Gypsum

Sulfate Minerals More than 100 different minerals, separated into hydrous (with H 2 O) or anhydrous (without H 2 O) groups Gypsum (CaSO 4 *2H 2 O) and anhydrite (CaSO 4 ) are the most common of the sulfate minerals Gypsum typically forms in evaporitic basins – a polymorph of anhydrite (  -CaSO4) forms when the gypsum is later dehydrated)

Halide Minerals Minerals contianing halogen elements as dominant anion (Cl - or F - typically) Halite (NaCl) and Sylvite (KCl) form in VERY concentrated evaporitic waters – they are extremely soluble in water, indicate more complete evaporation than does gypsum Fluorite (CaF 2 ) more typically occurs in veins associated with hydrothermal waters (F - in hydrothermal solutions is typically much higher – leached out of parent minerals such as biotites, pyroxenes, hornblendes or apatite)

Gypsum formation can demarcate ancient seas that dried up (such as the inland seas of the Michigan basin) or tell us about the history of current seas which have dried up before (such as the Mediterranean Sea)

Halite Structure NaCl  Na + (gray) arranged in CCP with Cl - (red) at edges and center (in octahedral cavities)

Flourite structure CaF 2  Ca 2+ (gray) arranged in CCP, F- ions (red) inside ‘cage’

Sulfate Minerals II Barite (BaSO 4 ), Celestite (SrSO 4 ), and Anglesite (PbSO 4 ) are also important in mining. These minerals are DENSE  Barite =4.5, Anglesite = 6.3 (feldspars are ~2.5)

Barite, Celestite, Anglesite Metals bond with sulfate much more easily, and thus are generally more insoluble – they do not require formation in evaporitic basins What do they indicate then? Ba, Pb, Sr – very low SO 4 2- Lots of SO 4 2- Not very much Ba, Sr, Pb

Just silica… Chert – extremely fine grained quartz –Forms as nodules in limestone, recrystallization of siliceous fossils –Jasper – variety with hematite inclusions  red –Flint – variety containing organic matter  darker color Chalcedony – microcrystaliine silica (very similar to low quartz, but different – it is yet uncertain how different…)  typically shows banding, often colored to form an agate (rock formed of multiple bands of colored chalcedony) Jasper – variety colored with inclusion of microcrystsalline oxides (often iron oxides = red) Opal – a hydrogel (a solid solution of water in silica) – forms initially as water + silica colloids, then slowly the water diffuses into the silica  making it amorphous (no XRD pattern!) –Some evidence opal slowly recrystallizes to chalcedony

Opal - Gemstone

Agates

Oxides - Oxyhydroxides FeOOH minerals  Goethite or Limonite (FeOOH)  important alteration products of weathering Fe-bearing minerals Hematite (Fe 2 O 3 )  primary iron oxide in Banded Iron Formations Boehmite (AlOOH)  primary mineral in bauxite ores (principle Al ore) which forms in tropical soils Mn oxides  form Mn nodules in the oceans (estimated they cover 10-30% of the deep Pacific floor) Many other oxides important in metamorphic rocks…

Mn oxides - oxyhydroxides Mn exists as 2+, 3+, and 4+; oxide minerals are varied, complex, and hard to ID –‘Wad’  soft (i.e. blackens your fingers), brown-black fine-grained Mn oxides –‘Psilomelane’  hard (does not blacked fingers) gray- black botroyoidal, massive Mn oxides XRD analyses do not easily distinguish different minerals, must combine with TEM, SEM, IR spectroscopy, and microprobe work

Romanechite Ba.66 (Mn 4+,Mn 3+ ) 5 O 10 *1.34H 2 O  Psilomelane Pyrolusite MnO2 Ramsdellite MnO2 Nsutite Mn(O,OH)2 Hollandite Bax(Mn4+,Mn3+)8O16 Cryptomelane Kx(Mn4+,Mn3+)8O16 Manjiroite Nax(Mn4+,Mn3+)8O16 Coronadite Pbx(Mn4+,Mn3+)8O16 Todorokite (Ca,Na,K)X(Mn4+,Mn3+)6O12*3.5H2O Lithiophorite LiAl2(Mn2+Mn3+)O6(OH)6 Chalcophanite ZnMn3O7*3H2O Birnessite (Na,Ca)Mn7O14*2.8H2O Vernadite MnO2*nH2O Manganite MnOOH Groutite MnOOH Feitknechtite MnOOH Hausmannite Mn 2+ Mn 2 3+ O4 Bixbyite Mn2O3 Pyrochroite Mn(OH)2 Manganosite MnO Mn Oxide minerals (not all…) Wad

Al oxides Aluminum occus in economic deposits principally as bauxite Bauxite is a mixture of Al oxides and oxyhydroxides: –Diaspore - AlO(OH) –Gibbsite - Al(OH)3 –Böhmite - AlO(OH) Al is a residual phase and bauxite occurs where weathering is extreme and thick layers of aluminum oxyhydroxide are left over

Iron Oxides Interaction of dissolved iron with oxygen yields iron oxide and iron oxyhyroxide minerals 1 st thing precipitated  amorphous or extremely fine grained (nanocrystaliine) iron oxides called ferrihydrite Fe 2+ O2O2

Ferrihydrite Ferrihydrite (Fe 5 O 7 OH*H 2 O; Fe 10 O 15 *9H 2 O  some argument about exact formula) – a mixed valence iron oxide with OH and water

Goethite Ferrihydrite recrystallizes into Goethite (  - FeOOH) There are other polymorphs of iron oxyhydroxides: –Lepidocrocite  -FeOOH –Akaganeite  -FeOOH

Iron Oxides Hematite (Fe 2 O 3 ) – can form directly or via ferrihydrite  goethite  hematite Red-brown mineral is very common in soils and weathering iron-bearing rocks

Magnetite (Fe 3 O 4 ) – Magnetic mineral of mixed valence  must contain both Fe 2+ and Fe 3+  how many of each?? ‘Spinel’ structure – 2/3 of the cation sites are octahedral, 1/3 are tetrahedral

Banded Iron Formations (BIFs) HUGE PreCambrian formations composed of hematite-jasper-chalcedony bands Account for ~90% of the world’s iron supply Occur only between 1.9 and 3.8 Ga  many sites around the world  Hammersley in Australia, Ishpeming in Michigan, Isua in Greenland, Carajas in Brazil, many other sites around the world…

BIFs and bacteria Early earth did not have free O 2, as microbial activity became widespread and photosynthetic organisms started generating O 2, the reduced species previously stable (without the O 2 ) oxidized – for Fe this results in formation of iron oxide minerals