ChemicalWeathering

RawMaterials To understand chemical weathering, we need to understand some of the reactions that can occur in the Earth-surface environment. In general, the 'raw materials' for these reactions are: oxygen, carbon dioxide and other gases from the atmostphere; water from rain and snow; and minerals.

Reactionsin the atmosphere Even before rain hits the Earth's surface, one reaction that is important for weathering has occurred. That is a reaction between water and carbon dioxide to produce carbonic acid. In a typical raindrop, carbon dioxide and water are perpetually joining and separating so that some of the carbon dioxide always exists as separate molecules and some of it exists in carbonic acid. Click here for details of the reaction. That reaction is not the end of the story for carbonic acid. It is involved in another reaction, producing hydrogen ions. (An ion is an atom or group of atoms that has an excess or deficiency of electrons, resulting in a negative or positive electric charge.) This is also an equilibrium. Rainwater that has dissolved carbon dioxide from the atmosphere will always contain some hydrogen ions. The hydrogen ions are very important because they are very reactive and can attack many minerals. Water with added hydrogen ions is described as acid. All rain is acid, to some extent, because of dissolved carbon dioxide. When we speak of 'acid rain', however, we are usually describing rain that has had its aciditity artificially increased by pollution. One common way that this happens is when sulphur dioxide from industrial operations is added to the atmosphere. Sulphur dioxide reacts with water to produce more hydrogen ions than carbon dioxide. It significantly acidifies rainwater in areas affected by sulphur dioxide pollution.

ChemicalWeatheringby Solution Pure water is effective at dissolving some minerals. The result is known as a solution . For example, the mineral halite (the main component of rock salt and ordinary table salt) consists entirely of sodium and calcium ions. When exposed to water, these ions stick to water molecules as a result of their electric charge and the mineral is dissolved. Rock salt is not a common rock type at the Earth's surface. Much more common

Sink hole near Stephenville, western Newfoundland is limestone, a rock composed of the mineral calcite. Calcite also weathers by solution, but it weathers faster in water that is acid. That is because hydrogen ions react with the calcite. Click here to see the details of the reaction. The end result of this reaction is that calcium ions and bicarbonate ions (negatively charged groups of carbon, oxygen and hydrogen atoms) enter the water in solution and solid rock is entirely dissolved. This is the main mechanism of the weathering of most limestones. Landscapes that have limestone in the bedrock often show features produced where the bedrock has been dissolved by water, such as sink holes. The enormous sink hole in this photograph has been formed by solution in limestones of western Newfoundland, near Stephenville. Note the trees near the edge of the sinkhole for scale. We will revisit solution processes in a later module that deals with groundwater. Next, let's look at some other types of chemical reaction during weathering.

ChemicalWeatheringof Silicates

Acids play a role in the weathering of many silicate minerals. Our most typical example is the weathering of feldspar given in your textbook. Feldspars, generally, are the most abundant group of minerals in igneous rocks and probably in the Earth's crust as a whole, so this is a good representative example. Click here to see the details of the chemical reaction. This type of reaction is called a hydrolysisreaction . Hydrolysis means 'splitting up with water'. It is a typical reaction in the weathering of silicates because it produces both a dissolved product (K+ ions) and a new mineral (a clay mineral). The equations shown in the separate windows here are looking increasingly

Photograph of rust-stained outcrop produced by oxidation weathering of iron-rich rock near Trout River, western Newfoundland complicated. Do you need to learn them by heart? No. The main purpose of showing the equations here is to illustrate where the atoms go during the reactions.

ChemicalWeathering:Oxidation Another gas from the atmosphere that has an effect on weathering is oxygen . Oxygen makes up about 20% of the Earth's atmosphere at present and consists largely of molecules containing two oxygen atoms (O 2). In weathering environments, the element that is most susceptible to oxidation is iron (Fe). In most of the minerals common in igneous and metamorphic rocks,

the iron occurs as Fe2+ ions (the iron has already lost two electrons). Iron can, however, lose a third electron by reacting with oxygen. This type of reaction usually requires the presence of water. The products include hydrated iron oxide, also known as limonite . This is an orange-brown material that is identical to rust. Click to see the chemical changes involved in this oxidation process.

