Silicates. The most common group of minerals forming the silicate Earth

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4 Silicates The most common group of minerals forming the silicate Earth 25% of all minerals (~1000) 40% of rock forming minerals 90% of earth s crust i.e those minerals you are likely to find ~100 of earth s mantle

5 Silicate Structure Basic building block: silica tetrahedron Si 4+ with four O 2- surrounding it Net charge is 4- Polymerization: tetrahedron can share oxygen atoms

6 Silica Tetrahedron

7 Silicates Quartz (and polymorphs) only minerals with only Si and O All other silicates are charge balanced by other cations glue that holds together silica tetrahedron

8 Degree of polymerization depends on availability of Si Quartz and feldspars (framework): Si-rich environments Si/O = ½ Olivine (orthosilicate): Si-poor environment Si/O = ¼

9 Six groups of silicate minerals Orthosilicates = Nesosilicates Single tetrahedron Disilicates = Sorosilicates Two tetrahedrons share single oxygen Ring silicates = Cyclosilicates 4, 5, or 6 tetrahedron share two oxygen

10 Chain silicates = Inosilicates 2 or 3 oxygen shared, arranged in single or double chain Sheet silicates = Phyllosilicates 3 oxygen shared in sheets Framework silicates = Tectosilicates All 4 oxygen are shared

11 Ortho- Di- Chain double and single Ring Sheet Tecto

12 Z/O ratios Z = Si tetrahedral sites Can be other cations, most commonly Al Z/O ratio depends on type of silicate Ortho = 1/4 Di = 2/7 Ring = 1/3 Chain, single = 1/3; double = 4/11 Sheet = 2/5 Framework = 1/2

13 Mafic vs Felsic Mafic rich in Magnesium and Iron (Ferrum), Si-poor E.g. biotite, amphiboles, pyroxenes, and olivines Commonly dark colored Felsic rich in Si and Al E.g. Feldspars, Quartz (SiO2), muscovite, feldspathoids Commonly light colored

14 Systematic Mineralogy

15 Orthosilicates Isolated tetrahedron Common examples Olivine, garnet, and zircon Al 2 SiO 5 polymorphs, staurolite, topaz, titanite Oxygen coordinate with other anions

16 I: Olivine Group - Structure Octahedron occupied with Fe 2+, Ca 2+, Mg 2+ Two distinct sites: M 1 and M 2 M 1 are stretched out along c axis edge sharing M 2 less distorted Crystals can be elongate along c axis

17 Composition Complete solid solution between forsterite (Mg) and fayalite (Fe) Mn end members as well rare Ca can be around 50% of cations Fe and Mg contents cause variations in physical properties Can be used to identify composition Zoning can be common

18 Structure and composition M 1 = distorted, so smaller than M 2 M 2 = regular octahedron Controls distribution of cations M 2 only site for Ca, 1.12 Å M 1 and M 2 both Fe = 0.78 Å and Mg = 0.72 Å

19 Distorted, small site, Ca will not fit If sufficient Ca present when olivine forms, all M1 sites filled with Ca. Ca = 50 mole % Fe + Mg = 50 mole %

20 Ca Mg Fe

21 Fig. 16-3

22 Occurrence Common mafic and ultramafic mineral Mantle Metamorphosed carbonate rocks

23 Factoids Olivine unstable at high pressure of mantle Convert to more dense phase (~6% more dense) Cubic closest packing or oxygen Very similar to spinel structure (metal oxide) Change in structure causes: Seismic velocity increases at 400 km (greater density) Deep earthquakes in subduction zones, >70 km depth

24 II: Garnet Group Structure Single Si tetrahedron bonded by octahedron and distorted 8-fold sites Octoahedron: Y-sites = Al, Fe 3+, (Cr) 8 fold: X-sites = Mg, Fe 2+, Mn, Ca

25 Garnet composition General formula = X 3 Y 2 (SiO 4 ) 3 Typically Al fixed in Y site, elements vary in X-site Ca fixed in X site, elements vary in y site

