Mineral-Mineral Silikat

Classification of Minerals
Classification of Minerals by Chemical Composition: Dana's System of Mineralogy (and its derivatives) ca. 15 major groups of minerals with a few important subgroups
named according to dominant anion or anionic group by far the most important group is the silicates - 6 subgroups based on crystal structur New Danas minerals classifiation (www.webmineral.com)
Minerals
Chemical Properties Physical Properties
Minerals
chemical composition + crystal structure
Optical Properties
Mineral Classification
CRYSTAL CHEMICAL CLASSES (Dana's System of Mineralogy) 1. native elements 2. sulphides, arsenides, tellurides 3. sulphosalts 4. simple oxides 5. hydroxides 6. multiple oxides 7. halides 8. carbonates 9. borates 10. sulphates 11. chromates 12. phosphates, arsenates, vanadates 13. vanadium oxysalts 14. molybdates, tungstates 15. SILICATES: 6 different subclasses based on crystal structure
Behavior of elements: Goldschmidts classification
Elements divided into four broad categories:
Lithophile
generally found within crust and mantle Concentrate in silica-rich melts
Siderophile
Generally concentrate in ironrich melt
Chalcophile
Generally occurs with sulfur
Atmophile
Generally found in the atmosphere
Most Common Elements of Earths Crust

Oxygen: Silicon: Aluminum: Iron: O-2 Si+4 Al+3 Fe+2 or +3 Calcium: Ca+2 Sodium: Na+1 Potassium: K+1 Magnesium: Mg+2
Plate tectonics: Mixing crust and mantle

Reference book: This Dynamic Earth by USGS http://pubs.usgs.gov/publications/text/dynamic.ht ml
Earths crust and mantle are rich in lithophile elements (those that concentrate in a silica-rich melt)
All types of magma contain silicon and oxygen as silica (SiO2) in different amounts (~40 -70%) Igneous rocks are almost exclusively made up of SILICATE minerals Containing the (SiO4)-4 anionic group
Silicate minerals
Contain the (SiO4)-4 anionic group Make up 95% of the continental crust, and almost all of the oceanic crust and the mantle
Mineral Groups
Non-ferromagnesian Silicates (K, Na, Ca, Al)
Ferromagnesian Silicates (Fe, Mg)
Oxides Carbonates Sulfides/sulfates Native elements
Silicate Nomenaclature
Silicate Subclass
Neso (or Ortho) Silicates Sorosilicates Cyclosilicates Inosilicates Phyllosilicates
Alternative Name
Island Couplet Ring Chain Layer
15
Tectosilicates (or Tekto-) Framework
Element of Mineral Silicates Structure

Silicate tetrahedron: the single most important structural element
in minerals
space-filling view
expanded ("stick") view
co-ordination polyhedron
Nesse Fig. 11.1
[SiO4]4-
top view schematic:
basal view
Sharing of Oxygen Anions
17
Mineral Structures
Silicates are classified on the basis of Si-O polymerism
[SiO4]4Independent tetrahedra Nesosilicates/ Othosilocates
Examples: olivine garnet
[Si2O7]6-
Double tetrahedra
Sorosilicates/ Disilicates
Examples: lawsonite
n[SiO3]2- n = 3, 4, 6
Cyclosilicates/ Ring Silicates
Examples: benitoite BaTi[Si3O9] axinite Ca3Al2BO3[Si4O12]OH beryl Be3Al2[Si6O18]
Mineral Structures
[SiO3]2- single chains pryoxenes pyroxenoids
Inosilicates
[Si4O11]4Double tetrahedra amphiboles
Mineral Structures
[Si2O5]2Sheets of tetrahedra micas talc clay minerals serpentine
Phyllosilicates/ Sheet Silicates
Mineral Structures
low-quartz
[SiO2]
3-D frameworks of tetrahedra: fully polymerized
Tectosilicates/ Framework Silicates
quartz and the silica minerals feldspars
feldspathoids zeolites
Nesosilicates
Characterized by independent Si04 tetrahedra, which are not linked together directly They are bonded together by ionic bonds to interstitial cations The structures of the nesosilicates are therefore, very dependent on the size and charge of the interstitial cations Because the tetrahedral do not share oxygen, the Si:0 ratio is 1:4.
Interstitial Cations
Since the SiO4 tetrahedron has a charge of 4, two divalent cations, a trivalent and a monovalent, or a quadravalent cation are required to maintain electrical neutrality Several structure types are possible in the silicate structures the letter A = non-silicon cations with lower valency then Si4+ , B = Si or Al or other higher valent cations, O = oxygen
Mineral Structures
Nesosilicates: independent SiO4 tetrahedra
Olivine Structure: (Mg,Fe)2SiO4

b
projection
Olivine (100) view blue = M1 yellow = M2

b
perspective

b
M1 in rows and share edges
M2 form layers in a-c that share corners

Some M2 and M1 share edges
M1 and M2 as polyhedra
Representing mineral structures: space-filling view

Mg2+
expanded (stick) view
Si4+ olivine: Mg2SiO4

(orthosilicate)
Nesse Fig 4.9
O2-
Mg2+ Si4+ O2-
atomic radius () 0.72 0.26 1.40
CN
Representing mineral structures: co-ordination polyhedra tetrahedra
polyhedra + sticks
Mg2+ octahedra SiO4atomic radius () 0.72 0.26 1.40
olivine: Mg2SiO4
(orthosilicate)
Nesse Fig 4.9
Mg2+ Si4+ O2-
CN 6 4
Representing mineral structures:

distances between atoms shown as % unit cell dimensions
(distances along a, b, c crystallographic axes)

