Average Composition of the Continental Crust. Table 3.4

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1 Minerlaogi II

2 Average Composition of the Continental Crust Si O Weight Percent O Volume Percent Table 3.4

3 Ionic Radii of some geologically important ions Fig. 3.8

4 Silika Tetraederet

5 Silicates are classified on the basis of Si-O polymerism [SiO 4 ] 4- Independent tetrahedra Nesosilicates Examples: olivine garnet [Si 2 O 7 ] 6- Double tetrahedra Sorosilicates Examples: epidote n[sio 3 ] 2- n = 3, 4, 6 Cyclosilicates Examples: benitoite BaTi[Si 3 O 9 ] axinite Ca 3 Al 2 BO 3 [Si 4 O 12 ]OH beryl Be 3 Al 2 [Si 6 O 18 ]

6 Silicates are classified on the basis of Si-O polymerism [SiO 3 ] 2- single chains Inosilicates [Si 4 O 11 ] 4- Double tetrahedra pyroxenes pyroxenoids amphiboles

7 Silicates are classified on the basis of Si-O polymerism [Si 2 O 5 ] 2- Sheets of tetrahedra Phyllosilicates micas talc clay minerals serpentine

8 Silicates are classified on the basis of Si-O polymerism low-quartz [SiO 2 ] 3-D frameworks of tetrahedra: fully polymerized Tectosilicates quartz and the silica minerals feldspars feldspathoids zeolites

9 Olivine: formed from single silica tetrahedra

10 Olivine picture gallery Forsterite Mg 2 SiO 4 Fayalite Fe 2 SiO 4 This is a cut crystal An olivine nodule in a volcanic rock Peridot - gem quality olivine

11 Nesosilicates: independent SiO 4 tetrahedra b c projection Olivine (100) view blue = M1 yellow = M2

12 Nesosilicates: independent SiO 4 tetrahedra b c perspective Olivine (100) view blue = M1 yellow = M2

13 Nesosilicates: independent SiO 4 tetrahedra b M1 in rows and share edges a M2 form layers in a-c that share corners Some M2 and M1 share edges Olivine (001) view blue = M1 yellow = M2

14 Nesosilicates: independent SiO 4 tetrahedra b c M1 and M2 as polyhedra Olivine (100) view blue = M1 yellow = M2

15 Nesosilicates: independent SiO 4 tetrahedra Olivine Occurrences: Principally in mafic and ultramafic igneous and meta-igneous rocks Fayalite in meta-ironstones and in some alkalic granitoids Forsterite in some siliceous dolomitic marbles Monticellite CaMgSiO 4 Ca M2 (larger ion, larger site) High grade metamorphic siliceous carbonates

16 The garnet picture gallery

17 Nesosilicates: independent SiO 4 tetrahedra Garnet: A 2+ 3 B 3+ 2 [SiO 4 ] 3 Pyralspites - B = Al Pyrope: Mg 3 Al 2 [SiO 4 ] 3 Almandine: Fe 3 Al 2 [SiO 4 ] 3 Spessartine: Mn 3 Al 2 [SiO 4 ] 3 Ugrandites - A = Ca Uvarovite: : Ca 3 Cr 2 [SiO 4 ] 3 Grossularite: Ca 3 Al 2 [SiO 4 ] 3 Andradite: Ca 3 Fe 2 [SiO 4 ] 3 Occurrence: Mostly metamorphic Some high-al igneous Also in some mantle peridotites Garnet (001) view blue = Si purple = B turquoise = A

18 Nesosilicates: independent SiO 4 tetrahedra Garnet: A 2+ 3 B 3+ 2 [SiO 4 ] 3 a 1 a 3 a 2 Pyralspites - B = Al Pyrope: Mg 3 Al 2 [SiO 4 ] 3 Almandine: Fe 3 Al 2 [SiO 4 ] 3 Spessartine: Mn 3 Al 2 [SiO 4 ] 3 Ugrandites - A = Ca Uvarovite: : Ca 3 Cr 2 [SiO 4 ] 3 Grossularite: Ca 3 Al 2 [SiO 4 ] 3 Andradite: Ca 3 Fe 2 [SiO 4 ] 3 Occurrence: Mostly metamorphic Pyralspites in meta-shales Ugrandites in meta-carbonates Some high-al igneous Also in some mantle peridotites Garnet (001) view blue = Si purple = A turquoise = B

19 Linking Silicate Tetrahedra Fig. 3.20

20

21 Chains (polymers) of silicate anions

22 Enkeltkjeder - eks. Diopside (en pyroxen-camgsi2o6)

23 Inosilicates: single chains- pyroxenes b Diopside: CaMg [Si 2 O 6 ] a sinβ Where are the Si-O-Si-O chains?? Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