26 X distorted cube, 8 fold, Larger cations Fe 2+, Mg 2+, Ca 2+ Y octahedral, smaller cations Al 3+, Fe 3+, (Cr)

27 III: Aluminum Silicates Common in pelitic metamorphic rocks Formula: Al 2 SiO 5 or AlAlOSiO 4 The second formula shows two distinct Al sites Also that they are orthosilicates

28 Andalusite extra Al in 5-fold coordination Open structure with low specific gravity VI Al V AlO IV SiO 4 Sillimanite extra Al in tetrahedral coordination VI Al IV AlO IV SiO 4 Kyanite extra Al in octahedral coordination VI Al VI AlO IV SiO 4 Most dense of all polymorphs

29 Al in 6 fold coordination High P = high density Al in 4 fold coordination High T = low density Al in 5 fold coordination Intermediate density

30 Disilicates and Ring Silicates Disilicates Not a common group of minerals not rock forming Widely distributed Most common are the epidote group Epidote Zoisite Clinozoisite Allanite

31 Characteristic structure Pair of single tetrahedrons Share single O Z/O ratio = 2/7

32 Ring Silicates Only three common species Tourmaline Beryl Cordierite All are 6 member rings Rings stacked on top of each other

33 Ring Z/O = 1/3 Beryl and Cordierite Tourmaline

34 Inosilicates (chain) Common Fe/Mg bearing silicates Two common groups Pyroxenes: single chains Amphiboles: double chains Pyroxenes are common in MORB Amphiboles more common on continents because of weathering

35 Pyroxene group General formula: XYZ 2 O 6 Z/O ratio = 1/3 Z cations usually Si, occasionally Al Single chain extend along c axis Chains are stacked along a axis, alternating: Base faces base Apex faces apex

36 View down a axis View down c axis Two distinct sites, depending on location relative to chains M1 and M2 Base facing base Apex facing Apex Fig. 14-1

37 X cations in M2 sites Between bases of tetrahedrons Distorted 6- and 8- fold coordination Depends on stacking and the size of the cations Y cations in M1 sites 6-fold coordination between apical oxygen

38 Classification Based on two linked things Which cations occurs in M2 sites (facing bases of tetrahedron) Cation determines symmetry Most plot on ternary diagram with apices: Wollastonite, Wo Enstatite, En Ferrosilite, Fe

39 Three major groups Orthopyroxenes (opx) orthorhombic Low-Ca clinopyroxenes (cpx) monoclinic Ca-rich clinopyroxenes (cpx) monoclinic The amount of Ca in the mineral controls the extinction angle

40 Orthopyroxenes: Fe and Mg, but little Ca Both M1 and M2 are octahedral Larger Fe ion more concentrated in M2 site (larger)

41 Low-Ca clinopyroxene: more Ca, but no solid solution with clinopyroxene Mineral species is Pigeonite Ca restricted to M2 sites, these still mostly Fe and Mg M1 sites all Mg and Fe

42 Ca- clinopyroxene Diopside Mg(+Ca) to Hedenbergite Fe (+Ca) M2 site contains mostly Ca M1 site contains mostly Fe and Mg Most common specie is augite Al substitutes in M1 site, and for Si in tetrahedral site Na, Fe or Mg substitutes for Ca in M2 site

43 Possible ranges of solid solutions Augite Clinopyroxene Orthopyroxenes Na bearing pyroxenes

44 Amphibole Group Structure, composition, and classification similar to pyroxenes Primary difference is they are double chains Z/O ratio is 4/11

45 Structure Chains extend parallel to c axis Stacked in alternating fashion like pyroxenes Points face points and bases face bases

46 Chains are linked by sheets of octahedral sites Three unique sites: M1, M2, and M3 Depend on location relative to Si tetrahedron Shared O Not shared O OH

47 Geometry produces five different structure sites M1, M2, and M3 between points of chains M4 and A sites between bases of chains

48 Composition W 0-1 X 2 Y 5 Z 8 O 22 (OH) 2 Each cation fits a particular site W cation Occurs in A site Has ~10 fold coordination Generally large, usually Na +