0 = bottom 100 = top 50 = half-way
olivine: Mg2SiO4
(orthosilicate)
Nesse Fig 4.9
Mg2+ Si4+ O2-
atomic radius () 0.72 0.26 1.40
CN 6 4
Look familiar?
Olivine
Light to dark green Really hard (6.5-7)
Olivine Series
Olivine itself is the compound (Fe, Mg)2 Si04 with a complete solid solution series As with other solid solution series the two end members are the most important
Fayalite Fe2Si04 Fa Forsterite Mg2Si04 Fo
Olivine Solid Solution Ranges
Forsterite Chrysolite Hyalosiderite Mortonolite Ferrohortonolite Fayalite
0-10% Fe 10-30% Fe 30-50% Fe 50-70% Fe 70-90% Fe 90-100% Fe
Solid Solution Nomenclature
As with some other important series an abbreviation is used for the end members compositions can be expressed using abbreviated symbols Example Fe0.6Mg1.4Si04 = Fa30 Fo70
Other Olivine Group Minerals
CaMgSi04 Mn2Si04 CaMnSi04 CaFeSi04
Monticellite Tephroite Glaucochroite Kirschsteinite

Olivine Occurrences:
Principally in mafic and ultramafic igneous and meta-igneous rocks Fayalite (Fe2SiO4) in meta-ironstones and in some alkalic granitoids Forsterite (Mg2SiO4) in some siliceous dolomitic marbles
Monticellite CaMgSiO4
Ca M2 (larger ion, larger site) High grade metamorphic siliceous carbonates

Garnet: A2+3 B3+2 [SiO4]3 Pyralspites - B = Al Pyrope: Mg3 Al2 [SiO4]3 Almandine: Fe3 Al2 [SiO4]3 Spessartine: Mn3 Al2 [SiO4]3 Ugrandites - A = Ca Uvarovite: Ca3 Cr2 [SiO4]3 Grossularite: Ca3 Al2 [SiO4]3 Andradite: Ca3 Fe2 [SiO4]3
Occurrence: Mostly metamorphic Some high-Al igneous Also in some mantle peridotites
Garnet (001) view blue = Si purple = A turquoise = B

Garnet: A2+3 B3+2 [SiO4]3 Pyralspites - B = Al Pyrope: Mg3 Al2 [SiO4]3 Almandine: Fe3 Al2 [SiO4]3 Spessartine: Mn3 Al2 [SiO4]3 Ugrandites - A = Ca Uvarovite: Ca3 Cr2 [SiO4]3 Grossularite: Ca3 Al2 [SiO4]3 Andradite: Ca3 Fe2 [SiO4]3
Occurrence: Mostly metamorphic
Pyralspites in meta-shales Ugrandites in meta-carbonates
a2 a1 a3
Some high-Al igneous Also in some mantle peridotites
Garnet (001) view blue = Si purple = A turquoise = B
Garnets, A3B2(SiO4)3
Larger A site is occupied by divalent cations which are relatively large, with a coordination number of VIII
Typical cations are Ca2+, Mg2+, Fe2+, Mn2+, and some trivalent lanthanides
The smaller B site is occupied by trivalent cations which are smaller, with a CN of VI
Typical cations A13+, Cr3+, Fe3+, and Ti4+
Calcium and Noncalcium Garnets
Ca2+ is larger than Mg2+, Fe2+ and Mn2+ Garnets can be split into two groups, the Ca and non-Ca garnets A similar division may be made for the B ions into A1, Fe3+ and Cr3+ garnets.
Ca Garnets
Name
Uvarovite
Formula
Ca3Cr2(Si04)3
Color
Emerald green White green, yellow, cinnamon brown, pale red Yellow, green, brown, black
Grossularite, also Ca3A12(Si04)3 called cinnamon stone, essonite Andradite Ca3Fe2(Si04)3
Non-Ca Garnets
Name
Pyrope Almandine Spessartite
Formula
Mg3A12(Si04)3 Fe3A12(Si04)3 Mn3A12(Si04)3
Color
Deep red to black Deep red to brown Brownish to red
Garnet Photos
Uvarovite Garnet (above)
Grossular garnet (above) Grossular, variety hessonite (left)
Garnet Photos
Andradite garnet (above)
Almandine garnet (left and right)
Garnet Ca3Al2(SiO4)3
Aluminosilicates
Aluminosilicates have aluminum in addition to silicon in the structure They may belong to any silicate subclass
Al2SiO5 Polymorphs
Kyanite, andalusite, and sillimaite have the same chemistry, but form under different P and T conditions
Al2SiO5 Structures
Topaz
A12 (Si04)(F, OH)2 H=8 {001} perfect Used as a gem stone
Staurolite

Fe2A1906(Si04)4(O,OH)2 Crystals are prismatic Often twinned (penetration twins), with two varieties of cruciform twins
Titanite

CaTiO(Si04) Formerly known as sphene An example of a titanosilicate N = 1.91 luster resinous to adamantine
Willimite
Zn2SiO4 Associated with other Zn ores Mn may replace Zn Often fluorescence
Willemite with Franklinite and Quartz New Jersey
54
Sorosilicates
Characterized by two Si04 tetrahedra joined through a single oxygen to give an Si:O ratio of 2:7
Sorosilicates
Characterized by two Si04 tetrahedra joined through a single oxygen to give an Si:O ratio of 2:7
Sorosilicates
schematic disilicate structure (e.g., epidote)
1 shared oxygen
how many Si atoms? 2 how many O atoms? 7 chemical formula? [Si2O7] net charge? -6
Nesse Fig. 11.2
Epidote Group
Contains both Si04 and Si207 groups General formula is X2VIIIY3VI(Si04)O(OH) X = Ca2+, Na+ Y = A13+, Fe3+, Mn3+, Cr3+
Epidote: Ca2(A1,Fe)A12O(Si2O7)(SiO4)(OH) Clinozoisite: Ca2A13O (Si2O7)(SiO4)(OH)
Vesuvianite