Over time (typically millions of years), hydrated iron oxide loses its water to produce the red mineral hematite (Fe2O3). Thus, environments in which oxidation of iron is taking place at the present day typically show rustcoloured staining, whereas ancient environments in which iron was oxidized can Ancient sandstones and shales stained red by hematite, indicating probable deposition in oxidizing generally be recognized conditions from the presence of red coloration, due to hematite. Another oxidation reaction that has major impacts in parts of Atlantic Canada is the oxidation of the iron sulphide mineral pyrite.

What happens here is that both the iron and the sulphur in pyrite FeS 2 are oxidixed. The iron and some of the water end up in rust-coloured hydrated iron oxide and the sulphur ends up as sulphuric acid. Sulphuric acid is a strong acid which generates high concentrations of hydrogen ions when dissolved in water. Click to see the details of the reaction. This reaction takes place slowly in natural environments in southern Nova Scotia wherever the pyrite-rich Halifax Formation is exposed. If bedrock is dug up and fresh, unweathered pyrite is suddenly exposed to weathering, large amounts of acid are produced. This acid may seriously contaminate rivers and lakes. To avoid this type of 'acid drainage' problem, some municipalities (including Halifax) limit the use of freshly quarried bedrock in landscaping and building operations.

ChemicalWeathering:MineralStability The strength of the bonds between atoms are dependent on the pressure and temperature. The minerals that form in igneous rocks have arrangements of atoms that are stable at the kinds of temperatures that exist in a solidifying magma, typically between 600 and 1100C. In many minerals, these arrangements of atoms are no longer very stable if the temperature is reduced to near 0C and water is supplied during exposure at the Earth's surface. Given the opportunity, the atoms will re-arrange themselves to make new minerals, such as the clay minerals described in the paragraphs above.

Sandy beach at Cape Sable Island, Nova Scotia (the rocks in the nearby outcrops contain more feldspar than quartz, but the sand on the beach is mostly quartz) Because chemical weathering depends on these stability relationships between minerals, we can make some generalizations about which minerals survive best during chemical weathering. In general, it is the minerals which formed at lower temperatures (particularly quartz) that survive chemical weathering for the longest times. Quartz is particularly durable because it is a hard mineral without strong cleavage. Therefore, it tends to survive mechanical weathering, as well. In contrast, a mineral such as olivine, which crystallizes at very high temperature, is particularly unstable at the Earth's surface and undergoes rapid chemical weathering. For this reason, when we look at sediments (at sandy beaches on our coasts, for example), we typically find that most of the sand grains are quartz. It is common to find a proportion of feldspar and mica grains, as well, but high-temperature

silicates like olivine and pyroxene have usually completely broken down long before sediment reaches the coast. This is only a general rule. Some high temperature minerals (such as the zircon grains that are used in isotopic dating, for example) also survive well at the Earth's surface

5) Weathering
5.1) Physical Weathering 5.2) Chemical Weathering 5.3) Biological Weathering 5.4) Weathering Resistance

Further Reading: Birkeland P.W. 1984. Soils and Geomorphology. New York, Oxford University Press. Nahon D.B., 1991. Introduction to the Petrology of Soils and Chemical Weathering. John Wiley & Sons, Inc., New York. Robinson D.A., and Williams R.B.G., 1994. Rock Weathering and Landform Evolution. John Wiley & Sons, Inc., New York. xxxback to:xxx Main Pagexxx Table of Contentsx xxxxxxxxxxxxxxxxxxxxxxx 4) Primary Mineral Components of Soils xxxforward to:xxx 6) Silicates

5.1) Physical Weathering

Weathering in general refers to a group of processes by which surface rock disintegrates into smaller particles or dissolve into water due to the impact of the atmosphere and hydrosphere. The weathering processes often are slow (hundred to thousands of years). The amount of time that rocks and minerals have been exposed at the earth's surface will influence the degree to which they have weathered. Weathering processes are divided into three categories:

