Solution weathering

Weathering is the deterioration of rocks, soils and minerals as well as wood and artificial materials through contact with water, atmospheric gases, and biological organisms. Weathering occurs ''in situ'' (on site, with little or no movement), and so is distinct from erosion, which involves the transport of rocks and minerals by agents such as water, ice, snow, wind, waves and gravity.

Weathering processes are divided into ''physical'' and ''chemical weathering''. Physical weathering involves the breakdown of rocks and soils through the mechanical effects of heat, water, ice, or other agents. Chemical weathering involves the chemical reaction of water, atmospheric gases, and biologically produced chemicals with rocks and soils. Water is the principal agent behind both physical and chemical weathering, though atmospheric oxygen and carbon dioxide and the activities of biological organisms are also important. Chemical weathering by biological action is also known as biological weathering.

The materials left over after the rock breaks down combine with organic material to create soil. Many of Earth's landforms and landscapes are the result of weathering processes combined with erosion and re-deposition. Weathering is a crucial part of the rock cycle, and sedimentary rock, formed from the weathering products of older rock, covers 66% of the Earth's continents and much of its ocean floor.

Physical weathering

Physical weathering, also called mechanical weathering or ''disaggregation'', is the class of processes that causes the disintegration of rocks without chemical change.Physical weathering involves the breakdown of rocks into smaller fragments through processes such as expansion and contraction, mainly due to temperature changes. Two types of physical breakdown are freeze-thaw weathering and thermal fracturing. Pressure release can also cause weathering without temperature change. It is usually much less important than chemical weathering, but can be significant in subarctic or alpine environments. Furthermore, chemical and physical weathering often go hand in hand. For example, cracks extended by physical weathering will increase the surface area exposed to chemical action, thus amplifying the rate of disintegration.

Frost weathering is the most important form of physical weathering. Next in importance is wedging by plant roots, which sometimes enter cracks in rocks and pry them apart. The burrowing of worms or other animals may also help disintegrate rock, as can "plucking" by lichens.

Frost weathering

''Frost weathering'' is the collective name for those forms of physical weathering that are caused by the formation of ice within rock outcrops. It was long believed that the most important of these is ''frost wedging'', which results from the expansion of pore water when it freezes. However, a growing body of theoretical and experimental work suggests that ''ice segregation'', in which supercooled water migrates to lenses of ice forming within the rock, is the more important mechanism.

When water freezes, its volume increases by 9.2%. This expansion can theoretically generate pressures greater that , though a more realistic upper limit is . This is still much greater than the tensile strength of granite, which is about . This makes frost wedging, in which pore water freezes and its volumetric expansion fractures the enclosing rock, appear to be a plausible mechanism for frost weathering. However, ice will simply expand out of a straight, open fracture before it can generate significant pressure. Thus frost wedging can only take place in small, tortuous fractures. The rock must also be almost completely saturated with water, or the ice will simply expand into the air spaces in the unsaturated rock without generating much pressure. These conditions are unusual enough that frost wedging is unlikely to be the dominant process of frost weathering. Frost wedging is most effective where there are daily cycles of melting and freezing of water-saturated rock, so it is unlikely to be significant in the tropics, in polar regions or in arid climates.

Ice segregation is a less well characterized mechanism of physical weathering. It takes place because ice grains always have a surface layer, often just a few molecules thick, that resembles liquid water more than solid ice, even at temperatures well below the freezing point. This ''premelted liquid layer'' has unusual properties, including a strong tendency to draw in water by capillary action from warmer parts of the rock. This results in growth of the ice grain that puts considerable pressure on the surrounding rock, up to ten times greater than is likely with frost wedging. This mechanism is most effective in rock whose temperature averages just below the freezing point, . Ice segregation results in growth of ice needles and ice lenses within fractures in the rock and parallel to the rock surface, that gradually pry the rock apart.

Thermal stress

''Thermal stress weathering'' results from the expansion and contraction of rock due to temperature changes. Thermal stress weathering is most effective when the heated portion of the rock is buttressed by surrounding rock, so that it is free to expand in only one direction.

Thermal stress weathering comprises two main types, thermal shock and thermal fatigue. Thermal shock takes place when the stresses are so great that the rock cracks immediately, but this is uncommon. More typical is thermal fatigue, in which the stresses are not great enough to cause immediate rock failure, but repeated cycles of stress and release gradually weaken the rock.