Formerly called Idocrase Ca10(Mg, Fe)2A14(Si04)5(Si207)2 (OH)7 Tetragonal H = 6 Brown or green
Hemimorphite
Zn4(Si207)(OH)2H20 is one mineral of the sorosilicate group with isolated Si207 groups, cross linked by Zn cations Formed as a secondary mineral in the oxidized portions of zinc deposits
Lawsonite

CaA12(OH)2Si2O7H2O Found only in metamorphic blue (glaucophane)-schist or similar low temperature, moderate to high pressure environments.
Cyclosilicates
When three or more Si tetrahedral groups are linked, a cyclical structure is possible The Si:O ratio is 1:3 Rings containing 3, 4, or 6 Si are possible, but only the rings with 6 Si are at all common
Cyclic Silicates
3 membered ring
6 membered rings
Beryl Structure
A single unit cell of beryl
Yellow Si tetrahedra are in the upper layer, the green ones in the lower layer The outer points of the tetrahedra are actually edges viewed along their length Purple tetrahedra contain Be and are viewed down their four-fold inversion axes They connect the bottom corners of the tetrahedra in the upper ring with the top corners of the tetrahedra in the lower ring Solitary blue atoms are Al, in VI-fold coordination with the adjacent tetrahedral oxygens
Complete Beryl Lattice
Shows the octahedral coordination of Al in blue
Gem Beryl
Upper left, emerald Lower left, morganite Upper right, aquamarine Lower right, golden beryl
Tourmaline
Elbaite, a gem variety of tourmaline
Schorl crystal, with Striations, typical of tourmaline
Chrysocolla
Amorphous but similar to dioptase, a six-membered cyclosilicate May contain Si4O10 units, which would make it a phyllosilicate
Inosilicates: single chains- pyroxenes

b
Diopside: CaMg [Si2O6]

a sin
Where are the Si-O-Si-O chains??
Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

b
a sin

b
a sin

b
a sin

b
a sin

b
a sin
Perspective view

SiO4 as polygons
IV slab VI slab IV slab a sin
(and larger area)
VI slab
IV slab VI slab IV slab b
M1 octahedron
M1 octahedron
(+)
M1 octahedron
(+) type by convention
(-)
M1 octahedron
This is a (-) type
T M1 T
Creates an I-beam like unit in the structure.
T M1
(+)
Creates an I-beam like unit in the structure
(+)
(+)
The pyroxene structure is then composed of alternating I-beams Clinopyroxenes have all I-beams oriented the same: all are (+) in this orientation
Note that M1 sites are smaller than M2 sites, since they are at the apices of the tetrahedral chains
(+)
(+)
(+)
(+)
(+)
The pyroxene structure is then composed of alternation I-beams Clinopyroxenes have all I-beams oriented the same: all are (+) in this orientation
(+)
(+)
(+)
Tetrehedra and M1 octahedra share tetrahedral apical oxygen atoms

The tetrahedral chain above the M1s is thus offset from that below a
(+) M1
(+) M2
The M2 slabs have a similar effect
(+) M2
The result is a monoclinic unit cell, hence clinopyroxenes

c
(-) M1
Orthopyroxenes have alternating (+) and (-) I-beams
(+) M2
a
(+) M1
the offsets thus compensate and result in an orthorhombic unit cell
(-) M2
This also explains the double a cell dimension and why orthopyroxenes have {210} cleavages instead of {110) as in clinopyroxenes (although both are at 90o)
Pyroxene Chemistry
The general pyroxene formula: W1-P (X,Y)1+P Z2O6
Where W = Ca Na 2+ Mn Ni Li X = Mg Fe Y = Al Fe3+ Cr Ti Z = Si Al Anhydrous so high-temperature or dry conditions favor pyroxenes over amphiboles
Orthopyroxenes
Enstatite Hypersthene Orthoferrosilite
MgSiO3 (Mg, Fe)SiO3 Fe SiO3
Enstatite
Brownish orthopyroxene (opx) Lower photo is of Bronzite, an opx containing some Fe, and displaying an iridescence known as Schiller luster
Clinopyroxenes
Diopside Hedenbergite Augite Pigeonite Aegirine Jadeite Spodumene
X Y Ca Mg Ca Fe2+ Ca (Mg, Fe2+) (Al, Fe3+, Ti) (Mg,Fe2+, Ca) (Mg, Fe2+) (Al, Fe3+) Na Fe3+ Na Al Li Al
Si2O6 Si2O6 Si2O6 Si2O6 Si2O6 Si2O6 Si2O6
Augite
Augite is distinguished by 2D cleavage @ 90 Al occurs at tetrahedral sites, so trivalent cations are present at normally divalent sites
Pyroxene Quad
The pyroxene quadrilateral forms part of a larger ternary system (CaSiO3-MgSiO3FeSiO3), that includes another single chain silicate wollastonite The Ca-rich clinopyroxenes are separated from the orthopyroxenes, and from the Ca-poor clionpyroxene pigeonite by a solvus (shown in green in the figure)
Pyroxene Chemistry
The pyroxene quadrilateral and opx-cpx solvus
Coexisting opx + cpx in many rocks (pigeonite only in volcanics)
Wollastonite
pigeonite orthopyroxenes
1200oC
Diopside
clinopyroxenes
Hedenbergite
1000oC
Solvus
800oC
pigeonite
orthopyroxenes Enstatite Ferrosilite
(Mg,Fe)2Si2O6
Ca(Mg,Fe)Si2O6
Pyroxene Chemistry
Non-quad pyroxenes
Jadeite NaAlSi2O6
Aegirine NaFe3+Si2O6
0.8 Omphacite Ca / (Ca + Na)
aegirineaugite
Spodumene: LiAlSi2O6
Ca-Tschermacks molecule CaAl2SiO6 Augite (Ca,Mg,Fe,Al) 2 (Si, Al)2O6
0.2
Diopside-Hedenbergite
Ca(Mg,Fe)Si2O6
Ideal pyroxene chains with 5.2 A repeat (2 tetrahedra) become distorted as other cations occupy VI sites
Pyroxenoids
17.4 A 7.1 A 5.2 A 12.5 A
Pyroxene 2-tet repeat
Wollastonite (Ca M1) 3-tet repeat
Rhodonite MnSiO3 5-tet repeat
Pyroxmangite (Mn, Fe)SiO3 7-tet repeat
Pyroxene vs. Pyroxenoid
7.1 A 5.2 A
12.5 A
Ideal pyroxene chains with 5.2 repeat (2 tetrahedra) become distorted as other cations occupy VI sites Note presence of Si2O7 couplets
Pyroxene 2-tet repeat
Wollastonite Rhodonite (Ca M1) MnSiO3 3-tet repeat 5-tet repeat
Pyroxenoids

