1. 1 Mineral Composition Variability GLY 4200 Fall, 2015

2. 2 Ionic Substitution - Size Size: Fe 2+ ↔ Mg 2+ ↔ Ni 2+  (0.86Å) (0.80Å) (0.77Å)

3. 3 Ionic Substitution - Charge Coupled substitution  Ca 2+ & A1 3+ ↔ Na + and Si 4+  Example: Plagioclase feldspar  NaAlSi 3 O 8 ↔ CaAl 2 Si 2 O 8 Void  Ca 2+ & Void ↔ 2 Na +

4. 4 Victor M. Goldschmidt Swiss-born Norwegian mineralogist and petrologist who laid the foundation of inorganic crystal chemistry and founded modern geochemistry Born 1888, died 1947

5. 5 Goldschmidt’s Rules - Size Atomic substitution is controlled by size (i.e., radii) of the ions  Free substitution can occur if size difference is less than ~15%  Limited substitution can occur if size difference is 15 - 30%  Little to no substitution can occur if size difference is greater than 30% If there is a small difference of ionic radius the smaller ion enters the crystal preferentially

6. 6 Goldschmidt’s Rules - Charge Atomic substitution is controlled by charge of the ions --> cannot differ by more than 1 For ions of similar radius but different charges, the ion with the higher charge enters the crystal preferentially

7. Other Factors Affecting Solid Solution Temperature  Minerals expand at higher T  Minerals contract at lower T  Greater tolerance for ionic substitution at higher T  Pressure  Increasing pressure causes compression  Less tolerance for ionic substitution at higher P  Availability of ions – ions must be readily available for substitution to occur

8. 8 Spin State High-spin versus low-spin

9. 9 Solid Solution

10. 10 Types of Crystalline Solution 1. Substitutional - Mg 2+ for Fe 2+ 2. Omission - Ca 2+ & void for 2 Na +

11. 11 Crystalline Substitution 2 3. Vacancy - normally vacant sites can be filled as part of a coupled substitution. An important example is in the mineral group amphibole. An abundant, end- member component of this group of minerals is tremolite which ideally has the formula:  []Ca 3 Mg 5 Si 8 O 22 (OH) 2  where [] represents a vacant crystallographic site. Minerals can utilize this vacant site in coupled substitutions such as: [] + Si 4+ = Na + + Al 3+

12. 12 Crystalline Substitution 3 4. Interstitial- Atom or ion occupies space in between the normal sites  Often this is H+, a very small cation  In some crystal structures these voids are channel-like cavities. A good example is the mineral beryl (Be 3 Al 2 Si 6 O 18 )

13. Beryl Cavities 13

14. 14 Schottky Defect

15. 15 Frenkel defect

16. 16 HCP Stacking Defect ABABABCABAB H H C H H

17. 17 CCP Stacking Defect ABCABCABABCABC C C H C C

18. 18 Grain Boundary Defect Two lattices grow together, with some displacement of ions (shown in blue)

19. 19 Polymorphous Minerals All have the formula Al 2 SiO 5

20. 20 Ditypous Minerals Top – sphalerite (aka zinc blende) CCP Bottom – wurzite HCP

21. Order-disorder If one type of ion substituting for another prefers a certain type of site over another the structure is ordered. Example: There are three polymorphs of potassium feldspar (KAlSi 3 O 8 )  Sanidine  Orthoclase  Microcline 21

22. Sanidine-Microcline Transition Sanidine has a high degree of structural symmetry and a relatively random distribution of Si and Al (both of these elements can fit into tetrahedral sites, surrounded by four oxygens) When cooled, contraction occurs This produces a tendency for Al to go into some of the smaller sites, and Si to go into some of the larger ones, which means the distribution of aluminum and silicon is more ordered The low-temperature polymorph formed from sanidine by disorder polymorphism is microcline. 22

23. Effect of Ordering The ordering of elements in the sanidine- microcline transition reduces the structural symmetry Sanidine has a 2-fold rotation axis and a mirror plane not found in microcline 23

24. 24 Pseudomorphism Pseudomorphic goethite after cubic pyrite crystals clustered on a terminated aegerine crystal Group is 4.6cm Eric Farquharson specimen

25. Non-crystalline matter Matter may form in a non-crystalline state, or may become non-crystalline as a result of alteration Examples  Metamict  Mineraloid 25

26. Metamict Certain minerals occasionally contain interstitial impurities of radioactive compounds, or are composed of radioactive elements Alpha radiation emitted from the radioactive elements is responsible for degrading a mineral's crystal structure through internal bombardment. If the structure is destroyed completely (or nearly) then it is said to be metamict 26

27. Effects Effects of metamictization are extensive The process lowers a mineral's refractive index, hardness, and specific gravity An example of a mineral containing a radioactive element is thorite (ThSiO 4 ) A frequent host of radioactive impurities is zircon, (ZrSiO 4 ) 27

28. 28 Mineraloids Upper left –amber Lower left – obsidian Right – tektite glass

29. 29 Exsolution Augite with pigeonite exsolution lamellae Pigeonite is a Ca- poor clinopryoxene Exsolution in pyroxene