GEOL 5310

ADVANCED IGNEOUS AND

METAMORPHIC PETROLOGY
Chemistry of Igneous Rocks

Nov. 2, 2009

WHOLE ROCK ANALYSIS OF A BASALT

Molecular
Wt%
Wt.
49.2
2.03
16.1
2.72
7.77
0.18
6.44
10.5
3.01
0.14
0.23
0.7
0.95
99.97
structural water
SiO2
TiO2
Al2O3
Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O
P2O5
H2O+
H2O-

adsorbed water Trace

Ba
Co
Cr
Ni
Pb
Rb

Wt%/
Mol. Wt. Mole%

60.09
95.9
101.96
159.7
71.85
70.94
40.31
56.08
61.98
94.2
70.98
18.02
18.02

0.8188
0.0212
0.1579
0.0170
0.1081
0.0025
0.1598
0.1872
0.0486
0.0015
0.0032
0.0388
0.0527
1.6174

Elements (ppm)
5
32
220
87
1.29
1.14

Sr
Th
U
V
Zr
La

190
0.15
0.16
280
160
5.1

50.62
1.31
9.76
1.05
6.69
0.16
9.88
11.58
3.00
0.09
0.20
2.40
3.26
100.00

Major elements:
usually > 1 wt.%
control properties of magmas
major constituents of essential
minerals

Minor elements:
usually 0.1 1 wt.%
substitutes for major elements in
essential minerals or may form small
amounts of accessory mins.

Trace elements:
usually < 0.1 wt.%
substitutes for major and minor elements
in essential and accessory minerals

1 wt.% = 10,000 ppm

1 ppm = 0.0001 wt.%

ANALYTICAL TECHNIQUES
Emitted
radiation

Energy Source

Emission
Detector

Absorbed
radiation
Sample

Output with
emission peak

Absorption
Detector

Whole Rock Analyses

- X-ray Fluorescence (XRF)
X-rays excite inner shell electrons producing
secondary X-rays

- Inductively Coupled Plasma (ICP)

dissolved rock mixed with Ar gas is turned into
plasma which excites atoms; generates X-rays

- Instrumental Neutron Activation (INAA)

nuclei bombarded with neutrons turning atoms
radioactive; measure emitted X-rays

- Mass Spectrometry(MS)
atoms ionized and propelled through a curved
electromagnet which seperates the ions by weight
(good for isotope analysis)

Output with
absorption trough

Mineral Chemical Analyses

- Electron Microprobe (EM)
incident electron beam generates X-rays
which whose characteristic wavelengths
are measured (WDS)

- Energy Dispersive Spectrometry (EDS)

incident electron beam generates X-rays
which whose characteristic energies are
measured; attached to UMDs SEM

- X-ray Diffractometry(XRD)
Incident X-rays are diffracted by
characteristic mineral structure

CHEMICAL ANALYSES OF COMMON ROCK TYPES

THAT APPROXIMATE MAGMA COMPOSITIONS
Magma - Ultramafic

Rock SiO2
TiO2
Al2O3
Fe2O3
FeO
MnO
MgO
CaO
Na2O
K2O
H2O+
Total

Mafic

Intermed.

Peridotite
42.26
0.63
4.23
3.61
6.58
0.41
31.24
5.05
0.49
0.34
3.91

Basalt
49.20
1.84
15.74
3.79
7.13
0.20
6.73
9.47
2.91
1.10
0.95

Andesite
57.94
0.87
17.02
3.27
4.04
0.14
3.33
6.79
3.48
1.62
0.83

98.75

99.06

99.3

Felsic

Alkalic

Rhyolite Phonolite
72.82
56.19
0.28
0.62
13.27
19.04
1.48
2.79
1.11
2.03
0.06
0.17
0.39
1.07
1.14
2.72
3.55
7.79
4.30
5.24
1.10
1.57
99.50

99.23

CIPW NORMATIVE CALCULATIONS

Mode is the volume % of minerals observed
Norm is the weight % of minerals calculated from
whole rock geochemical analyses by distributing
major elements among rock-forming minerals

Numbers show the order that

mineral are figured.
See Winter (2001) Appendix for
instructions.