Top, pectolite Middle, wollastonite Bottom, rhodonite
Amphibole Chain
Double chain of SiO4 tetrahedra connected by corner sharing
Amphibole Structure
Amphiboles have a double chain structure formed by sharing three corners All have the basic Si4O11 double chains, with larger X ions are in VIII coordination, while smaller Y cations are in VI coordination Si:O = 1:2.75
100
Amphibole Formula
The general formula is: W0-1X0-7Y7-14Z16O44(OH)4 X: Na+, Ca2+, minor K+, Mn2+, Fe2+, Mg2+, Li+ Y: Mg2+, Fe2+, Fe3+, Al3+, Mn2+, Mn3+, Ti4+ Z: Si4+, Al3+
101
Inosilicates: double chains- amphiboles

b
Tremolite: Ca2Mg5 [Si8O22] (OH)2

a sin
Tremolite (001) view blue = Si purple = M1 rose = M2 gray = M3 (all Mg) yellow = M4 (Ca)

b Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2 a sin
Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 light blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purple ball = A (Na) little turquoise ball = H

b
(+)
(+)
Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2 Same I-beam architecture, but the I-beams are fatter (double chains)
a sin
(+)
(+)
(+)
All are (+) on clinoamphiboles and alternate in orthoamphiboles
Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2 M1-M3 are small sites M4 is larger (Ca) A-site is really big
Variety of sites great chemical range
Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2 (OH) is in center of tetrahedral ring where O is a part of M1 and M3 octahedra
(OH) Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 light blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purple ball = A (Na) little turquoise ball = H
Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2
Same I-beam architecture, but the I-beams are fatter (double chains)
Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 light blue = M3 (all Mg, Fe)
Pyroxene Cleavage
Aegirine
a sodic pyroxene
Amphibole Cleavage
Hornblende
Look familiar?
Hornblende:
striated appearance hexagonal crosssection Dark-dark green to black
Orthoamphibole
Orthoamphibole X,Y
Anthopyllite (Mg, Fe2+)7
Z
(Si8O22) (OH, F)2
Clinoamphiboles
Clinoamphiboles W Cummingtonite Grunerite Tremolite Actinolite Hornblende X,Y Fe2+5Mg2 Fe7 Ca2 Mg5 Ca2(Mg,Fe2+)5 Z (Si8O22)(OH, F)2 (Si8O22)(OH, F)2 (Si8O22)(OH, F)2 (Si8O22)(OH, F)2
(Na,K)0-1 (Ca,Na)2 (Mg, Fe2+, Al, Fe3+)5 {(A1, Si)2Si6O22}(OH, F)2 Na2 Na2 Mg3 Al2 Fe32+Fe23+ Si8 O22 (OH)2 (Si8O22)(OH, F)2
Glaucophane Riebeckite
Amphibole Chemistry
See handout for more information General formula:
W0-1 X2 Y5 [Z8O22] (OH, F, Cl)2

