Geokimia

temu kedelapan
2013
Weathering:
decomposition and
disintegration of rock

Product of weathering
is regolith or soil

Regolith or soil that is

transported is called
sediment

Movement of
sediment is called
erosion
 Primary minerals
• Most rocks are composed of minerals that weather to a
degree. Most common are
• Silicates
– Neosilicate (olivine) (Fe-Mg)2SiO4
– Cyclosilicate (beryl, tourmaline)
– Chain/Iono (pyroxene & amphibole) (CaMg)2Si2O6
– Sheet/Phyllo (mica, kaolin, talc, chlorite)
KFeAlSi3O10(OH)
– Framework/Tecto (quartz & feldspar) K-Na-CaAlSi3O
– Glass (unstructured)
• Sulphides (pyrite, galena etc)
• Oxides (magnetite, rutile, spinel)
Observed Silicate Mineral Weathering Pathways in Soils

PRIMARY SILICATES SECONDARY MINERALS

NESOSILICATES smectite kaolinite gibbsite

silicon silicon silicon
opal
iron Si(OH)4

INOSILICATES Fe oxides
calcium
calcite
calcium
-K
PHYLLOSILICATES biotite trioctahedral trioctahedral
illite vermiculite
-K
muscovite dioctaheral dioctahedral
illite vermiculite

TECTOSILICATES plagioclase

feldspars

quartz
Si(OH)4

INCREASING DEGREE OF DESILICATION

 Products of Weathering

• Lithic (Rock) Fragments

(granite, basalt, schist, etc.)
• Dissolved Ions
(Calcium, Potassium, Sodium, etc.)
• Rust Minerals (Hematite, Goertite, etc.)
• Clay Minerals
(Bentonite, Montmorillonite, etc.)
• Residual Minerals
(Quartz, Orthoclase, Muscovite, etc.)
 Products of weathering

Clay minerals further decompose to aluminum hydroxides

(bauxite) and dissolved silica.
Chemical Weathering
 Types of regolith minerals
• Phyllosilicates or clay minerals
Smectites, kaolinite, illite, vermiculite & interstratified
varieties of these
• Silicates – Opal A & opal-CT, quartz
• Oxides & hydroxides – Fe, Mn, Al & Ti
Geothite, hematite, maghemite, gibbsite, lithiophorite,
pyrolusite
• Sulphates - Gypsum, jarosite, alunite
• Carbonates – Calcite, dolomite, magnesite, siderite
• Chlorides - Halite
• Phosphates – Crandalite, florencite
 Mineral weathering – what
does it involve?
The main processes achieved via mechanisms
such as hydrolysis, ion exchange, oxidation
• Replacement of more soluble ions by
protons (hydrolysis)
– K-feldspar + water > kaolinite + solutes
• Change of Al coordination from 4 to 6
(hydrolysis facilitated)
• Oxidation of Fe (oxidation)
Replacement of soluble ions by
protons (H)
Primary
• Feldspar (K,Na,Ca)AlSi3O8
• Pyroxene (Mg,Ca,Fe)SiO3
• Amphibole Ca2+, Na+, Mg2+ & K+
(Ca,Mg,Fe)Si8O22(OH)2
Released as solutes
• Olivine (Mg,Fe)2SiO4
• Mica (K,Fe)Al3Si3O10(OH)2

Secondary
• Kaolinite Al2Si2O5(OH) H+ & H2O
• Smectite
(Ca,Mg,Fe)AlSi3O10(OH)2.H2O
• Illite KAl3Si3O10(OH)2
• Goethite FeOOH
• Hematite Fe2O3
 Hydrolysis

Feldspar + carbonic acid +H2O

= kaolinite (clay)
+ dissolved K (potassium) ion
+ dissolved bicarbonate ion
+ dissolved silica

Clay is a soft,
platy mineral, so
the rock
disintegrates
 Hydrolysis
• Water combines with atmospheric and soil CO2 to form a weak
acid - carbonic acid> H2O + CO2  H2CO3; H2CO3  H+ +
HCO3-
• Metals in minerals are replaced or exchanged by H+ with cation
release as metal cation (K+, Ca2+, Na+ etc) and potential formation
of a new clay mineral (kaolinite, smectite etc) from retained ions
(Al3+, O2-, Si4+)
K-feldspar + H+  kaolinite + K+ + H4SiO4
• Ligand exchange is another variant, where ligand (oxalate)
enhances break up the Metal (M) – O bond and facilitates
replacement of M cation by H+ and OH-
• Ligand exchange via oxalates and other organic acids enables
dissolution of the insoluble Fe-Al oxides and hydroxides
Change of Al coordination on
weathering

