Accessory minerals. Al 2 SiO 5 modifications and other Al-rich minerals. Thesis: Prof. RNDr. Milan Novák, CSc.
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1 Accessory minerals Prof. RNDr. Milan Novák, CSc. Al 2 SiO 5 modifications and other Al-rich minerals Thesis: 1. Introduction 2. Al 2 SiO 5 modifications 3. Alteration of Al 2 SiO 5 4. Related minerals 5. Other Al-rich minerals
2 1. Introduction Minerals Al 2 SiO 5 are very important accessory and locally also rockforming minerals typical for Al-rich rocks from low- to high-grade metamorphic to various acid magmatic. Along these most common Al-rich minerals also several paragenetically and structurally related minerals occur (e.g., staurolite, boralsilite and mullite), or originated during low-t alteartions (e.g. diaspore, pyrofylite). Andalusite, Dolní Bory
3 2. Al 2 SiO 5 Minerals Al 2 SiO 5 Sillimanite Al 6 Al 4 O SiO 4 ortorombic Pbnm, 2/m2/m2/m. Andalusite Al 6 Al 5 O SiO 4 ortorombic Pnnm, 2/m2/m2/m Kyanite Al 6 Al 6 O SiO 4 triclinic C1, 1 Sillimanite a 7.486, b 7.657, c Å, V Å 3, Z 4 Andalusite a 7.795, b 7.896, c Å, V Å 3, Z 4 Kyanite a 7.112, b 7.844, c Å, α 88.9, β 101.1, γ 105.9, V Å 3, Z 4 Chemical composition is commonly close to the ideal formula. minor and trace elements: Sillimanite B 3+, Mg, Fe 3+ Andalusite Mn 3+, Fe 3+, Cr 3+ Kyanite Cr 3+, V 3+, Fe 3+
4 Crystal structures 2. Al 2 SiO 5
5 2. Al 2 SiO 5 Commonly close to ideal formula except Mn 3+ and partly in Fe 3+ in andalusite where - kanonaite Mn 3+6 Al 5 O SiO 4 is further member of this group. Entering of Al instead Si into T-site in sillimanite tends to mullite. Andalusite-kanonaite Mn 3+ - full miscibility. Sillimanite-mullite Al - limited miscibility.. Sillimanite-boralsilite B - miscibility exists but not clear. Minor and trace elements commonly enter both Al-sites, but more into octahedral site (Mn 3+ in Mn-andalusite), B enters T-site.
6 Properties: 2. Al 2 SiO 5 Sillimanite grey, white, yellowish Andalusite - pink, red, brown-red, grey, green pleochroic Kyanite - blue, grey colorless Hardness 6-7, kyanite 7-5, density = 3,2-3,6 (kyanite). Variety: fibrolit fibrous sillimanite viridine green Mn-andalusite chiastolite andalusite se with sectorial zoning Kyanit, Frymburk
7 Tripl point Al 2 SiO 5 All modifications have triple point and its position in PT diagrams is extremekly important for geological implications. Richardson et al. (1969) Holdaway (1971) Robie a Hemingway (1984) Holland and Powell (1985) Pattison (1989) 2. Al 2 SiO 5 Sillimanite, Něchov
8 2. Al2SiO5
9 2. Al2SiO5
10 2. Al 2 SiO 5 From all figures it is clear that the position of the triple point is still not strictly defined. Recently triple point of Holdaway (1971) or from Pattison (1989) is used. Chiefly the position of the univariant reaction andalusite=sillimanite is problematic. Sillimanite Problem of fibrolite fibrous sillimanite-fibrolite is more abundatnt then prismatic sillimanite. Its stability likely overlaps field of andalusite in PT diagrams due to distinct grain-size used in experiments.