W = Na K X = Ca Na Mg Fe2+ (Mn Li) Y = Mg Fe2+ Mn Al Fe3+ Ti Z = Si Al Again, the great variety of sites and sizes a great chemical range, and hence a broad stability range The hydrous nature implies an upper temperature stability limit
Amphibole Chemistry
Ca-Mg-Fe Amphibole quadrilateral (good analogy with pyroxenes)
Tremolite Ca2Mg5Si8O22(OH)2
Actinolite
Ferroactinolite Ca2Fe5Si8O22(OH)2 Clinoamphiboles
Anthophyllite Mg7Si8O22(OH)2
Cummingtonite-grunerite
Orthoamphiboles
Fe7Si8O22(OH)2
Al and Na tend to stabilize the orthorhombic form in low-Ca amphiboles, so anthophyllite gedrite orthorhombic series extends to Fe-rich gedrite in more Na-Al-rich compositions
Amphibole Chemistry
Hornblende has Al in the tetrahedral site
Geologists traditionally use the term hornblende as a catch-all term for practically any dark amphibole. Now the common use of the microprobe has petrologists casting hornblende into end-member compositions and naming amphiboles after a well-represented end-member.
Sodic amphiboles
Glaucophane: Na2 Mg3 Al2 [Si8O22] (OH)2 Riebeckite: Na2 Fe2+3 Fe3+2 [Si8O22] (OH)2 Sodic amphiboles are commonly blue, and often called blue amphiboles
Amphibole Occurrences
Tremolite (Ca-Mg) occurs in meta-carbonates Actinolite occurs in low-grade metamorphosed basic igneous rocks Orthoamphiboles and cummingtonite-grunerite (all Ca-free, Mg-Fe-rich amphiboles) are metamorphic and occur in meta-ultrabasic rocks and some meta-sediments. The Fe-rich grunerite occurs in meta-ironstones The complex solid solution called hornblende occurs in a broad variety of both igenous and metamorphic rocks Sodic amphiboles are predominantly metamorphic where they are characteristic of high P/T subduction-zone metamorphism (commonly called blueschist in reference to the predominant blue sodic amphiboles Riebeckite occurs commonly in sodic granitoid rocks
Inosilicates
+ + + + + + + + Clinopyroxene + + + + + + + + +
Clinoamphibole
Orthopyroxene
Orthoamphibole
Pyroxenes and amphiboles are very similar:

Both have chains of SiO4 tetrahedra The chains are connected into stylized I-beams by M octahedra High-Ca monoclinic forms have all the T-O-T offsets in the same direction Low-Ca orthorhombic forms have alternating (+) and (-) offsets
Inosilicates
pyroxene amphibole
b a
Cleavage angles can be interpreted in terms of weak bonds in M2 sites (around I-beams instead of through them)
Narrow single-chain I-beams 90o cleavages in pyroxenes while wider doublechain I-beams 60-120o cleavages in amphiboles
Phyllosilicates
SiO4 tetrahedra polymerized into 2-D sheets: [Si2O5]
Apical Os are unpolymerized and are bonded to other constituents
Sheet Silicates (Nesse, Ch.13, p.235-39; 244-48)

phlogopite
muscovite
biotite
photos: mindat.org
lepidolite
Sheet Silicates Nesse, Ch.13, p.235-39; 244-48)

sheet silicate, general formula: AY2-3T4O10(OH)2
where A = K,Na; Y = Al,Mg,Fe,Mn,Ti; T = Al,Si two structural groups of mica are recognised depending on number of octahedral (Y) sites: dioctahedral micas: Y = 2 (e.g., muscovite, paragonite) Y-site occupied by trivalent cations (mainly Al3+) root formula: muscovite = KAl2AlSi3O10(OH)2 trioctahedral micas: Y = 3 (e.g., biotite, lepidolite) Y-site occupied by divalent cations (mainly Mg,Fe) root formula: phlogopite = KMg3AlSi3O10(OH)2
Sheet Silicates(Nesse, Ch.13, p.235-39; 244-48)

OH
O
T
octahedral Y-sites with OH- at apices [SiO4]4- sheet (T-site) top view of octahedral layer
(light grey)
with superimposed T-layer

(dark grey; note 6-fold symmetry)
apical oxygen in T-layer replaces OH- group in O-layer linking O-layers and T-layers forms OT or TOT (I-beam) structures
O T I-beam T O T
Sheet Silicates(Nesse, Ch.13, p.235-39; 244-48)

octahedral Y-sites with OH- at apices
trioctahedral
trioctahedral: 3/3 of Y-sites filled divalent cations (Mg, Fe2+, Mn) dioctahedral: 2/3 of Y-sites filled trivalent cations (Al3+, Cr3+, Fe3+)
dioctahedral
Sheet Silicates (Nesse, Ch.13, p.235-39; 244-48)

TO kaolinite serpentine TOT pyrophyllite talc
linking O-layers and T-layers forms OT or TOT (I-beam) structures OT or TOT structures linked by: van der Waals bonds (weak) extra O layers (a little stronger) large cations (a little stronger) type of linkage determines type of sheet silicate O T
TOT + cation micas
TOT + O chlorite
I-beam T O T
Phyllosilicates
Tetrahedral layers are bonded to octahedral layers (OH) pairs are located in center of T rings where no apical O
Phyllosilicates
Octahedral layers can be understood by analogy with hydroxides
Brucite: Mg(OH)2
Layers of octahedral Mg in coordination with (OH) Large spacing along c due to weak van der waals bonds
Phyllosilicates
a2
a1
Gibbsite: Al(OH)3 Layers of octahedral Al in coordination with (OH) Al3+ means that only 2/3 of the VI sites may be occupied for charge-balance reasons Brucite-type layers may be called trioctahedral and gibbsite-type dioctahedral
Phyllosilicates
Yellow = (OH)
Kaolinite: Al2 [Si2O5] (OH)4 T-layers and diocathedral (Al3+) layers (OH) at center of T-rings and fill base of VI layer
weak van der Waals bonds between T-O groups
T O T O T O
vdw
vdw
Phyllosilicates
Yellow = (OH)
Serpentine: Mg3 [Si2O5] (OH)4 T-layers and triocathedral (Mg2+) layers (OH) at center of T-rings and fill base of VI layer
weak van der Waals bonds between T-O groups
T O T O T O
vdw
vdw
Serpentine
Antigorite maintains a sheet-like form by alternating segments of opposite curvature
Chrysotile does not do this and tends to roll into tubes
Octahedra are a bit larger than tetrahedral match, so they cause bending of the T-O layers (after Klein and Hurlbut, 1999).
Phyllosilicates
Yellow = (OH)
Pyrophyllite: Al2 [Si4O10] (OH)2 T-layer - diocathedral (Al3+) layer - T-layer