13)
14)

15)
11)
7)
8)
9)
10)

12)
4)
5)

2)

1)
6)
3)

GEOCHEMICAL PLOTS
Objective: to show the co-variation of elemental
components that may give insight to magmatic
processes such aspartial melting
magma mixing
country rock assimilation/contamination
fractional crystallization
(or crystallization differentiation)

Types:
bivariate (X-Y)
triangular
normalization plots (spider diagrams)

MOST PLOTS ARE APPROPRIATE FOR

LIQUID COMPOSITIONS ONLY!!!

HARKER
VARIATION
DIAGRAMS

Liquid
Lines of
Descent

Variation of major and

minor oxide abundances
vs. SiO2 (thought to be and
indication of the evolved character
of a magmatic system)

The Daly Gap

Real or an artifact of
the variation of SiO2
concentration with
differentiation

Winter (2001) Figure 8-2. Harker

variation diagram for 310
analyzed volcanic rocks from
Crater Lake (Mt. Mazama),
Oregon Cascades. Data compiled
by Rick Conrey (personal
communication).

Primitive

Evolved

DIFFERENTIATION INDEXES

from Winter (2001)

INTERPRETING TRENDS ON
VARIATION DIAGRAMS
Extraction Calculations

Addition-Subtraction Diagram

Figure 8.7.
Stacked variation
diagrams of
hypothetical
components X
and Y (either
weight or mol %).
P = parent, D =
daughter, S = solid
extract, A, B, C =
possible extracted
solid phases. For
explanation, see text.
From Ragland (1989).
Basic Analytical
Petrology, Oxford Univ.
Press. (From Winter

Rollinson (1993)

INTERPRETING TRENDS ON
VARIATION DIAGRAMS
Scattered Trends
-not all liquids
-not comagmatic
-polybaric fractionation
-sample heterogeneity
-varied data sources

MAGMA SERIES
RELATED TO TECTONIC PROVINCES

Subalkaline

Characteristic
Plate Margin
Series
Convergent Divergent
Alkaline
yes
Tholeiitic
yes
yes
Calc-alkaline
yes

Within Plate
Oceanic Continental
yes
yes
yes
yes

16
Phonolite

14

Tephriphonolite

12

Na2O + K2O

10
Na 2O+K 2O

Foidite
8
6
4
2

Winter (2001) Figure 8.11. Total alkalis vs. silica diagram for
the alkaline and sub-alkaline rocks of Hawaii. After MacDonald
(1968). GSA Memoir 116

0
35

40

Trachyte

PhonoTephrite

Trachy- Trachydacite
andesite
Rhyolite
Basaltic
Tephrite
trachyBasaniteTrachy-andesite
basalt
Dacite
Andesite
Basaltic
Basalt
andesite
Picrobasalt
45

50

55

SiO
SiO2 2

60

65

70

75

SUBALKALINE DISCRIMINATION DIAGRAMS

AFM Diagram

Calc-Alkaline

Fe2O3 + FeO
20

Tholeiitic--Calc-Alkaline
boundary after Irvine and
Baragar (1971). Can. J. Earth
Sci., 8, 523-548

Al2O3
15

10
100

Tholeiitic

90

80

70
AN

Na2O + K2O

MgO

60

50

40

ALUMINA/ALKALI DISCRIMINATION DIAGRAMS

Winter (2001) Figure 18.2. Alumina saturation classes

based on the molar proportions of
Al2O3/(CaO+Na2O+K2O) (A/CNK) after Shand (1927).
Common non-quartzo-feldspathic minerals for each
type are included. After Clarke (1992). Granitoid
Rocks. Chapman Hall.

Winter (2001) Figure 8-10 b. Alumina saturation

indices (Shand, 1927) with analyses of the
peraluminous granitic rocks from the Achala
Batholith, Argentina (Lira and Kirschbaum, 1990). In
S. M. Kay and C. W. Rapela (eds.), Plutonism from
Antarctica to Alaska. Geol. Soc. Amer. Special
Paper, 241. pp. 67-76.

