na2SO4(s) 2 Na+(aq) + SO42-(aq)

Dissolution - solubilization

e.g. CaSO4. 2H2O dissolution Ca2+ + SO42- + 4H2O

3. Oxidation

(Reaction with oxygen from air):

e.g. 2FeS2(s) + 7.5O2(g) + H2O -> 2Fe3+ + 4SO42- + 2H+

4. Oxidation-Reduction

(Loss/gain of electrons)

e.g. 4Fe + O2 + 2H2O -> oxidation -> 4FeOOH

← reduction ←

5. Hydrolysis

(Splitting of water molecule, reaction of H+ or OH- with a mineral)

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 e.g. KAlSi3O8 + HOH -> HAlSi3O8 + K+ +OH-
Microcline

2HAlSi3O8 + 11HOH -> Al2O3 + 6H4SiO4

6. Dissolution + hydrolysis

(Solution followed by reaction with water):

e.g.

CaCO3(s) + H2O -> Ca2+(aq) + HCO3-(aq) + OH-(aq)

MgSiO4(s) + 4CO2(aq) + 4H2O -> 2Mg(HCO3)2(aq) + H4SiO4(aq)

7. Complexation (metal complex formation):

by oxalate ion, humic acid etc.

e.g.

K2(Si6Al2)Al4O20(OH)4(s) + 6C2O42-(aq) + 20H-(aq) ->

Muscovite oxalate ion

6[Al(C2O4)]+ (aq) + 6H4SiO4(aq) + 2K+(aq)

metal complex

8. Carbonation

CO2 + H2O -> H2CO3

H2CO3 -> dissociation -> H+ + HCO3-

H2CO3 + CaCO3 -> carbonation -> Ca2+ + 2HCO3-

Weathering of Minerals:

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Action of Rainwater

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 Chapter 7: 3) Chemical weathering

See Fig. 7.6

See Fig. 7.6

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1. Quartz - slow process and largely ineffective.

Quartz remains quartz. Grains are rounded.

2. Feldspar –

Weathers to clay with the cations Na, Ca, and K going into
solution.

Clays that can form include kaolinite (pure aluminum silicate),

illite and montmorillonite.

Factors which dictate clay formation are (a) climate; (b) time; (c)
parent material.

3. Muscovite - Same as above

4. Ferromagnesian minerals –

Weather to clay plus highly insoluble iron oxides, essentially

varieties of limonite (rust).

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The weathering of iron-bearing silicate minerals, such as olivine
and pyroxene, are another class of important weathering reactions.

When iron-bearing silicates dissolve, they release ferrous iron

(Fe2+) into solution.

There the iron becomes oxidized to ferric iron (Fe3+) after which it
combines with oxygen and precipitates as the very insoluble
compound iron oxide or hematite (Fe3O4), which is red in color,
forms iron ores, and is responsible for the red color in many clays.

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◊FURTHER CHEMICAL REACTIONS

A. Dissolution

i) Congruent Dissolution:

Complete dissolution (congruent: no residue).

Halite, gypsum (CaSO4 .2H2O) or calcite dissolve completely in water.

+ –
NaCl  Na + Cl

Evaporite minerals commonly dissolve in pure water, e.g.,

Halite (NaCl) = Na+ and Cl-

Most commonly affected are limestones:

CaCO3 + H2O + CO2 = Ca2+ + 2HCO3-

(H2O + CO2 = H2CO3 = carbonic acid)

What is the source of the CO2?

• Atmospheric - rainwater.
• Biological activity - soil waters.

An equation for weathering of "generic" organic matter:

C106H263O110N16P+138O2 = 106CO2+16NO3+HPO4+122H2O+18H+

The organic matter is altered (commonly with the aid of microbes such
as bacteria and fungi), yielding CO2 to soil waters plus H- ions that
lower the pH.
What happens to quartz during weathering?

SiO2 + 2H2O = H4SiO4

Silicic acid (weak acid) is formed, but silica has low solubility in most
fluids except at high pH (> 9) and high temperature.

ii) Incongruent dissolution:

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Partial dissolution followed by recrystallization to new mineral.

Feldspars tend to undergo incongruent dissolution.

They lose some cations and silicon and end up as clay minerals e.g.,

Albite + Water  Kaolinite + H4SiO4 + K

More generally,

Feldspar + Water  Clay Mineral + H4SiO4 + K, Na, Ca

Clay minerals comprise the mineral component of soils, mud, and

ancient shales.

Handful of mud = handful of clays.

Without clay formation, we would have no soils to support plant life.

Surface of continents would not store the nutrients needed to support

life as we know it leading to a very barren planet.

B. Hydration

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This is the process by which ions are taken into solution...ions "attract"
water molecules:

Weathering of silicates commonly takes place by hydrolysis

C. Hydrolysis

This is a reaction of a silicate mineral with water (or acid dissolved in

water) that results in a loss of cations.

Feldspar dissolution is an example of hydrolysis.

The weathering of olivine and pyroxene also go (congruently) by

hydrolysis:

Mg2SiO4 (olivine)+ 4H+  2Mg2+ + H4SiO4

2CaMg2SiO6 (pyroxene) + 16H +  2Ca2+ + 2Mg2+ + 4H4SiO4

D. Oxidation

This is a reaction where elements in a mineral combine with oxygen.

4FeS2 (pyrite) + 3O2  2Fe2O3 (rust)+ 8S (sulfur gives a

yellowish color to rocks)
4FeS2 (pyrite)+ 19O2  2Fe2O3 (rust) + 8SO4-- (sulfate)

If calcite is dissolving, lots of Ca is available.

If water can evaporate (i.e. weathering is near the surface), CaSO4 will
precipitate. Nice gypsum crystals!

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