Using geochemical data in igneous petrology

Useful books
Title borrowed from
H. Rollinson Using geochemical data (Longman, London, 1993) Chronically out of print; ca. US$60-$100 on
www.amazon.com

See also
F. Albarde Introduction to geochemical modelling (quite arduous) & Geochemistry M. Wilson Igneous petrology, a global tectonic approach

1. Some background information 2. Major elements 3. Major elements behaviour during magmatic processes (FC, PM, mixing) 4. Trace elements 5. Trace elements behaviour during magmatic processes 6. Geochemical models 7. Useful software

1. Some background concepts

1. 2. 3. 4. 1. 2. 3. 4. Getting geochemical data: the hardware Major and trace elements Earth structure and geochemistry Cosmochemistry and elements abundance Why using wt%? Norms Magmatic series Some diagrams with major elements

2. Major elements

1.1 Analytical methods

Spectrometry (electromagnetic waves, mostly X-rays) Mass spectrometry Excitation of the source:
Primary X-rays Plasma

Spectrometry

Emitted radiation

Emission Detector

Output with emission peak

Energy Source

Absorbed radiation Sample

Absorption Detector

Output with absorption trough

X-ray spectrum of an olivine

Main (modern) devices

XRF (X-ray fluorescence) Microprobe The ICP family (Inducively Coupled Plasma):
ICP-AES (Atomic Emission Spectrophotometry) ICP-MS and LA-ICP-MS

TIMS (Thermo-Ionization Mass Spectrometry) SHRIMP (High Resolution Ion Microprobe)

In situ? XRF Microprobe ICP-AES ICP-MS LA-ICP-MS

Y Y

Major
Y Y (difficult) (difficult) (difficult)

Traces
Some

Isotopes
Cheap and robust Cheap

Y Y Y (possible)

Replaced by ICP-MS De facto standard Increasingly popular; expensive, robust once set up. Lot of potential for isotopes Basic tool for geochronology. Complicated to use (clean chemistry) Regarded as stadard for geochrono, but extremely expensive and difficult to use. Will probably be replaced by LA ICP MS

ID-TIMS

(possible)

SHRIMP

SF Laser ablation?

ChemCam instrument Mars Science Laboratory

(Artist rending)

1.2 Major and traces

Definitions
Major elements:
Concentration > arbitrary value (0.1 or 1 wt% depending on the authors) Components of main mineral phases

Trace elements:
Concentration < 0.1 % Substitue in crystals but do not form phases of their own

Note that...
The above definition means that major and traces will behave in significantly different ways
Major: control by mineral stability limits (P-T conditions) Traces: independant (or partially independant, as will be discussed)

Conceptually, some elements could be major in some systems, traces in other (cf .K in the mantle or Zr in crustal magmas)

Common types of magma

1.3 Earth structure and geochemistry

Composition of Earth shells

Elements wt% Crust Continental O Si Al Fe Ca K Na Mg Ti C H Mn Ni Cr 0.51 41.2 28 14.3 4.7 3.9 2.3 2.2 1.9 0.4 0.3 0.2 0.07 0.15 0.07 0.33 5 20 Oceanic 43.7 22 7.5 8.5 7.1 0.33 1.6 7.6 1.1 44.7 21.1 1.9 5.6 1.4 0.08 0.15 24.7 0.12 Mantle Upper Lower 43.7 22.5 1.6 9.8 1.7 0.11 0.84 18.8 0.08 80--85 80 Outer 10--15 Core Inner

1.4 Cosmochemistry (how all this formed?)

Nuclosynthesis in stars Planetary nebulas Accretion Differenciation

Nucleosynthesis

Bethes cycle

Elements stability

Elements abundance
Lights > Heavies Even > Odd Abundance peak close to Fe (n=56)

Solar system abundance

Formation of a planetary nebula

Planetary nebulas

Temperature gradients in the planetary nebula

Differenciation of planets

Atmophile Lithophile Siderophile

Elements abundance patterns in Earth are a product of

Nucleosynthesis
Lights > Heavies Even > Odd Abundance peak close to Fe (n=56)

Differenciation
Lithophile mantle (+ crust) Siderophile core

2. Major elements

Typical major elements are

Si Al Fe Mg Ca Na K Ti Mn P Ni Cr
Major elements concentrations are expressed as wt % oxydes (SiO2, Al2O3, etc.)
(note the subscripts, by the way)

And O !