Change from four fold (tetrahedral) to six-fold (octahedral) on weathering

 Oxidation of Fe (& Mn)
• Fe2+ in biotite, pyroxene,
olivine, pyrite
• Oxidation > higher charge
Fe3+, smaller ionic radii
• Fe3+ - combines readily with
O2- to form oxides and
hydroxides > goethite,
hematite, maghemite,
lepidocrocite, ferrihydrite
• Fine grained > reddish-brown
hues
 Oxidation
Oxidation can affect any
iron bearing mineral, for
example, ferromagnesian
silicates which react to
form hematite and limonite
 Oxidation
• Oxidation & reduction accomplished by electron
transfer
• Oxidation - loss of electrons
• Reduction -gain of electrons of ions
• Oxidation causes change in ionic radii – facilitates
bond breakage
• Commonly oxidized elements and visible in the
regolith are
– Fe2+  Fe3+ Mn2+  Mn3+ So  S6+
• Reduced Fe/Mn/S bearing minerals (olivines,
pyroxenes, sulphides) undergo oxidation
Mineral stability to weathering

A: Related to connectedness of tetrahedras

B: Does not always follow the above rule - unusual
geochemical conditions can reverse the trends!
 Fresh Granodiorite
Saprolite

Hb Bt

Fld
Soil B horizon Soil B horizon
 Pyroxene Wethering
Pyroxenes weather to smectite
+ goethite
Space is created, some Ca-Mg
lost, some Ca,Mg,Al,Si in
smectite, Fe in geothite

Secondary mineral assemblages

along cleavages – dissolution leaves
behind space – boxwork fabric
Plagioclase altering to Al-
smectite (incongruent)

Ca2Al2Si2O8 + H+ + H2O > Ca2+ + Al2Si2O5(OH)4

Mineral weathering – applications
• Silicate and carbonate weathering
– consumes acid (H+) > buffers acidity
– consumes water (hydrolysis) > extra salt in profile
– releases cations to solutes (groundwater) > changes composition of
groundwater along flow path and vertically

• Sulphide weathering & secondary iron oxide formation

– Generates acid within mine waste piles, tailings, underground &
open cut mines
– Results in formation of gossans (indicators of massive sulphides)

• Solutes can accumulate in lower parts of landscape – salts

(halite), oxides (ferricrete), silicates (smectite) & carbonates
(calcrete)
 Carbonate Geochemistry
• Low-temperature geochemistry
– Calcite and water; pH ~ 10, 12-15 ppm Ca++
• Effectively insoluble!
– Calcite, water, and air CO2; pH ~ 8.4, 50 ppm
• Very slow – like soil formation. The initial step.
– Calcite, water, and soil CO2; pH ~ 4-7, ~700 ppm
• H2O + CO2 → H2CO3 [carbonic acid] which dissociates to:
• H2CO3 → H+ + HCO3- and the proton reacts with calcite:
• CaCO3 (s) + 2H+ (aq) → Ca++ (aq) + CO2 (g) + H2O
Bioturbation – Biomechanical
Processes
• Burrowing invertebrates - earthworms, ants,
termites and vertebrates (mammals)
– Turn over huge amounts of regolith material which via
attrition reduces particle size
• Roots
– Penetrate rocks and weathered mantle and force apart
material – water access
• Tree fall
– Transfer subsurface rock and regolith to surface
– mixing and breakdown of material at surface
 Bioturbation in action
Tree fall moving and
breaking down sub surface
material

Termetaria recycling top

soil, quartz gravel and
branches
 Biochemical weathering
• Microbes & vegetation (rhizosphere) release organic
acids - facilitate hydrolysis of minerals – complex ions
within the mineral and help their release
– e.g. K release from biotite is faster
• Microbes and vegetation change solution pH that
strongly affects silicate & carbonate weathering by
– Microbial metabolism enhances regolith (especially
soil) CO2 levels – carbonic acid
– Produce acid and alkaline compounds that affect
solution pH
• Catalyze oxidation-reduction reactions of metals
 Some other processes..
• Fire or heat
– Forest fires – new minerals and transform soil
minerals
– Goethite + organic matter + heat = maghemite
– Calcium oxalate = calcite in plants
• Impacts
– Impacts vapourize and reduce size of rock and
surface materials
– Change the composition of material
– Regolith on the moon is mostly produced by
impacts!
 What changes accompany
rock weathering?
• Colour - from rock colour to grey, red or yellow
hues due to oxidation of iron (Fe2+ to Fe3+)
• Density - removal (decrease) or addition
(increases) of material; collapse (decrease) or
dilation (increase) of original materia
• Composition- mineralogical and chemical change
towards more stable forms - solubility of elements,
mineral susceptibility and secondary mineral types
• Fabric or texture - change from rock fabric to soil
fabric (development of new structures)
See you soon.......coz