Geochemistry

• The study of the distribution of chemical elements and natural

compounds on the earth and in the atmosphere and the chemical
processes that affect the earth – USGS
• Extends beyond earth
• Dynamic --- exchange of chemical elements in the different
environments
Week 2
• Rock forming minerals
• Major elements
• Major element discrimination diagrams
• Major element ratios
• Mineral chemistry
Rock forming minerals:
Essential minerals: minerals used to classify the rock

• Igneous: minerals in the Bowen’s reaction series

• Sedimentary: all igneous and metamorphic minerals plus carbonates
and halides, sulphates, phosphates…(minerals in lithic and skeletal
fragments included)
• Metamorphic: Example: andalusite, kyanite, sillimanite, garnet… plus
igneous and sedimentary minerals
Rock forming minerals (Igneous): crystallized from melt
orthopyroxene plagioclase Groundmass glass
PL SiO2 52.32 SiO2 56.09 SiO2 65.96
TiO2 0.12 TiO2 0.01 TiO2 0.88
GM OPX Al2O3 1.684 Al2O3 27.98 Al2O3 12.71
FeO 22.92 FeO 0.52 FeO 6.60
MnO 0.28 MnO MnO 0.13
MgO 21.79 MgO 0.09 MgO 1.08
CaO 2.038 CaO 10.93 CaO 3.36
Na2O 4.80 Na2O 2.70
K2O 0.27 K2O 3.11
*note: opx is ferromagnesian
Bulk
• Minerals crystallized from SiO2 55.83
TiO2 0.76
melt (glass when solidified)
Al2O3 16.74
• If for example you melt OPX, Fe2O3 9.55
SiO2 content of the melt MnO 0.16
(glass) will decrease, MgO MgO 4.97
will increase CaO 7.88
Na2O 2.68
• Whole rock (bulk rock) K2 O 1.29
composition if it is a closed P2O5 0.14
system will remain the same Total(norm) 100.00
Total 100.20
 Example from Makaopuhi lava lake From Wright and Okamura, (1977)
USGS Prof. Paper, 1004

Less More
crystallized crystallized

=
in whole rock
composition
(for equilibrium
crystallization (i.e. no
Note: not the actual components are
sample, for added or
representation only subtracted))

Powdered whole rock sample

Fused disk for analysis https://onlinelibrary.wiley.com/

https://www.hamilton.edu/acad doi/10.1002/9780470027318.a95
emics/analytical-lab 62

Whole rock (bulk rock) composition for the less crystallized and more crystallized sample should be similar if they
crystallized from the same magma, and if the system is closed
Example bulk rock compositions (Major elements, wt. %)
Harzburgite eclogite Limestone
SiO2 41.4 53.41 2.58
TiO2 0.01 0.97 -
Al2O3 0.6 17.77 0.68
Fe2O3* 8.78 7.03 0.33
MnO 0.16 0.12 -
MgO 48 3.83 0.64
CaO 0.2 5.34 52.39
Na2O 0.03 9.75 -
K2O 0.02 0.12 0.11
P2O5 0.01 0
H2O -
L.O.I. 41.88

Essential
Minerals olivine, opx cpx, garnet calcite

Yilmaz and Olgun,

Maury et al., 1992 Usui et al., 2006 2007
Bowen Reaction Series
Major elements
• Used for chemical classification
• For determining trends (ex. primitive to evolved
compositions)
• For discriminating between fresh and weathered samples
•…
Chemical classification: general classification,
binary
• Total alkalis – Silica (TAS diagram after LeBas et al., 1986)
16

14 Phonolite

(Na2O+K2O) (wt. %)
12 Foidite
TephriPhonolite
Trachyte
10 Trachydacite
Phonotephrite
Trachy-
8 andesite
Tephrite Basaltic Rhyolite
Trachy-
Basanite andesite
6 Trachy
Basalt

4 Dacite
Basaltic Andesite
Basalt Andesite
2 Picro
Basalt

35 40 45 50 55 60 65 70 75
SiO2 (wt. %)
 Chemical classification: general classification,
binary
• Total alkalis – Silica (TAS diagram after Cox et al., 1979)
16 16

14 14 Nepheline-
Phonolite
Syenite

12 12
Phonolitic Trachyte Syenite

(Na20+K2O)
Phono-
(Na20+K2O)

Nephelinite tephrite
10 Benmoreite 10 Syenite

Rhyolite Granite
8 Nephelinite Mugearite 8 ijolite
Tephrite Trachy- Syeno-Diorite
Andesite
Basanite Hawaiite Gabbro
6 6 Quarz
Dacite
Diorite

4 Basalt 4 Gabbro
Basaltic Andesite Diorite
Andesite
2 2

0 0

35 40 45 50 55 60 65 70 75 35 40 45 50 55 60 65 70 75

SiO2 SiO2

For volcanic rocks For plutonic rocks

Chemical classification: general classification,
binary
• Andesite classification (after
Gill, 1981)
Bivariate plots: Harker Diagrams
Bivariate plots:
Harker Diagrams
Element ratios
• K2O/Na2O
• Mg#:
𝑀𝑔
• molar Mg# = 𝑚𝑜𝑙𝑎𝑟 × 100
𝑀𝑔+𝐹𝑒

Indicators of magma differentiation

• Higher Mg#, more primitive composition
• Lower K2O/Na2O, more primitive composition

Note that continental crust is more evolved than oceanic crust

Major elements are
usually not used to
discriminate between
magmatic sources

• When you do use it for this purpose,

use ratios, and compare samples only
for a narrow range of silica
Some mineral chemistry
𝐶𝑎
• % An or An# = 𝑚𝑜𝑙𝑎𝑟 × 100
𝐶𝑎+𝑁𝑎+𝐾
𝑀𝑔
• Fo# (for olivine) = 𝑚𝑜𝑙𝑎𝑟 × 100
𝑀𝑔+𝐹𝑒

FW CaO: 56.08 g/mol; Na2O: 61.98 g/mol; K2O: 94.2 g/mol

Classifying igneous rocks using the norm
• Norm (normative composition): mineralogy of a rock from a chemical
analysis
• CIPW norm: devised by 3 petrologists (Cross, Iddings and Pirrson) and 1
geochemist (Washington)
• The norm of a rock may be substantially different from the observed
mineralogy – the mode
• Based entirely on chemistry, rocks with different crystallinity but with the
same composition, igneous protolith and metamorphic rock will have the
same normative composition
• There are assumptions for its calculation and restrictions on its use
- H. Rollinson. Using geochemical data
Classifying igneous rocks using the norm
Example bulk rock compositions (Major elements, wt. %)
Harzburgite eclogite Limestone
SiO2 41.4 53.41 2.58
TiO2 0.01 0.97 -
Al2O3 0.6 17.77 0.68
Fe2O3* 8.78 7.03 0.33
MnO 0.16 0.12 -
MgO 48 3.83 0.64
CaO 0.2 5.34 52.39
Na2O 0.03 9.75 -
K2O 0.02 0.12 0.11
P2O5 0.01 0
H2O -
L.O.I. 41.88

Essential
Minerals olivine, opx cpx, garnet calcite

Yilmaz and Olgun,

Maury et al., 1992 Usui et al., 2006 2007
This program was written by Kurt Hollocher, Geology Department, Union College, Schenectady, NY, 12308, hollochk@union.edu
A preview of week 3 and 4
Rollinson, 2017