24 Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

25 Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

26 Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

27 Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

28 Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

29 Inosilicates: single chains- pyroxenes Perspective view Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)

30 Inosilicates: single chains- pyroxenes T M1 T Creates an I-beam like unit in the structure.

31 Inosilicates: single chains- pyroxenes T (+) M1 T Creates an I-beam like unit in the structure

32 Inosilicates: single chains- pyroxenes (+) (+) (+) 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

33 Inosilicates: single chains- pyroxenes (+) (+) (+) The pyroxene structure is then composed of alternation I-beams Clinopyroxenes have all I-beams oriented the same: all are (+) in this orientation (+) (+)

34 Pyroxene Chemistry The general pyroxene formula: W 1-P (X,Y) 1+P Z 2 O 6 Where W = Ca Na X = Mg Fe 2+ Mn Ni Li Y = Al Fe 3+ Cr Ti Z = Si Al Anhydrous so high-temperature or dry conditions favor pyroxenes over amphiboles

35 Pyroxene Chemistry The pyroxene quadrilateral and opx-cpx solvus Coexisting opx + cpx in many rocks (pigeonite only in volcanics) Wollastonite orthopyroxenes pigeonite clinopyroxenes 1200 o C Diopside clinopyroxenes Hedenbergite Solvus 1000 o C 800 o C Enstatite pigeonite orthopyroxenes Ferrosilite (Mg,Fe) 2 Si 2 O 6 Ca(Mg,Fe)Si 2 O 6

36 Pyroxene Chemistry Non-quad pyroxenes Jadeite NaAlSi 2 O 6 Aegirine NaFe 3+ Si 2 O Ca / (Ca + Na) Omphacite aegirineaugite Spodumene: LiAlSi 2 O Diopside-Hedenbergite Augite Ca(Mg,Fe)Si 2 O 6 Ca-Tschermack Tschermack s molecule CaAl2SiO 6

37 Inosilicates: double chains- amphiboles b Tremolite: Ca 2 Mg 5 [Si 8 O 22 ] (OH) 2 a sinβ Tremolite (001) view blue = Si purple = M1 rose = M2 gray = M3 (all Mg) yellow = M4 (Ca)

38 Inosilicates: double chains- amphiboles b Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 a sinβ 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

39 Inosilicates: double chains- amphiboles Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (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)

40 Inosilicates: double chains- amphiboles a sinβ (+) (+) (+) b (+) (+) Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 Same I-beam architecture, but the I-beams are fatter (double chains) All are (+) on clinoamphiboles and alternate in orthoamphiboles 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

41 pyroxene Inosilicates amphibole a b 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 90 o cleavages in pyroxenes while wider doublechain I-beams o cleavages in amphiboles

42 Pyroxene Cleavage in the Amphibole Chain Silicates Fig. 3.24

43 Amphibole Chemistry See handout for more information General formula: W 0-1 X 2 Y 5 [Z 8 O 22 ] (OH, F, Cl) 2 W = Na K X = Ca Na Mg Fe 2+ (Mn Li) Y = Mg Fe 2+ Mn Al Fe 3+ 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

44 Amphibole Chemistry Ca-Mg-Fe Amphibole quadrilateral (good analogy with pyroxenes) Tremolite Ca 2 Mg 5 Si 8 O 22 (OH) 2 Actinolite Ferroactinolite Ca 2 Fe 5 Si 8 O 22 (OH) 2 Anthophyllite Mg 7 Si 8 O 22 (OH) 2 Orthoamphiboles Cummingtonite-grunerite Clinoamphiboles Fe 7 Si 8 O 22 (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

45 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: Na 2 Mg 3 Al 2 [Si 8 O 22 ] (OH) 2 Riebeckite: Na 2 Fe 2+ 3 Fe3+ 2 [Si 8 O 22 ] (OH) 2 Sodic amphiboles are commonly blue, and often called blue amphiboles

46 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

47

48 Phyllosilicates SiO 4 tetrahedra polymerized into 2-D sheets: [Si 2 O 5 ] Apical O s are unpolymerized and are bonded to other constituents

49

50 Phyllosilicates Tetrahedral layers are bonded to octahedral layers (OH) pairs are located in center of T rings where no apical O

51 Phyllosilicates Octahedral layers can be understood by analogy with hydroxides Brucite: Mg(OH) 2 c Layers of octahedral Mg in coordination with (OH) Large spacing along c due to weak van der waals bonds

52 Phyllosilicates a 2 a 1 Gibbsite: Al(OH) 3 Layers of octahedral Al in coordination with (OH) Al 3+ 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

53 Phyllosilicates Kaolinite: Al 2 [Si 2 O 5 ] (OH) 4 T-layers and diocathedral (Al 3+ ) layers Yellow = (OH) (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

54 Phyllosilicates Serpentine: Mg 3 [Si 2 O 5 ] (OH) 4 T-layers and triocathedral (Mg 2+ ) layers Yellow = (OH) (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

55 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).

