Systematic Classificatin of Minerals

Carbonates, Sulfates, and Phosphates

Classification of the Minerals

Carbonates

(Nesse, Ch. 17, p. 326-339)

dolomite

calcite

magnesite

rhodochrosite
photos: mindat.org

aragonite

Carbonates

(Nesse, Ch. 17, p. 326-339)

diverse group of non-silicate minerals

basic formula:

XCO3 or XY(CO3)2

X , Y = divalent cations (Ca,Mg,Fe,Mn)

4 main carbonate groups distinguished based on

structure + composition:

calcite group
dolomite group
aragonite group
OH-bearing group

Carbonates

Reason for electrostatic valency calculations:

Amount of residual charge indicates relative strength of
bonds with cations, which are reflected in the hardness
of the mineral

Carbonates

(Nesse, Ch. 17, p. 326-339)

basic building block: [CO3]23-fold symmetry underlies typical

rhombohedral (trigonal) structure
of most carbonates

[CO3]2-

Mg2+

Ca2+

[CO3]2Ca2+

calcite

dolomite

Carbonates
Aragonite
(High-P) Orthorhombic

Calcite
(Low-P - Hexagonal)

Most are Hexagonal

Calcite Structure

Calcite

The structure of calcite is described as a "modified NaCl"

structure, but calcite is not cubic. The carbonate groups
stretch the atomic planes and distort the cube into a
rhombohedron.

Kelompok Mineral Karbonat

Kalsit
(Rhombohedral)

Dolomit
(Rhombohedral)

Aragonit
(Orthorombik)

Kalsit

CaCO3

Dolomite

CaMg(CO3)2

Aragonite

CaCO3

Magnesit

MgCO3

Ankerite

Ca(Mg,Fe)(CO3)2 Witherite

BaCO3

Siderit

FeCO3

Kutnoherite CaMn(CO3)2

Rhodochrosite

MnCO3

Smithsonite

ZnCO3

Strontianite

SrCO3

Cerrusite

PbCO3

Aragonite Group
Carbonate minerals with a single divalent cation of radius > 1.00 . With
increasing radius the species are Aragonite (CaCO3), Strontianite (SrCO3),
Cerussite (PbCO3), and Witherite (BaCO3). Aragonite is denser than calcite,
and is the high P polymorph. It crystallizes at ambient conditions and
persists metastably for millions of years. The orthorhombic structure is
nearly hexagonal with c as the unique axis.

Dolomite CaMg(CO3)2
Forms during seasonal high tides that flood limestone (calcite) islands
with seawater. Mg++ in the seawater replaces some of the Calcium ions.
Has very distinctive crystals

Carbonates

(Nesse, Ch. 17, p. 326-339)

NB: calcite and dolomite are

not end members in a single
solid solution series

distinguishing features
(carbonates in general):
variable relief in PPL
uniaxial ve
very high birefringence

Carbonates

(Nesse, Ch. 17, p. 326-339)

distinguishing features
(calcite vs dolomite):
orientation of twins
relative to cleavage

Carbonates

(Nesse, Ch. 17, p. 326-339)

other calcite group minerals

(limited solid solution with calcite)

other dolomite group minerals

(solid solution with dolomite):
ankerite
CaFe(CO3)2
kutnahorite CaMn(CO3)2

Carbonates

(Nesse, Ch. 17, p. 326-339)

aragonite:

orthorhombic polymorph of CaCO3

other aragonite group minerals:
witherite
BaCO3
strontianite SrCO3
cerussite
PbCO3

Carbonates

(Nesse, Ch. 17, p. 326-339)

aragonite:

orthorhombic polymorph of CaCO3

stable at high P,
low T

also formed by some organisms

(metastable; reverts to calcite
during diaganesis)

Other Carbonates
Azurite - Cu3(CO3)2(OH)2 (Blue)
Malachite Cu2CO3(OH)2 (Green)

Rhodochrosite MnCO3

Calsite Group

Dolomite
Group

Aragonite
Group

OH-bearing group

Carbonates

(Nesse, Ch. 17, p. 326-339)

occurrence:

dominant constituents of limestones and dolostones

form primary phases in some igneous rocks
common in veins and other secondary assemblages
marbles and other metcarbonate rocks

use:

calcite: essential component of industrial cement;

raw material for lime (CaO) which has
a wide variety of uses; pharmaceuticals;
agriculture; neutralising agent; building stone
dolomite: a variety of industrial uses including
agriculture, ceramics, cement, aggregate;
mined for Mg in some places

Borate Groups

Borates
Kernite Na2B4O6(OH)23H2O
H 3; SG 1.95

Borax - Na2B4O5(OH)48H2O
H 2-2.5; SG 1.7

Ulexite NaCaB5O6(OH)65H2O
H 1-2.5; SG 1.96

Television Rock

Borate
Minerals

Sulphates
gypsum

(Nesse, Ch. 17, p. 340-346)

anhydrite

desert rose:

intergrown crystals
of gypsum or barite
cementing fine sand

barite

photos: mindat.org

Carbonates
Next time

Sulfates
SO 4-Today

Phosphates

Silicates
After Thanksgiving

NEXT:

Mineral
Groups
formed with
Anionic
Complexes

The Sulfate Ion has Sulfur in tetrahedral coordination with 4 oxygens.