weak van der Waals bonds between T - O - T groups
T O T T O T T O T
vdw
vdw
Phyllosilicates
Yellow = (OH)
Talc: Mg3 [Si4O10] (OH)2 T-layer - triocathedral (Mg2+) layer - T-layer

weak van der Waals bonds between T - O - T groups
T O T T O T T O T
vdw
vdw
Phyllosilicates
Muscovite: K Al2 [Si3AlO10] (OH)2 (coupled K - AlIV) T-layer - diocathedral (Al3+) layer - T-layer - K
K between T - O - T groups is stronger than vdw
T O T K T O T K T O T
Phyllosilicates
Phlogopite: K Mg3 [Si3AlO10] (OH)2 T-layer - triocathedral (Mg2+) layer - T-layer - K

K between T - O - T groups is stronger than vdw
T O T K T O T K T O T
Other Sheet Silicates

(Nesse, Ch. 13 p. 235-44; 252-57)
chrysotile
chlorite
talc clay minerals
lizardite
serpentine
kaolinite
illite
photos: mindat.org

(Nesse, Ch. 13 p. 235-44; 252-57)
Clay minerals: group of very fine-grained (< 2 mm) sheet silicates
too fine-grained to be distinguished by conventional optical or physical tests identification requires a combination of XRD and electron microscopy methods
illite
dominant constituent of clay (finegrained sediment)

characterised by high Al, OH contents in addition to Si and other cations
kaolinite kaolinite
varieties include: kaolinite, smectite, illite, vermiculite, chlorite

(Nesse, Ch. 13 p.252-57)
Clay minerals: group of very fine-grained (< 2 mm) sheet silicates
Al2Si2O5(OH)4 (Mg,Fe,Al)6 (Si,Al)4O10(OH)8
expandable clay mixed layer clays

Ca0.2(Al,Mg,Fe)2(Al,Si)4O10(OH)2.nH2O
K0.5Al2(Al0.8Si3.2)O10(OH)4 muscovite-like
Phyllosilicates
A Summary of Phyllosilicate Structures
Fig 13.84 Klein and Hurlbut Manual of Mineralogy, John Wiley & Sons
Phyllosilicates
Chlorite: (Mg, Fe)3 [(Si, Al)4O10] (OH)2 (Mg, Fe)3 (OH)6
= T - O - T - (brucite) - T - O - T - (brucite) - T - O - T Very hydrated (OH)8, so low-temperature stability (low-T metamorphism and alteration of mafics as cool)
Framework Silicates/ Tectosilicates
The tectosilicates are three dimensional, or framework, silicates They involve linkage of SiO4 tetrahedra through all four oxygen atoms The resulting structure is stable and strongly bonded Si:O ratio is 1:2
MoW 7: Silica Group (Nesse, Ch. 12, p. 201-208)

a framework silicate with the formula: SiO2 by far the most abundant silica group mineral is
a-quartz
other SiO2 polymorphs are preserved in the geological record under special circumstances
a number of non- or micro-crystalline varieties of SiO2 also form important minerals
Tectosilicates
Stishovite
10
Pressure (GPa)
Coesite
- quartz a- quartz
Cristobalite Tridymite
600 1000 1400 1800 2200 2600
Liquid
After Swamy and Saxena (1994) J. Geophys. Res., 99, 11,787-11,794.
Temperature oC
Silica Group (Nesse, Ch. 12, p. 201-208)

phase diagram for SiO2 system
certain SiO2 polymorphs indicate specific P-T ranges and geological environments
ultra-high pressure (UHP) conditions
ultra-high temperature (UHT) conditions

phase diagram for SiO2 system
restricted to impact craters
Coesite diagnostic of UHP metamorphism (continental subduction) a-quartz -quartz transformation always takes place; -quartz not stable at surface
restricted to volcanic environments

non- or micro-crystalline varieties of SiO2
microcrystalline: moganite alternating sheets of rightand left-handed a-quartz chert (including jasper, flint) microcrystalline, granular chalcedony (including agate) microcrystalline, fibrous
non-crystalline: opal - a form of colloidal silica - important gemstone
Varieties of Crystalline Quartz

Blue Amethyst
Milky
Citrine
Rose
Varieties of Cryptocrystalline Quartz

Jasper Chalcedony
Chert
Chrysoprase
Stishovite
Tectosilicates
Coesite
Low Quartz
a- quartz
- quartz Liquid
001 Projection Crystal Class 32
Stishovite
Tectosilicates
Coesite
High Quartz at 581oC

a- quartz
- quartz Liquid
001 Projection Crystal Class 622
Stishovite
Tectosilicates
Coesite
Cristobalite
a- quartz
- quartz Liquid
001 Projection Cubic Structure
Stishovite
Tectosilicates
Coesite
Stishovite
a- quartz
- quartz Liquid
High pressure SiVI
Tectosilicates
Low Quartz Stishovite
SiIV
SiVI
Tectosilicates
Feldspars
Substitute Al3+ for Si4+ allows Na+ or K+ to be added
Substitute two Al3+ for Si4+ allows Ca2+ to be added

Albite: NaAlSi3O8
Feldspars
Alkali Potassium and Ab95-100 Plagioclase An5-100 Barium