TECTONIC
PROVINCE
DISCRIMINATION
DIAGRAMS

Rollinson (1993)

TECTONIC PROVINCE DISCRIMINATION DIAGRAMS

Figure 9.8 Examples of discrimination diagrams used to infer tectonic setting of ancient (meta)volcanics. (a) after Pearce and Cann
(1973), (b) after Pearce (1982), Coish et al. (1986). Reprinted by permission of the American Journal of Science, (c) after Mullen
(1983) Copyright with permission from Elsevier Science, (d) and (e) after Vermeesch (2005) AGU with permission.

TRACE ELEMENTS IN IGNEOUS PROCESSES

Ionic Field Strength
(Charge/Radius)

Transition Metals

Precious
Metals
Rare Earth Elements

Goldschmidts (1937) Rules of Element Affinity

1.

2.

Two ions with the same valence and radius should

exchange easily and enter a solid solution in amounts equal
to their overall proportions (e.g. Rb~K, Ni~Mg, Mn~Fe)
If two ions have a similar radius and the same valence: the
smaller ion is preferentially incorporated into the solid over
the liquid (e.g., Mg > Fe in Olivine)

TRACE ELEMENT COMPATIBILITY

Compatibility degree to which an element prefers to partition into the solid over
the liquid phase .
Kd(i)1 Mineral-Liquid Partition Coefficient for element i in mineral 1

Kd(i)1 = C(i)mineral 1/ C(i)liquid

(C(i) - concentration of element i in wt. %)

Kd(i)1 > 1 Compatible,

Kd(i)1 < 1 Incompatible

D(i) Bulk Rock Partition Coefficient for element i

D(i) = x1 Kd(i)1 + x2 Kd(i)2 + x3 Kd(i)3 + ....

(x1 proportion of mineral 1)

INCOMPATABILITY OF TRACE ELEMENTS

PARTITION COEFFICIENTS (CS/CL)

Rb
Sr
Ba
Ni
Cr
La
Ce
Nd
Sm
Eu
Dy
Er
Yb
Lu

Rare Earth Elements

Table 9-1. Partition Coefficients (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks
Olivine
0.010
0.014
0.010
14
0.70
0.007
0.006
0.006
0.007
0.007
0.013
0.026
0.049
0.045

Opx
0.022
0.040
0.013
5
10
0.03
0.02
0.03
0.05
0.05
0.15
0.23
0.34
0.42

Data from Rollinson (1993).

Cpx
Garnet
0.031
0.042
0.060
0.012
0.026
0.023
7
0.955
34
1.345
0.056
0.001
0.092
0.007
0.230
0.026
0.445
0.102
0.474
0.243
0.582
1.940
0.583
4.700
0.542
6.167
0.506
6.950

Plag
Amph Magnetite
0.071
0.29
Compatible
1.830
0.46
0.23
0.42
0.01
6.8
29
0.01
2.00
7.4
0.148
0.544
2
0.082
0.843
2
0.055
1.340
2
0.039
1.804
1
0.1/1.5*
1.557
1
0.023
2.024
1
0.020
1.740
1.5
0.023
1.642
1.4
0.019
1.563
* Eu3+/Eu2+

Italics are estimated

BEHAVIOR OF TRACE ELEMENTS DURING

PARTIAL (BATCH) MELTING
Normal Range
of Partial
Melting in the
Mantle

CL/Co = 1/[D(i)(1-F) + F]
F - Fraction of Liquid
D(i)- Bulk Distribution
Coefficient for Element i

As D(i) 0 (strongly IE)

CL/Co 1/F

Degree of
Partial
Melting (F)

Incompatible

Compatible

BEHAVIOR OF RARE EARTH ELEMENTS DURING

PARTIAL (BATCH) MELTING OF THE MANTLE

From Rollinson (1993)

Winter (2001) Figure 9-4. Rare Earth concentrations

(normalized to chondrite) for melts produced at various
values of F via melting of a hypothetical garnet lherzolite
using the batch melting model (equation 9-5).