Sulfur, element 16, with 1S2 2S2 2P6 3S2 3P4 electrons, so 6 electrons in
the outer shell of the neutral atom. These 6 electrons shared with the
Oxygens,1S2 2S2 2P4,
leaving the Sulfate Ion SO4 with a charge of -2, SO4 --

Two double bonds and two single bonds

Notice BOTH S and O have 6 valence electrons

Pp 60-61
Electronegativities: S 2.4, O 3.5
Difference 1.1, only 25% ionic
K&D Fig 3.21 So mostly covalent, i.e.
electrons spend almost as much
time near Sulfur

Figure 17.1 b Sulfate Ion

SO 4-- We consider the
S valence +6 (as if ionic)
O valence always -2

Residual charge on each

Oxygen = -1/2
x 4 Oxygens = -2
Amount of residual charge
(charge not neutralized)
indicates relative strength
available for bonds with
cations, reflected in the
hardness of the mineral

Sulfates: Metals + Sulfate Ion

Again: The Sulfate Ion: strong covalent bonds, acts as a unit.

The Sulfate Ion has Sulfur in tetrahedral coordination with 4 Oxygens.

Sulfur, element 16, with 1S2 2S2 2P6 3S2 3P4 electrons, so 6 electrons in
the outer shell of the neutral atom. These 6 electrons shared with the

Oxygens, leaving the Sulfate Ion SO4 with a charge of -2, SO4 --

Sulphates

(Nesse, Ch. 17, p. 340-346)

minerals containing [SO4]2forms tetrahedral groups

linked by divalent cations

gypsum
CaSO4.2H2O
anhydrite
CaSO4
barite BaSO4

gypsum: strongly bonded CaSO4 layers

alternate with H2O layers

anhydrite: [SO4]2- groups linked by Ca2

in 8-fold co-ordination

Sulphate Group

Sulphates

(Nesse, Ch. 17, p. 340-346)

gypsum: low relief, low d

inclined extinction
anhydrite: moderate relief,
moderate to high d
parallel extinction

Sulphates

(Nesse, Ch. 17, p. 340-346)

[SO4]2- groups linked by

Ba2+
in 12-fold co-ordination
barite:

official IMA name is spelled baryte

moderate relief, low d
parallel extinction

Sulphates

(Nesse, Ch. 17, p. 340-346)

occurrence:

common in marine evaporite deposits

anhydrite can precipitate directly or form by
dehydration of gypsum
barite: common in hydrothermal deposits but can also form
in terrestrial evaporites
gypsum, anhydrite:

use:
important construction material (gyprock)
also used in cement, agriculture
anhydrite: agriculture, cement
barite: main ore mineral for Ba;
also used in drilling mud, pharmaceuticals, glass,
ceramics, and a variety of other industrial uses
gypsum:

Common Sulfates
HYDROUS

ANHYDROUS

H: 2
SG: 2.32

Gypsum CaSO42H2O

H: 3-3.5
SG: 2.9

Anhydrite CaSO4
H: 3-3.5
SG: 4.5

Barite BaSO4 and similar

Sulfate Ion Radius = ~1.49 Angstroms

S in SO4 TETRAHEDRAL [4] Coordination w Oxygen
In all three, cation in 12fold coordination w
Oxygens O

Cation

Val.

Cation Radii

Barium

Ba+2

1.68 [12]

Barite

e.g. in Barite, each BaO12

group is bonded to seven
individual (SO4)-2
tetrahedra

Strontium Sr+2

1.48 [12]

Celestite

Lead

1.57 [12]

Anglesite

Pb+2

Solid solutions limited within these species. Why?

(Angstroms)

XSO4

These three very difficult to distinguish in hand specimens

Barite Group Structure

Cation of Barium Ba++, of Strontium Sr++, of Lead Pb++ surrounded by 12 oxygens

Barite
BaSO4 Orthorhombic 2/m 2/m 2/m
H 3 - 3.5 G 4.5
Gangue in hydrothermal veins, w/ Ag,
Pb, Cu. Often near hot springs.
Use for heavy drilling mud
Absorbs x-rays in medical diagnostic
studies of the digestive tract.