physical weathering chemical weathering biological weathering

Primary minerals and rocks are splitted in fragments due to physical weathering. This leads to environmental conditions (e.g. a higher surface area) that favor chemical weathering. There are several forms of physical weathering: Abrasion: Water carrying suspended rock fragments has a scouring action on surfaces. Examples are the grinding action of glaciers, gravel, pebbles and boulders moved along and constantly abraded by fast-flowing streams. Particles carried by wind also have a 'sand-blasting effect'. Wetting and drying: Water penetrates into rocks and reacts with their constituent minerals. Freezing and thawing: When water is trapped in the rock (or in cracks) repeatedly freezing and thawing results in forces of expansion and contraction (when water freezes, the increase in its volume is about 9 %). Thermal expansion and contraction of minerals: Rocks are composed of different kind of minerals. When heated up by solar radiation each different mineral will expand and contract a different amount at a different rate with surface-temperature fluctuations. With time, the stresses produced are sufficient to weaken the bonds along grain boundaries, and thus flaking of fragments. For instance, the difference in temperature in desert environments or mountain regions may range from 30 - 50 degrees C between day and night. Rocks are heated and cooled from the outside by change in solar radiation, which results in high temperature gradients inside and outside of the rocks (the heat conductivity of rocks is very low). Pressure unloading or pressure-release jointing: There is a reduction in pressure on a rock due to removal of overlying material. This allows rocks to split along planes of weakness, called joints. Crystallization: In arid environments, water evaporates at the surface of rocks and crystals form from dissolved minerals. Over time, the crystals grow (They expand their volume) and exert a force great enough to separate mineral grains and break up rocks. Action of organisms: They aid in the physical disintegration of rocks.

Plant roots: They aid in the physical disintegration of rocks. Pressures exerted by roots during growth are able to rupture rocks.

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5.2) Chemical Weathering

The difference between physical and chemical weathering is that with the latter one the mineral composition of the mineral or rock is changed. The larger the surface area, i.e, the smaller the fragments, the better for chemical weathering. Water is the dominant agent because it initiates chemical weathering. In the following there is a brief description of the most important chemical weathering processes: Hydration: Ions have the tendency to hydrate when H O is present and dissociate. This kind of weathering happens in arid environments where salts are present. For example, chlorides and sulfates weather due to hydration. In general, ions with the same charge but smaller ion radius have a larger layer of H O ions and therefore do not tend to adsorb tight. The small Li ion tends to remain hydrated at the surface, whereas the large Al ion tends to dehydrate and become tightly adsorbed. The strength of adsorption increases in the following sequence:
2 2 + 3+

Li x
+

x Na x
+

xK x
+

x Mg x
2+

x Ca x
2+

xAl

3+

Hydrolysis: Water molecules at the mineral surface dissociate into H and OH and the mobile H ions (actually H O ) penetrate the crystal lattice, creating a charge imbalance, which causes cations such as Ca , Mg , K and Na to diffuse out. For example, the feldspar orthoclase hydrolyses to produce a weak acid (silicic acid), a strong base (KOH), and leaves a residue of clay mineral illite, which is a secondary mineral:
+ + 3 + 2+ 2+ + +

3KAl + Si O + 14H O <- -> K(AlSi ) Al O (OH) + 6Si(OH) + 2KOH

4 3 8 2 3 4 2 4 10 2 4

In hydrolysis reactions it has to be taken into account the important role played by dissolved CO . This is shown in the hydrolysis of Mg-olivine:
2

Mg SiO + 4CO + 4H O <- -> 2Mg + 4HCO + H SiO

2 4 2 2 2+ 3 4

This reaction uses an acid (carbonic acid - H CO )and therefore the solution becomes increasingly alkaline during completion of hydrolysis reactions.
2 3

Oxidation-Reduction: Several primary minerals contain Fe and Mn . If there are oxidizing environmental conditions the Fe is oxidized to Fe (precipitates as an insoluble oxyhydroxide, usually either ferrihydrite or the stable mineral goethite) and Mn to Mn or Mn partly inside the minerals, which results in a positive charge and the mineral becomes unstable. This charge imbalance is neutralized by a loss of some oxidized iron and manganese ions and/or some cations dissociate from the mineral. The precipitate may form a coating over the mineral surface, which slows down the subsequent rate of hydrolysis. Note that the oxidation of Fe to Fe according to:
2+ 2+ 2+ 3+ 2+ 3+ 4+ 2+ 3+

Fe + 2H O + 1/2O < - -> Fe(OH) + H

2+ 2 2 3

is an acidifying reaction (acid solution weathering). The H ions produced by this reaction will generally accelerate the rate of hydrolysis.
+

Complexation: Metals released from primary minerals such as Fe, Mn, and Al, build complexes with organic components, such as fulvic acids and humic acids, which are very stable. Important referring to chemical weathering is the loss of the cations out of the active system, therefore causing an imbalance between cations and anions.

Figure 5.2.1. Chemical weathering processes.

Summary Weathering of primary minerals produce secondary minerals. Elements released from primary minerals are prone to leaching if they do not form complexes. The area of weathering is depleted first by Na , Ca , and Mg .
+ 2+ 2+