Celsian BaAl2Si2O8 Hyalophane (K, Ba)(A1,Si)2Si2O8
MoW 3: Feldspar (Nesse, Ch. 12, p. 208-225)
photos: mindat.org
Feldspar Composition
Alkali Feldspars
K-spar shows a variety of polymorphic forms
Sanidine Orthoclase Microcline
Microcline
Orthoclase
Sanidine
Perthite and Antiperthite
Albite in K-spar host = perthite K-spar in plagioclase host = antiperthite
Perthite
Plagioclase Name
Plagioclases are triclinic Their a-b and b-c angles are a bit more oblique than microcline Hence the name: plagio-, oblique and clase, break
Albite
Plagioclase Feldspars
Albite
An0-10 - Found only in very sodic rocks, hence usually metamorphic or formed in marine conditions as a sedimentary cement, or by ion exchange with more calcic plagioclase. An10-30 - The dominant plagioclase in granitic rocks An30-50 - Found in intermediate igneous rocks An50-70 - The dominant plagioclase in gabbro and basalt. Also, despite their name, most anorthosites are made up of labradorite.
Oligoclase
Andesine
Labradorite
Bytownite
An70-90 - The rarest. Requires both a lot of calcium and also significant sodium. Most igneous settings have too much sodium, most calc-silicate metamorphic settings have too little sodium.
An90-100 - Generally a metamorphic mineral in calc-silicate rocks.
Anorthite

a framework silicate with the general formula: AT4O8 where A = Ca, Na, K; T = Al, Si 2 solid solution series: plagioclase: CaAl2S12O8 NaAlSi3O8 anorthite (An) albite (Ab)
An0-10: albite An50-70: labradorite An10-30 : oligoclase An70-90: bytownite An30-50: andesine An90-100: anorthite
alkali feldspar: NaAlSi3O8 KAlSi3O8 albite (Ab) orthoclase (Or)

Or100-35: orthoclase Or35-10: anorthoclase Or10-0: albite 3 K-feldspar polymorphs: sanidine, orthoclase, microcline (high T low T)
Feldspar (Nesse, Ch. 12, p. 208-225)

a framework silicate with the general formula: AT4O8 where A = Ca, Na, K; T = Al, Si
Or100
feldspar nomenclature and solid-solution limits

very limited solid soution between K- and Caend members
Ab100
An10-30 An30-50 An50-70 An70-90
An100

a framework silicate with the general formula: AT4O8 where A = Ca, Na, K; T = Al, Si
crystal structure of feldspar
[SiO4]4- groups T site (Al, Si)
crankshaft arrangement crankshafts linked by A-site cations K, Na, Ca (CN = 9)

ordering in feldspar structure
both Si and Al occupy tetrahedral (T) sites (3:1 in K-Na- feldspar, 2:1 in Ca-plag)
at high T, random distribution of Si, Al: disordered monoclinic symmetry
(sanidine, orthoclase)
at low T, non-random distribution of Si, Al: ordered triclinic symmetry

(microcline) increasing order
sanidine
increasing order, decreasing T
25% Al, 75% Si 50% Al, 50% Si 100% Al 100% Si
orthoclase microcline
3 K-feldspar polymorphs distinguished by degree of ordering of Si, Al in crystal lattice

a) b)
twinning in feldspar
a) albite twins: reflection on (010)
(polysynthetic or barcode twinning in plag)
b) pericline twins: rotation on [010]

c) d)
(also very common in plagioclase)
c) Carlsbad twins: rotation on [001]

(typical simple twins in K-feldspar)
d) Manebach twins: reflection on (001) e) Braveno twins: reflection on (021)

cross-hatched (tartan) twinning in microcline: albite + pericline produced during inversion from orthoclase
e)
Nesse, Fig. 12.11

plagioclase: normal zoning from Ca-rich cores to Na-rich rims reflects crystallisation from a fractionating magma
distinguishing features (plag vs Kfd or qtz): polysynthetic (barcode) twinning; zoning common; exsolution rare biaxial +ve (An0-20) or ve (An20-100), 2V large

alkali feldspar: exsolution lamellae (perthite) form during unmixing of homogeneous K,Na-feldspar during slow cooling (subsolidus solvus) anorthoclase distinguishing features 1:
(Kfd vs plag or qtz):
simple (Carlsbad) or crosshatched (tartan) twins; exsolution common; zoning relatively rare; biaxial ve
distinguishing features 2:
(sanidine vs orthoclase vs microcline):
sanidine: small 2V, simple twins orthoclase: large 2V, simple twins microcline: large 2V, tartan twins

occurrence: most abundant mineral in Earths crust (generally not stable in the mantle)
plag essential (dominant) mineral in mafic and intermediate igneous
rocks (basalts, andesites, etc.) - important constituent of most felsic and alkaline igneous rocks - present in metamorphic equivalents of these rocks, as well as metasedimentary rocks (marbles, pelites) - common detrital mineral in sedimentary rocks - present in many hydrothermal vein deposits
alkali fd essential mineral in felsic and alkaline igneous rocks,