2.1 The wt% inheritance

Comes from the days of wet chemistry analysis Is sadly inconsistent with both
Trace elements analysis (ppm weight) Mineral formulas (number of atoms)

Molecular weight

m M n

Mass (or mass %)

Nb of moles (or of atoms)

Example 1
What is the wt% analysis of albite? Of a plagioclase An30?
NaAlSi3O8 CaAl2Si2O8
M(atom) M(oxyde)

Si
Al

28.086
26.982

60.09
101.94

Ca
Na O

40.08
22.989 15.999

56.08
61.982

Example 2
What is the atom formula of this rock?
SiO2 Al2O3 CaO MgO FeO K2O Na2O 73.44 14.29 1.10 0.58 2.06 5.39 2.60

(Darling granite)

NaAlSi3O8 CaAl2Si2O8

In a feldspar, Al = (Na + K + 2Ca) In this case, Al > Na + K + 2Ca This rock has excess aluminium (it is peraluminous)

biotite muscovite cordierite andalusite garnet

pyroxene hornblende biotite

aegirine riebeckite arfvedsonite

CaO CaO

moles

CaO K2O Al2O3 K2O Al2O3 Al2O3

K2O

Na2O

Na2O

Na2O

Peraluminous

Metaluminous

Peralkaline

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.

Some useful ratios

A/CNK = Al / (2 Ca + Na + K) A/NK = Al/ (Na + K)
6 7
Metaluminous Peraluminous

A/NK 1 2 3

Peralkaline

0.6

0.8

1.0

1.2 A/CNK

1.4

1.6

1.8

2.0

Some other useful (?) ratios

Mg# = Mg/(Mg+Fe) an% = Ca/(Na+Ca) K/Na

Not that all or most use cation numbers not wt% !! Still, igneous petrologists are very attached to wt% and are used to them. It might make more sense to switch to cation prop altogether, but it is probably not going to happen.

2.2 Norms
Norms are a way to link major elements with mineral proportions Normative composition ( modal) = mineral proportions calculated from chemistry Norms are a way to compare rocks with different mineralogy Whether they are more informative than the plain analysis is questionnable They were once extremely popular but are getting out of fashion The most common: CIPW norm (Cross, Iddings, Pearson & Washington)

CIPW normative minerals

Q: quartz Feldspars:
Or: orthoclase Ab: albite An: anorthite

Pyroxenes
Ac: acmite (NaFe pyroxene) Di: diopside Hy: hypersthene Wo: wollastonite

Feldspathoids
Lc: leucite Ne: nepheline

Ol: olivine C: corundum

+ minor minerals: apatite Ap, titanite (sphene) Tn

(some rare minerals omitted)

Some important features

Only anhydrous minerals are used in CIPW no micas, amphibole

When making norms, feldpars are constructed first (or early) they are the major component of igneous rocks Many things are therefore by comparison to the Fsp.

Peraluminous and peralkaline

Peraluminous = Corundum normative Peralkaline = Acmite normative

Saturated and undersaturated

If there is not enough silica to build Fsp: undersaturated rocks ( saturated)
Orthoyroxene => olivine + qz Feldspars => feldspathoids + qz

Alkali-rich rocks are commonly undersaturated (not enough SiO2 to accomodate all alkalis in Fsp)

Saturation line

 In norms, rocks are either qz- or olnormative (saturated or under saturated) In real life, they can have neither Note that it has nothing to do with the notion of basic-acid (purely defined as SiO2 %) or felsic-mafic (linked to the amount of light or dark minerals)

Ol- and foid normative = undersaturated

Saturation line

Quartz Normative = saturated

 In norms, rocks are either qz- or olnormative (saturated or under saturated) In real life, they can have neither Note that it has nothing to do with the notion of basic-acid (purely defined as SiO2 %) or felsic-mafic (linked to the amount of light or dark minerals)

Undersaturated

Felsic

Mafic

Saturated

Basic

Acid

2.3 Magmatic series

12 10

Alkaline

Subalkaline
35 40 45 50 55 60 65

%SiO

Nepheline-Fayalite-SiO2

Not a very good system, as it is a poor equivalent of magmatic rocks but allows to see nice fetaures.