11 2. Skupina Al 2 SiO 5 Occurrences: Al-rich rocks with low Na+K/Al. Sillimanite regional metamorphosed rocks of medium- to high grade, migmatites Andalusite contakt and regional metamorphic rocks (Branná), granites, pegmatites (Dolní Bory) Kyanite regional metamorphic rocks of medium- to high grade, (Frymburk, Kovářová, Branná), granulites Andalusit, Dolní Bory
12 3. Al 2 SiO 5 - alterations Refractority of Al 2 SiO 5 during hydrothermal alterations is moderate to high, highly refraktory to weathering, so they are common in clastic sediments. Produkts of alterations are: in systems with low activity of alkalis diaspore, pyrofylite, kaolinite in systems with high activity of alkalis muscovite, paragonite Dia Dia Prf Msc Prf And Foi And Alteration of andalusite to pyrofylite and muscovite (Dolní Bory)
13 3. Al 2 SiO 5 - alterations
14 4. Related minerals Kanonaite Mn 3+ Al O SiO 4 ortrombic, Pnnm, 2/m2/m2/m, a 7.959, b 8.047, c Å, V Å3, Z 4 substitution: Mn 3+ - Al dark green with strong pleochroism, in Mn-rich rocks Mn-andalusite and spessartine, Kojetice
15 Kanonaite-Mnandalusite, Kojetice 4. Related minerals
16 4. Related minerals Mullite Al 4+2x Si 2-2x O 10-x ortorombic, Pbam, 2/m2/m2/m, a , b , c Å, V Å3, Z 2, substitution: 2Al O - 2Si Fine-graind fibrous in HT contact metamorphism and ceramics
17 4. Related minerals Boralsilite Al 16 B 6 Si 2 O 37 ortorombic substitution: 2B - 2Si O Extremely rare Brs Grd Boralsilite on grandidierite, Horní Bory
18 Staurolite 4. Related minerals General formula A 4 B 4 C 18 D 4 T 8 O 40 X 8 Monoclinic (pseudoortorombic) A = Fe 2+, Mg, ( > 2) M(4A),M(4B) B = Fe 2+, Zn, Co, Mg, Li, Al, Fe 3+, Mn, T(2) C = Al, Fe 3+, Cr,V,Mg,Ti M(1A),M(1B),M(2) D = Al,Mg, ( > 2) M(3A), M(3B) T = Si, Al T(1) X = OH,F,O O(1A), O(1B) End-member compositions A B C D T O X 4 Fe 2+ 4 Al 16 Al 2 2 Si 8 O 40 (OH) 2 O 6 2 Fe Al 16 Al 2 2 Si 8 O 40 (OH) 6 O 2 4 Fe 2+ 4 Al 16 4 Si 8 O 40 (OH) 8 4 Fe 2+ 4 Al 16 Al 2 2 Si 4 Al 4 O 40 (OH) 6 O 2 4 Fe 2+ 4 Al 12 Mg 4 Al 2 2 Si 8 O 40 (OH) 6 O 2 4 Li 4 Al 16 Al 2 2 Si 8 O 40 (OH) 6 O 2
19 4. Related minerals Properties: Color: brown to black pleochroic refractory indices: a , , , density: , hardness: 7-71/2
20 Substitutions: 4. Related minerals
21 occurrences: Al-rich metamoprhic rocks 4. Related minerals Typical features of natural staurolites: high Fe: decrease in X Mg Metapelites of medium-grade tourmaline > cordierite > chlorite > biotite > staurolite > garnet typically minor Li: decrease in X Li Metapelites of medium-grade staurolite > cordierite > biotite > muscovite > garnet, tourmaline, chloritoid commonly high Zn: ratio Zn/Fe in staurolite 10x to 100x highre then in associated minerals (garnet, biotite, chlorite).
22 5. Additional Al-rich minerals Safiríne (Mg,Fe 2+,Fe 3+,Al) 8 O 2 (Al,Si) 6 O 18 monoclinic, space group P2 1 /m Rare accessory phase in Al-rich Si-poor metamorphic rocks Propeeties: Color: green, blue, grey strongly pleochroic: Indexy lomu: a , b , g , Density: g/cm 3, hardness: 71/2 Typical substitution MgSi Al -2
23 Corundum Al 2 O 3 trigonal R 3 c 5. Additional Al-rich minerals Color: grey, bluish, blue, red, yellow and others (ruby, sapphire) Density: 4,0-4,1 g/cm 3, hardness: 9
24 5. Additional Al-rich minerals korund
25 5. Additional Al-rich minerals Spinels Spinel MgAl 2 O 4 hercynite FeAl 2 O 4 Gahnite ZnAl 2 O 4 Cubic Fd3m Color: grey, bluish, blue, red, yellow, black, green and others Density: 3,6-4,5 g/cm 3, hardness: 7-8 substitutions: Mg-Fe 2+ -Zn-Mn, Al-Fe 3+ -Cr
26 5. Additional Al-rich minerals spinel
27 Yoderite 5. Additional Al-rich minerals Mg 2 (Al,Fe 3+ ) 6 Si 4 O 18 (OH) 2 monoclinic, space group P2 1 /m, class 2/m. Rare mineral known only from quartz-kyanite-talc schists (~ 10 kbar, ~ 800 o C). Yoderit je indicator of high fo 2 in deep part of earth crust. Color: dark violet to emerald green pleochroic Indexy lomu: a 1.689, b 1.691, g 1.715, Density: 3.39 g/cm 3, hardness: 6
28 5. Additional Al-rich minerals : Kornerupine (Mg,Fe) (Al,Mg,Fe) 9 (Si,Al,B) 3 (O,OH,F) 22 Grandidierite (Mg,Fe) Al 3 O 2 (BO 3 )SiO 4 Werdingite (Mg,Fe) 2 Al 12 (Al,Fe) 2 Si 4 (B,Al) 4 O 37 In high-grade Al,B-rich rocks Cor Tur Grd Grandidierite replaced by tourmaline and corundum, Horní Bory
29 6. Conclusions Al-rich mineráls are important for geological implications due to: 1. Al 2 SiO 5 modifications are important for estimation of PT-conditions. 2. Presence of Al-rich rocks incicates: - high Al in rock interpretation of source sedimentary rock) - ratio Al/Si. - Low activity of alkalis. 3. Late alterations of Al-rich minerals indicate PTX-conditions of these proceses
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