common in some intermediate igneous rocks - present in some high-grade metamorphic rocks (granitioid and pelitic gneisses, migmatites) - common detrital mineral in sedimentary rocks (also authigenic) - present in many hydrothermal vein deposits (var. adularia)
use:
semi-precious stone (moonstone, labradorite) aggregate, decorative stone filler, abrasive, whitener, ceramics
Charge Balance
Since Na and Ca differ in valence, Al has to substitute for Si to compensate The Al-Si orderings of albite and anorthite are different, and at low temperatures, plagioclases in the middle of the composition range also exsolve, but on a submicroscopic scale These submicroscopic textures are probably responsible for the iridescence of some plagioclases
Feldspathoids
Alumino silicates but contain less SiO2 than feldspars They are rich in alkalis The feldspathorids often include unusual anions such as Cl-, CO3-, etc.
Important Feldspathoids
Nepheline (Na, K)AlSiO4 Leucite K(AlSi2O6) Sodalite Na8(Al Si O4)6Cl2 Lazurite (Na,Ca)8(AlSiO4)6(SO4, S, Cl)2 Petalite Li (Al Si4O10) K Cl SO4, S, Cl
Scapolites
Metamorphic rock minerals probably derived from feldspars The alumino-silicate framework forms chains in the c-direction and has large open spaces which can accommodate large anions such a Cl, CO3, SO4
Scapolite Minerals
Marialite Na4(AlSi3O8)3(Cl2,CO3,SO4) Meionite Ca4(Al2Si2O8)3(Cl2,CO3,SO4)
Marialite cluster
Zeolites
Stilbite
Hydrous aluminosilicates with very open structures. Rings of A1O4 and SiO4 tetrahedra are penetrated by open channels in the structure Non-silicon cations hold the structure together.
Cation Exchange
Water can easily pass though these channels and dissolve and replace the cations present in the structure This process in known as cation exchange and is reversible Thus, the zeolites can serve as catalysts and watersoftening agents Petroleum companies have been particularly interested in zeolites for this reason
Important Natural Zeolites
Chabazite Ca2(Al2Si4O12)6H2O Heulandite Ca(Al2Si7018)6H2O Stilbite (Na,K,Ca0.5)9Na(Al9Si27O72)28H2O Natrolite Na2(Al2Si3O10)2H2O Analcime Na(AlSi2O6)H2O
% Systematic Silicate of Tot. # of atoms Fe/Mg: Silicon: Mineralogy Olivine 29% 14%
Pyroxene Fig. 2.9 <20% Group From bottom to top
20%
Increasing Amphibole Fe/Mg/Ca Group <3% Decreasing silica Increasing density Mica <2% Group Darker minerals
23%
25%
Decreasing Silica
Increasing Fe/Mg/Ca
Quartz K and Na Feldspar Ca Feldspar
Increasing Density
(0) (0) (0)
33% 23% 15%*

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Classification of Minerals

Behavior of elements: Goldschmidts classification

Elements divided into four broad categories:

Most Common Elements of Earths Crust

Plate tectonics: Mixing crust and mantle

Ferromagnesian Silicates (Fe, Mg)

Oxides Carbonates Sulfides/sulfates Native elements

Tectosilicates (or Tekto-) Framework

Element of Mineral Silicates Structure

expanded ("stick") view

Nesse Fig. 11.1

top view schematic:

Sharing of Oxygen Anions

Examples: olivine garnet

Cyclosilicates/ Ring Silicates

Examples: benitoite BaTi[Si3O9] axinite Ca3Al2BO3[Si4O12]OH beryl Be3Al2[Si6O18]

[SiO3]2- single chains pryoxenes pyroxenoids

[Si4O11]4Double tetrahedra amphiboles

[Si2O5]2Sheets of tetrahedra micas talc clay minerals serpentine

Phyllosilicates/ Sheet Silicates

3-D frameworks of tetrahedra: fully polymerized

Tectosilicates/ Framework Silicates

quartz and the silica minerals feldspars

Olivine Structure: (Mg,Fe)2SiO4

Nesosilicates: independent SiO4 tetrahedra

Olivine (100) view blue = M1 yellow = M2

Nesosilicates: independent SiO4 tetrahedra

Olivine (100) view blue = M1 yellow = M2

Nesosilicates: independent SiO4 tetrahedra

M1 in rows and share edges

M2 form layers in a-c that share corners

Olivine (001) view blue = M1 yellow = M2

Nesosilicates: independent SiO4 tetrahedra

Olivine (100) view blue = M1 yellow = M2

Representing mineral structures: space-filling view

expanded (stick) view

Si4+ olivine: Mg2SiO4

Mg2+ Si4+ O2-

atomic radius () 0.72 0.26 1.40

Representing mineral structures: co-ordination polyhedra tetrahedra

Mg2+ octahedra SiO4atomic radius () 0.72 0.26 1.40

Mg2+ Si4+ O2-

Representing mineral structures:

(distances along a, b, c crystallographic axes)

Mg2+ Si4+ O2-

atomic radius () 0.72 0.26 1.40

Fayalite Fe2Si04 Fa Forsterite Mg2Si04 Fo

Olivine Solid Solution Ranges

Forsterite Chrysolite Hyalosiderite Mortonolite Ferrohortonolite Fayalite

0-10% Fe 10-30% Fe 30-50% Fe 50-70% Fe 70-90% Fe 90-100% Fe

Solid Solution Nomenclature

Other Olivine Group Minerals

CaMgSi04 Mn2Si04 CaMnSi04 CaFeSi04

Monticellite Tephroite Glaucochroite Kirschsteinite

Nesosilicates: independent SiO4 tetrahedra

Nesosilicates: independent SiO4 tetrahedra

Garnet (001) view blue = Si purple = A turquoise = B

Nesosilicates: independent SiO4 tetrahedra

Some high-Al igneous Also in some mantle peridotites

Garnet (001) view blue = Si purple = A turquoise = B

Typical cations A13+, Cr3+, Fe3+, and Ti4+

Calcium and Noncalcium Garnets

Grossularite, also Ca3A12(Si04)3 called cinnamon stone, essonite Andradite Ca3Fe2(Si04)3