49 W 0-1 X 2 Y 5 Z 8 O 22 (OH) 2 X cations Located in M4 sites Analogous to M2 sites in pyroxenes Have 6 or 8 fold coordination depending on arrangement of chains If 8-fold, X usually Ca If 6-fold, X usually Fe or Mg

50 W 0-1 X 2 Y 5 Z 8 O 22 (OH) 2 Y cations Located in M1, M2, and M3 sites; Octahedral cations in TOT strips Usually Mg, Fe 2+, Fe 3+, Al Z cations Usually Si and Al

51 Water Tetrahedron pointing up Tetrahedron pointing down

52 W 0-1 X 2 Y 5 Z 8 O 22 (OH) 2 Tremolite Ferroactinolite ~30% Ca exactly 2/7 of sites available for Ca Anthophylite Orthorhomic Grunerite Monoclinic

53 Sheet Silicates Abundant and common minerals throughout upper 20 km of crust Felsic to intermediate igneous, metamorphic, and sedimentary rocks All are hydrous Contain H Bonded to O to form OH- Z/O ratio of 2/5 2 Major groups: Micas & Clays

54 Groupings Two kinds of layers within the sheets T layers tetrahedral layers Tetrahedral coordination of Si and Al O sheets octahedral layers Octahedral coordination of mostly Al and Mg, occasionally Fe

55 T and O layers join to form sheets The sheets are repeated in vertical direction The spaces between the sheets may be: Vacant Filled with interlayer cations, water, or other sheets Primary characteristic - basal cleavage Single perfect cleavage Occurs because bonds between sheets are very weak

56 Dioctahedral mica muscovite KAl 2 (AlSi 3 O 10 )(OH) 2 Trioctahedral mica Phlogopite/biotite K(Mg, Fe) 3 (AlSi 3 O 10 )(OH) 2

57 Framework Silicates 2/3 of crust is framework silicates Quartz and feldspars are most common All with similar structures TO4 tetrahedral framework T = Si or Al Each oxygen is shared with another tetrahedron Sharing of highly charged cation (Si4+) make open structures

58 Consequences of open framework Compositional Accommodate large cations Ca, Na, and K Charge balance maintained by exchange of Al and Si

59 Physical properties Specific gravity lower than most other minerals E.g. quartz = 2.65, olivine = 3.27 Not stable at high P Restricted to crust

60 Four major groups: Silica group (SiO 2 ) Feldspars Feldspathoids Zeolites

61 Silica group Eight possible polymorphs Rare forms High P Stishovite Si in octahedral coordination Coesite Common forms Quartz, a & b Tridymite, a & b Cristobalite, a & b

62 Reconstructive polymorphism between qtz, tridymite and cristobalite Displacive polymorphism between a and b varieties Tridymite and Cristobalite not stable at surface P and T Will convert to quatz

63 Amethyst biolet or purple from trace amounts of Fe Rose quartz pink colored, may be caused by mineral inclusions Citrine yellow quartz from Fe, radiation or combination Smoky quartz irradiation and small amounts of Al Milky quartz minute fluid inclusions

64 Feldspar Group Three compositional end members K-feldspar (KAlSi 3 O 8 ) Ks or Or Sanidine Orthoclase Microcline Albite (NaAlSi 3 O 8 ) Ab Anorthite (CaAl 2 Si 2 O 8 ) An Plagioclase An and Ab Alkali Ab and Ks (Or)

65 Plagioclase feldspars At high T, continuous solid solution CaAl substitutes for NaSi Generally described as fraction of An, assuming An + Ab = 100%

66 Compositions divided into ranges and given names Albite: An0 An10 Oligoclase: An10 An30 Andesine: An30 An50 Labradorite: An50 An70 Bytownite: An70 An90 Anorthite: An90 An100

67 Alkali feldspars Continuous solid solution at high T K and Na same charge compensates for difference in size K and Ca don t have solid solution because different size and charge

68 solid solution

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