Major and Trace Element Geochemistry

Just as seismology is an important tool to image the earth’s

interior, so too are chemical and isotopic compositions of
igneous rocks that originate at great depths with the upper
mantle and lower crust.

• Importance of chemical compositions of igneous rocks

– Petrogenesis of primary magmas
• these reflect mineralogy and chemistry of the source rock
– Differentiation of magmas
• need to decipher shallow processes to infer deep source
– Radiogenic isotopes
• allow a time-integrated view of changing composition

Major and Trace Element Geochemistry

• Major elements
– Comprise most of the rock
– Expressed as weight (wt.) % oxides, each >0.1%
– Analyzed by XRF, ICP-MS
• Trace elements
– Present in concentrations <0.1%
– Expressed in ppm or ppb
– Analyzed by XRF, ICP-MS, INAA
• Volatile elements
– H2O, CO2, SO4
– Rare gases: He, Ar, Ne, etc.
– Analyzed by spectroscopy or mass spectrometry
• Radiogenic isotopes
– Ratios of radiogenic to nonradiogenic isotopes of an element
• recall isotopes of an element have same atomic no., but variable # of neutrons
– Variations in ratios reflect differences produced over time by radioactive decay in source
– Variations are extremely small: analyzed by magnetic sector mass spectrometry
• Stable Isotopes
– Lighter masses fractionated by geological processes
– Analyzed by magnetic sector mass spectrometry

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 Major and Trace Element Geochemistry
• Variation Diagrams
– Plot chemical differences and trends among related rocks (lavas = magmas?)
• Only true for liquids (aphyric lavas and tephras)
• Can define and help model products of partial melting and crystallization
• Plot ME, TE or both
• Major elements, Harker diagrams
• Cogenetic lavas = well-defined trends
• Lever-rule can quantify fractionating mineral assemblage
• Inflected trends = changes in crystallizing mineral assemblage
• Simple, yet powerful way to compare/distinguish suites of rocks (magmas)

A Qot Geologic Map

00

3327
25

Qot Qot Volcán Volcán San Pedro

Cerro Pellado Surficial Deposits
Qt 2750 San Qal
Pedro 3213 Qal Alluvium - Colluvium
Qt
3621 m Qpv
Qm Neoglacial Moraines
Qsp
Tvs Qda Debris avalanche deposit
3250

00
30 PED12

ice
H70 2 1 Volcán San Pedro
H72 Qsp Younger Holocene Summit Lavas
00
30

ice Qcf
4 2 Qcf Younger Holocene Composite Flow
0

Qtd
275

36o S ice Qoh H20 H12

Qm
H11i Qoh Older Holocene Lavas
Qoh H14 H16
Tgh
Qal H73
Tvs Volcán Tatara 120-20 ka
Qt Qal Qt Mainly Basaltic Andesite Lavas
Qt
Qt 3 H8
Qtd Tatara Dacite 68 ka
E. Queb

0 Tgh H23
250 Qal
QH2-1 pre-Volcán Tatara
Tvs

Qt Tvs Qcf Qpv Volcan Pellado 190-80 ka

rada

22 50
Qcg Guadal Lavas 500-350 ka
Hon
Ester o San Pedro

do
Pe ro

Qcg
do

Qoh Qot Older TSPC lavas 930-220 ka

te
lla

2000 Tgh
Es

Tvs QH1-2
El

Tvs Basement Rocks

0
17
5 Tgh Huelmul Granite 6.2-6.4 Ma
Qda Tvs Tvs Volcanics metamorphosed 7-9 Ma
Contour interval = 250 m 00
15 NTE
0 1 2 km 3 P UE
DE LA Qal Flow H23 Sample
R IO Vent
direction locality
70 o 35' W 70 o 50' W

B Volcan San Pedro C Volcan San Pedro

Costa and Singer Older

Holocene
H72 H70 3621 m

H72
H70
3621 m
Older
Volcan
Pellado
Older 2 Holocene
(2002) H73
Holocene

Journal of Petrology QH2-1

Volcan
Tatara
Moraine PED12
Volcan Moraine 1
Tatara 4
Volc<n San Pedro H20
2
Southern Volcanic QH1-2 H14 H12
1
Zone 3
H16

Guadal Lavas

Chilean Andes H23

H8
4
d o
ella
ro P
E ste

2
Costa and Singer (2002) Harker Diagrams, Volc<n San Pedro Lavas

3
 Major and Trace Element Geochemistry
• Trace elements
– Partitioning between crystalline and liquid phases
• Partition coefficient:
liq concentration in mineral
Dxtal =
concentration in liquid
• D << 1, incompatible elements
– Large Ion Lithophile Elements
(LILE)
» K, Rb, Sr, Ba,
» Zr, U, Th, REE, etc.