Thermal stress weathering is an important mechanism in deserts, where there is a large diurnal temperature range, hot in the day and cold at night. As a result, thermal stress weathering is sometimes called insolation weathering, but this is misleading. Thermal stress weathering can be caused by any large change of temperature, and not just intense solar heating. It is likely as important in cold climates as in hot, arid climates. Wildfires can also be a significant cause of rapid thermal stress weathering.

The importance of thermal stress weathering has long been discounted by geologists, based on experiments in the early 20th century that seemed to show that its effects were unimportant. These experiments have since been criticized as unrealistic, since the rock samples were small, were polished (which reduces nucleation of fractures), and were not buttressed. These small samples were thus able to expand freely in all directions when heated in experimental ovens, which failed to produce the kinds of stress likely in natural settings. The experiments were also more sensitive to thermal shock than thermal fatigue, but thermal fatigue is likely the more important mechanism in nature. Geomorphologists have begun to reemphasize the importance of thermal stress weathering, particularly in cold climates.

Pressure release

''Pressure release'' or ''unloading'' is a form of physical weathering seen when deeply buried rock is exhumed. Intrusive igneous rocks, such as granite, are formed deep beneath the Earth's surface. They are under tremendous pressure because of the overlying rock material. When erosion removes the overlying rock material, these intrusive rocks are exposed and the pressure on them is released. The outer parts of the rocks then tend to expand. The expansion sets up stresses which cause fractures parallel to the rock surface to form. Over time, sheets of rock break away from the exposed rocks along the fractures, a process known as exfoliation. Exfoliation due to pressure release is also known as ''sheeting''.

As with thermal weathering, pressure release is most effective in buttressed rock. Here the differential stress directed towards the unbuttressed surface can be as high as , easily enough to shatter rock. This mechanism is also responsible for spalling in mines and quarries, and for the formation of joints in rock outcrops.

Retreat of an overlying glacier can also lead to exfoliation due to pressure release. This can be enhanced by other physical wearing mechanisms.

Salt-crystal growth

''Salt crystallization'' (also known as salt weathering, salt wedging or haloclasty) causes disintegration of rocks when saline solutions seep into cracks and joints in the rocks and evaporate, leaving salt crystals behind. As with ice segregation, the surfaces of the salt grains draw in additional dissolved salts through capillary action, causing the growth of salt lenses that exert high pressure on the surrounding rock. Sodium and magnesium salts are the most effective at producing salt weathering. Salt weathering can also take place when pyrite in sedimentary rock is chemically weathered to iron(II) sulfate and gypsum, which then crystallize as salt lenses.

Salt crystallization can take place wherever salts are concentrated by evaporation. It is thus most common in arid climates where strong heating causes strong evaporation and along coasts. Salt weathering is likely important in the formation of tafoni, a class of cavernous rock weathering structures.

Biological effects on mechanical weathering

Living organisms may contribute to mechanical weathering, as well as chemical weathering (see § Biological weathering below). Lichens and mosses grow on essentially bare rock surfaces and create a more humid chemical microenvironment. The attachment of these organisms to the rock surface enhances physical as well as chemical breakdown of the surface microlayer of the rock. Lichens have been observed to pry mineral grains loose from bare shale with their hyphae (rootlike attachment structures), a process described as ''plucking'', and to pull the fragments into their body, where the fragments then undergo a process of chemical weathering not unlike digestion. On a larger scale, seedlings sprouting in a crevice and plant roots exert physical pressure as well as providing a pathway for water and chemical infiltration.

Chemical weathering

Most rock forms at elevated temperature and pressure, and the minerals making up the rock are often chemically unstable in the relatively cool, wet, and oxidizing conditions typical of the Earth's surface. Chemical weathering takes place when water, oxygen, carbon dioxide, and other chemical substances react with rock to change its composition. These reactions convert some of the original ''primary'' minerals in the rock to ''secondary'' minerals, remove other substances as solutes, and leave the most stable minerals as a chemically unchanged ''resistate''. In effect, chemical weathering changes the original set of minerals in the rock into a new set of minerals that is in closer equilibrium with surface conditions. However, true equilibrium is rarely reached, because weathering is a slow process, and leaching carries away solutes produced by weathering reactions before they can accumulate to equilibrium levels. This is particularly true in tropical environments.

Water is the principal agent of chemical weathering, converting many primary minerals to clay minerals or hydrated oxides via reactions collectively described as hydrolysis. Oxygen is also important, acting to oxidize many minerals, as is carbon dioxide, whose weathering reactions are described as carbonation.