BEHAVIOR OF TRACE ELEMENTS DURING

FRACTIONAL CRYSTALLIZATION
Rayleigh Distillation:
CL/Co = F(D(i)-1)
F - Fraction of Liquid Remaining
D(i)- Bulk Distribution
Coefficient for Element i

From Rollinson (1993)

BEHAVIOR OF TRACE ELEMENTS DURING FRACTIONAL

CRYSTALLIZATION
Compatible

Bulk Rock Partition Coefficient of Ce,Yb, and Ni

for Crystallization of:

1) Troctolite (70% Pl, 30% Ol)

D(Ce) = xPl Kd(Ce)Pl + xOl Kd(Ce)Ol
= .7*.103 + .3*.007 = 0.092
D(Yb) = xPl Kd(Yb)Pl + xOl Kd(Yb)Ol
= .7*.07 + .3*.065 = 0.069

Incompatible

D(Ni) = xPl Kd(Ni)Pl + xOl Kd(Ni)Ol

= .7*.01 + .3*25= 7.5
2) Olivine Gabbro (63% Pl, 12% Ol, 25% Cpx)
D(Ce) = xPl Kd(Ce)Pl + xOl Kd(Ce)Ol + xCpx Kd(Ce)Cpx
= .63*.103 + .12*.007 + .25*.09 = 0.088
D(Yb) = xPl Kd(Yb)Pl + xOl Kd(Yb)Ol + xCpx Kd(Yb)Cpx
= .63*.07 + .12*.065 + .25*.09 = 0.074

D(Ni) = xPl Kd(Ni)Pl + xOl Kd(Ni)Ol + xCpx Kd(Ni)Cpx

= .63*.01 + .12*25 + .25*8 = 5
From Rollinson (1993)

TRACE ELEMENT BEHAVIOR DURING

FRACTIONAL CRYSTALLIZATION
Rayleigh Distillation: CL/Co = F(D-1)
100.000

100.000

CL/Co

Troctolite

CL/Co

Olivine Gabbro

10.000

10.000
Tr(Yb)

OG(Yb)
OG(Ce)
Ce/Yb
OG(Ni)

Tr(Ce)
Ce/Yb
Tr(Ni)
1.000

1.000

0.100
0.00

0.100
0.00

0.20

0.40

0.60

0.80

F (fraction of liquid remaining)

1.00

0.20

0.40

0.60

0.80

F (fraction of liquid remaining)

Conclusions: Fractional crystallization of mafic magmas gradually increases the

concentrations of similarly incompatible elements, but has a minimal effect on their
ratios; and strongly decreases the concentrations of compatible elements

1.00

TRACE ELEMENT BEHAVIOR DURING

FRACTIONAL CRYSTALLIZATION
EXAMPLE FROM THE SONJU LAKE INTRUSION
E. Compatible Elements

RARE EARTH ELEMENT(REE)DIAGRAMS

COMPARES RATIOS AND NORMALIZES TO A STANDARD COMPOSITION
Fractional crystallization of olivine from a komatiitic melt

REE commonly normalized

to chondrite composition
thought to approximate the
unfractionated composition
of the earth.

Fractional crystallization
increases the REE abundance,
but has a neglible effect on the
REE pattern

Light REE

Heavy REE
From Rollinson (1993)

REE RATIO DIAGRAMS

From Rollinson (1993)

Fractional Crystallization
- minimal change in
REE ratios
Partial Melting
- significant
change in REE
ratios

TRACE ELEMENT NORMALIZATION PLOTS

(SPIDER DIAGRAMS)

Rock/Standard Comp*

Positive
Anomaly

Enriched

Negative
Anomaly

Depleted

Most

Least
Incompatible Elements
(likes magma)

Common Standard Compositions for Normalizing

Chondritic meteorite
Avg. Mid-ocean Ridge Basalt (MORB)
Primitive Mantle
Primitive Ocean Island Basalt (OIB)

Compatible
Elements
(likes minerals)