Thermal divide separates the silica-saturated (subalkaline) from the silica-undersaturated (alkaline) fields at low pressure Cannot cross this divide by FX, so cant derive one series from the other (at least via low-P FX)
Ol Opx
1713

Liquid Thermal Divide

1070
Ne + L Ne + Ab Ab + LAb + L Ab + Tr

Tr + L

1060
Q

Ne

Ab

Ne

Ab

AFM diagram: can further subdivide the subalkaline magma series into a tholeiitic and a calc-alkaline series
Figure 8-14. AFM diagram showing the distinction between selected tholeiitic rocks from Iceland, the MidAtlantic Ridge, the Columbia River Basalts, and Hawaii (solid circles) plus the calc-alkaline rocks of the Cascade volcanics (open circles). From Irving and Baragar (1971). After Irvine and Baragar (1971). Can. J. Earth Sci., 8, 523-548.

Alkaline Calc-alkaline Tholeitic

Series
Alkaline

Alkali content High

Low to moderate Low

Fe-Mg
Fe-rich Mg-rich

Al
Metaluminous to peralkaline Metaluminous to peraluminous Metaluminous

Subalkaline

Calcalkaline Tholeitic

Fe-rich

A world-wide survey suggests that there may be some important differences between the three series

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

Within Plate Oceanic Continental yes yes yes yes

After Wilson (1989). Igneous Petrogenesis. Unwin Hyman - Kluwer

Series and subseries

Alkaline series
Saturated Undersaturated

Calc-alkaline series
Low K Med K High K

East African rift (Afar) mildly alkaline

Central African Rift Strongly alkaline

Series and subseries

Alkaline series
Saturated Undersaturated

Calc-alkaline series
Low K Med K High K

Figure 16-6. a. K2O-SiO2 diagram distinguishing high-K, medium-K and low-K series. Large squares = high-K, stars = med.-K, diamonds = low-K series from Table 16-2. Smaller symbols are identified in the caption. Differentiation within a series (presumably dominated by fractional crystallization) is indicated by the arrow. Different primary magmas (to the left) are distinguished by vertical variations in K2O at low SiO2. After Gill, 1981, Orogenic Andesites and Plate Tectonics. Springer-Verlag.

Classifications based on major elements

Classification of sub-alkaline lavas

 At that stage, the notion of magmatic series become to some degree blurred and irrelevant. As usual, nature does not like pigeon holes and classifications and rocks have to be studied on a case by case basis

2.4 Some useful diagrams

They will obviously reflect the fundamental aspects outlined previously:
Magmatic series Saturated vs. Undersaturated Peraluminous vs. Peralkaline Etc.

There is no rule forbiding to plot whatever vs. anything else But some diagrams tend to give better results

Harker type diagrams

The most commonly used X: something related to differenciation (SiO2 or MgO) Y: any other element

22 10

Bivariate (x-y) diagrams

Harker diagram for Crater Lake

Al2O3
17 5

MgO

12

0 15

FeO* 10

10

CaO

0 4

Na2O
4

3 2 1 0 50 55 60 65 70 75 45 50 55 60 65 70 75

K2O

0 45

SiO2

SiO2

Harkem problems
Differenciation not always moves to the right they can be misleading When using SiO2, closure effect due to the overwhelming weight of SiO2
It has been proposed to use oxyde* instead of oxyde, with e.g. K O

K 2O *

(100 SiO2 )

Differenciating between magmatic series

TAS Si-K AFM Everything with Mg# (thol. vs. CA)

See all previous examples

Showing some fundamental features

Diagrams using A/CNK, K/Na, etc. tend to work quite nicely feldspar triangle (Oconnor)

Generally helpful to differenciate between rocks of different origins (S vs I type granites, etc)

Classification based on normative composition

OConnor diagram for quartz-bearing plutonic rocks

Classifying/naming rocks
Rocks already have perfectly well defined names (IUGS classification) Therefore, why would you use another scheme?
Strongly weathered Strongly metamorphosed Geochem geek

Some people even do it with traces (SiO2 vs. Ti/Zr)

Classification based on cationic proportions

Jensen cationic plot

Classification based on cationic proportions

De la Roche et al. R1-R2 diagram

More creative use of the same diagram

4000
Di

3000

Ha An Fo

Sp

R2= 6Ca + 2Mg + Al

Hd

2000

En

Ph

Mantle Fractionates Pre-plate Post- Collision collision Uplift Lateorogenic Syn-collision Anorogenic PostFs

1000

Ab Or Bt Fa

orogenic

0
-1000

1000

2000

3000

4000

R1= 4Si - 11(Na + K) - 2(Fe + Ti)

Batchelor-Bowden interpretation of de la Roches diagram

The data Im working on: plutonic rocks of the Abitibi sub province (Canada)
Blue: pre-tectonic Green and red: syn to post tectonic Purple: post tectonic

Note the nice trend of evolution with time