56 Serpentine Veblen and Busek, 1979, Science 206, Nagby and Faust (1956) Am. Mineralogist 41, S = serpentine T = talc The rolled tubes in chrysotile resolves the apparent paradox of asbestosform sheet silicates

57 Phyllosilicates Pyrophyllite: Al 2 [Si 4 O 10 ] (OH) 2 Yellow = (OH) T-layer - diocathedral (Al 3+ ) layer - T-layer weak van der Waals bonds between T - O - T groups T O T - T O T - T O T vdw vdw

58 Phyllosilicates Talc: Mg 3 [Si 4 O 10 ] (OH) 2 Yellow = (OH) T-layer - triocathedral (Mg 2+ ) layer - T-layer weak van der Waals bonds between T - O - T groups T O T - T O T - T O T vdw vdw

59 Phyllosilicates Muscovite: K Al 2 [Si 3 AlO 10 ] (OH) 2 (coupled K - Al T-layer - diocathedral (Al 3+ ) layer - T-layer - K K between T - O - T groups is stronger than vdw Al IV IV ) T O T K T O T K T O T

60 Phyllosilicates Phlogopite: K Mg 3 [Si 3 AlO 10 ] (OH) 2 T-layer - triocathedral (Mg 2+ ) 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

61 Phyllosilicates A Summary of Phyllosilicate Structures Fig Klein and Hurlbut Manual of Mineralogy, John Wiley & Sons

62

63 Clay: a sheet silicate Fig. 3.25

64 Phyllosilicates Chlorite: (Mg, Fe) 3 [(Si, Al) 4 O 10 ] (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)

65 Biopyriboles Why are there single-chain-, double-chain-, and sheet-polymer types, and not triple chains, quadruple chains, etc??

66 Biopyriboles It turns out that there are some intermediate types, predicted by J.B. Thompson and discovered in 1977 Veblen, Buseck, and Burnham Cover of Science: anthophyllite (yellow) reacted to form chesterite (blue & green) and jimthompsonite (red) Streaked areas are highly disordered Cover of Science, October 28, 1977 AAAS

67 Fig. 6, Veblen et al (1977) Science 198 AAAS anthophyllite jimthompsonite chesterite HRTEM image of anthophyllite (left) with typical double-chain width Jimthompsonite (center) has triple-chains Chesterite is an ordered alternation of double- and triple-chains

68 Biopyriboles Fig. 7, Veblen et al (1977) Science 198 AAAS Disordered structures show 4-chain widths and even a 7-chain width Obscures the distinction between pyroxenes, amphiboles, and micas (hence the term biopyriboles: biotite-pyroxene-amphibole)

69

70 Tectosilicates Stishovite 10 Pressure (GPa) 8 6 Coesite 4 2 α - quartz β - quartz Liquid Cristobalite Tridymite After Swamy and Saxena (1994) J. Geophys. Res., 99, 11,787-11, Temperature o C

71 Tectosilicates Stishovite Low Quartz Coesite β - quartz α - quartz Liquid Cristobalite Tridymite 001 Projection Crystal Class 32

72 High Quartz at 581 o C Tectosilicates Stishovite Coesite β - quartz α - quartz Liquid Cristobalite Tridymite 001 Projection Crystal Class 622

73 Tectosilicates Stishovite Cristobalite Coesite β - quartz α - quartz Liquid Cristobalite Tridymite 001 Projection Cubic Structure

74 Tectosilicates Stishovite Stishovite Coesite β - quartz α - quartz Liquid Cristobalite Tridymite High pressure Si Si VI

75 Tectosilicates Low Quartz Stishovite Si IV Si VI

76 Quartz structure

77

78 Banded Agate Fig. 3.27

79 Green Feldspar Fig. 3.28

80 Feltspat

81 Ortoklas/Mikroklin Albitt Anortitt

82 Avblanding av feltspat ved avkjøling

83 Kalifeltspat (mikroklin) Plagioklas

84 Tectosilicates Feldspars Substitute Al 3+ for Si 4+ allows Na + or K + to be added Substitute two Al 3+ for Si 4+ allows Ca 2+ to be added Albite: NaAl AlSi 3 O 8

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