The process of mountain block uplift is important in exposing new rock strata to the atmosphere and moisture, enabling important chemical weathering to occur; significant release occurs of Ca²⁺ and other ions into surface waters.

Dissolution

Dissolution (also called ''simple solution'' or ''congruent dissolution'') is the process in which a mineral dissolves completely without producing any new solid substance. Rainwater easily dissolves soluble minerals, such as halite or gypsum, but can also dissolve highly resistant minerals such as quartz, given sufficient time. Water breaks the bonds between atoms in the crystal:

The overall reaction for dissolution of quartz is
:

The dissolved quartz takes the form of silicic acid.

A particularly important form of dissolution is carbonate dissolution, in which atmospheric carbon dioxide enhances solution weathering. Carbonate dissolution affects rocks containing calcium carbonate, such as limestone and chalk. It takes place when rainwater combines with carbon dioxide to form carbonic acid, a weak acid, which dissolves calcium carbonate (limestone) and forms soluble calcium bicarbonate. Despite a slower reaction kinetics, this process is thermodynamically favored at low temperature, because colder water holds more dissolved carbon dioxide gas (due to the retrograde solubility of gases). Carbonate dissolution is therefore an important feature of glacial weathering.

Carbonate dissolution involves the following steps:

:CO₂ + H₂O → H₂CO₃
:carbon dioxide + water → carbonic acid

:H₂CO₃ + CaCO₃ → Ca(HCO₃)₂
:carbonic acid + calcium carbonate → calcium bicarbonate

Carbonate dissolution on the surface of well-jointed limestone produces a dissected limestone pavement. This process is most effective along the joints, widening and deepening them.

In unpolluted environments, the pH of rainwater due to dissolved carbon dioxide is around 5.6. Acid rain occurs when gases such as sulfur dioxide and nitrogen oxides are present in the atmosphere. These oxides react in the rain water to produce stronger acids and can lower the pH to 4.5 or even 3.0. Sulfur dioxide, SO₂, comes from volcanic eruptions or from fossil fuels, can become sulfuric acid within rainwater, which can cause solution weathering to the rocks on which it falls.

Hydrolysis and carbonation

Hydrolysis (also called ''incongruent dissolution'') is a form of chemical weathering in which only part of a mineral is taken into solution. The rest of the mineral is transformed into a new solid material, such as a clay mineral. For example, forsterite (magnesium olivine) is hydrolyzed into solid brucite and dissolved silicic acid:

:Mg₂SiO₄ + 4 H₂O ⇌ 2 Mg(OH)₂ + H₄SiO₄
:forsterite + water ⇌ brucite + silicic acid

Most hydrolysis during weathering of minerals is ''acid hydrolysis'', in which protons (hydrogen ions), which are present in acidic water, attack chemical bonds in mineral crystals. The bonds between different cations and oxygen ions in minerals differ in strength, and the weakest will be attacked first. The result is that minerals in igneous rock weather in roughly the same order in which they were originally formed ( Bowen's Reaction Series). Relative bond strength is shown in the following table:

This table is only a rough guide to order of weathering. Some minerals, such as illite, are unusually stable, while silica is unusually unstable given the strength of the silicon-oxygen bond.

Carbon dioxide that dissolves in water to form carbonic acid is the most important source of protons, but organic acids are also important natural sources of acidity. Acid hydrolysis from dissolved carbon dioxide is sometimes described as ''carbonation'', and can result in weathering of the primary minerals to secondary carbonate minerals. For example, weathering of forsterite can produce magnesite instead of brucite via the reaction:

:Mg₂SiO₄ + 2 CO₂ + 2 H₂O ⇌ 2 MgCO₃ + H₄SiO₄
:forsterite + carbon dioxide + water ⇌ magnesite + silicic acid in solution

Carbonic acid is consumed by silicate weathering, resulting in more alkaline solutions because of the bicarbonate. This is an important reaction in controlling the amount of CO₂ in the atmosphere and can affect climate.

Aluminosilicates containing highly soluble cations, such as sodium or potassium ions, will release the cations as dissolved bicarbonates during acid hydrolysis:

:2 KAlSi₃O₈ + 2 H₂CO₃ + 9 H₂O ⇌ Al₂Si₂O₅(OH)₄ + 4 H₄SiO₄ + 2 K⁺ + 2 HCO₃⁻
:orthoclase (aluminosilicate feldspar) + carbonic acid + water ⇌ kaolinite (a clay mineral) + silicic acid in solution + potassium and bicarbonate ions in solution

Oxidation