Barite BaSO4

Orthorhombic 2/m 2/m 2/m

Mined locally Hopewell

All photos courtesy of

John Betts

http://rruff.geo.ari
zona.edu/doclib/
cm/vol15/CM15_
522.pdf

Barite BaSO4

Other Sulfates in the Barite Group

Celestite SrSO4
Orthorhombic
2/m 2/m 2/m
Cleavage {001} perfect,
{210} good
H 3-3.5
G 3.95-3.97
Also called Celestine

Often light sky blue in color

Other Sulfates in the Barite Group

Anglesite PbSO4
Orthorhombic
2/m 2/m 2/m
Cleavage {001} good,
{210} imperfect
H3
G 6.2-6.4
Much greater SG

Gypsum Hydrous CaSO4

CaSO4 . 2H2O Monoclinic 2/m
{010} perfect H 2, G 2.3
Luster vitreous to pearly
Varieties Selenite clear simple 2/m
Satin Spar fibous
Alabaster fine-grained massive
Source for drywall (gypsum board,
sheetrock) and Plaster of Paris

Gypsum (continued)
Monoclinic
2/m

Pictures courtesy John Betts and mindat.org

Gypsum Structure

From Klein and Hurlburt Manual of Mineralogy 20th Edition.

Looking down along c-axis. Note perfect (010) cleavages.

Anhydrite

CaSO4 Orthorhombic 2/m 2/m 2/m

Xtals rare {010} {001} {100} tabular
H 3-3.5, G ~3
Luster vitreous to pearly on cleavage

Used in making H2SO4

Anhydrite

Photos by Martins da Pedra courtesy Mindat.org

Anhydrite Structure CaSO4

CaSO4 . 2 H2O
Gypsum
68oC
Hemihydrate

CaSO4 . 1/2 H2O

95oC

CaSO4
Anhydrite
Anhydrite may be formed by the dehydration of Gypsum

Evaporite Minerals
Most of Evaporites are Halides and Sulfates
Volume of water
50% calcite precipitates,
gypsum at 20% volume,
halite at at 10% volume

Evaporites

Discussion: Dead Sea, Playas

Messinian Crisis

Precipitate when concentration in water at To

reaches their saturation limit.
Minerals precipitate in reverse order of their
solubilities,
Order of precipitation from sea water is:
Calcite (first, but very little volume)
Gypsum (CaSO4-2H2O) and/or Anhydrite
(CaSO4). To dependant.
Halite (i.e. common salt, NaCl)
Potassium and magnesium salts KCl, KNO3,
MgSO47H2O

Conditions for precipitation

Seawater influx into confined basins
New rift, shallow bay, playa, isolated
basin in dry climate.

Freshwater evaporates away

Lower freshwater influx than
evaporates
Saturated solution exists

Playas (cont'd)

A Playa in Death Valley, California

Evaporite crust

Swimmers in hypersaline Dead Sea

Evaporite deposits indicate high aridity index.

Salt Domes: evaporites rise

Mainly NaCl Halite as evaporite
deposits, very low density.
Rising columns deflect sediments
Forms hydrocarbon traps that make
petroleum affordable
Gulf Coast Jurassic rifting confined
basin

Gulf Coast continental margin

Rising Salt Domes

Salt Dome lease

351-17
Gulf Of Mexico
Courtesy Shell
Exploration,
Houston
Used with
Permission

Evaporation
of mixed
Waters

Influx of
sea water

1. Aragonite
2. Gypsum
3. Anhydrite
4. Dolomite
5. Halite
accumulate
in this order

GEOL 751 Lecture 6:

Cementation & Diagnesis

Influx of
Magnesium
Rich
Continental
Ground
Waters

Phosphate Minerals

Phosphates
Apatite Ca5(PO4)3(F,Cl,OH)
prismatic hexagonal crystals
common in igneous rocks and
hydrothermal deposits
- variable colors the deceiver

Other Common Phosphates

Monazite (Ce,La,Y,Th)PO4

Ore mineral for Rare Earth Elements

Useful mineral in U-Pb and Th age dating

Wavellite Al3(PO4)2(OH)35H2O
Radiating globular aggregates

Turquoise
CuAl6(PO4)4(OH)85H2O

Chromate: Crocoite
PbCrO4
Monoclinic 2/m.
Commonly in prismatic crystals,
vertically striated
b=102o33
Cleavage {110} perfect
H 2.5 3
G 5.9-6.1
Luster Adamantine
Color bright red to orange- red
Streak orange-yellow

Arsenate

Vanadates

Tungstates & Molybdates

Tungstates & Molybdates

Wolframite (Fe,Mn)WO4
SG: 7-7.5

Scheelite CaWO4
SG: ~6

Wulfenite PbMoO4
SG: 6.8

Tungstates & Molybdates