• D > 1, compatible elements

» Ni, Cr, Co, etc.

Major and Trace Element Geochemistry

• Rare Earth Elements (REE)
– 15 elements from mass 57 to 71 (14 occur naturally)
• La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
• Useful because similar in geochemical behavior
• Trivalent except Eu can be Eu3+ or Eu2+, depending on fO2
• To eliminate Oddo-Harkins effect, normalize to chondritic meteorites

Basalt, garnet-bearing source

Basalt, plag fractionation

or plag in source

Basalt, garnet-free source

4
 Major and Trace Element Geochemistry
• Rare Earth Elements (REE)
– Particular minerals influence shape of chondrite-normalized REE pattern by
virtue of D values:
• Feldspar: 2+ negative Eu anomaly
• Garnet: high D for Heavy REE (HREE)
• Olivine: D < 0.1 for all REE; uniform effects on magma
• Hornblende: D > 1.0 for middle REE
• Zircon, Sphene, Apatite: strong affinity, high D for REE

– Mantle REE: originally flat pattern, 2-3x chondritic

• Partial melting leaves upper mantle depleted in LREE
• Degree of enrichment of REE in melts
– Abundances and mineralogy in source
– Degree (percentage) of melting
– Extent of fractional crystallization

• See Wilson Fig. 2.3 from previous panel

Major and Trace Element Geochemistry

• Rare Earth Elements (REE)
– Extend normalization approach to several other elements = Spiderdiagrams
• Plot in order of increasing D
• Normalization is arbitrary: to primordial mantle, chondrites, MORB
• Peaks, troughs, slopes, anomalies indicative of specific crystal-liquid equilibria
processes

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 Major and Trace Element Geochemistry
• Primary Magmas
– Formed by partial melting of upper mantle in equilibrium with olivine+pyroxene
unmodified by fractional xtlln, assimilation/contamination, magma mixing, etc.
• Truly primary magmas are rare to nonexistant
– most basaltic magmas fractionated olivine and assimilated some lithosphere on way up
– Criteria not firm but:
Kd = (Fe2+/ Mg)olivine /(Fe2+/Mg)melt

Kd = 0.3
so that:
Mg’ = Mg/(Mg+ Fe2+) of basalt in equilibrium with Fo91 is 0.68-0.75

Typically:
Ni > 400-500 ppm
Cr > 1000 ppm
SiO2 < 50%

– Metasomatism (addition of fluids + new minerals) of mantle may change

possible primary magma composition

Radiogenic Isotopes
• Rutherford and Soddy (1902) [Nobel Prize in Physics]
– Experiments indicated that thorium decay to radium is exponential over time.
– Radioactivity is an atomic property. Atoms in radioactive elements are unstable. Within
a given amount of time, a fixed proportion of atoms disintegrate to form new atoms.
– Disintegration accompanied by emission of alpha or beta particles. Activity, or intensity,
of radioactivity is proportional to number of atoms that disintegrate per unit time.
– Thus activity is directly proportional to number of atoms of substance present:

− dN
= λN
dt
where 8 is the decay constant, i.e., probability that atom will decay in unit time.
N t
dN
∫No N = − to∫ λ t

ln N/No = -8t
N = No e -8t
basic radioactive decay formula.
No is initial number of atoms
N is number of atoms at time t.

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 Radiogenic Isotopes
• The age equation
N = No e -8t
need to realize that daughter atoms D can be expressed as
D = No - N
No = D + N from above
N = (D + N) e -8t
D = N (e -8t - 1)
ln(1+D/N) = 8t
t = 1/8 ln(1+D/N) need to measure D, daughter atoms present, N parent atoms left.
• Half-life used to determine decay constants
t = ln2/8 = 0.693/8
• If some daughter isotope was incorporated into mineral at to , this must be
subtracted from the amount measured today:

1  D − Do 
t= ln 1 + 
λ  N 

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 Radiogenic Isotopes
• The K-Ar system
– 40K undergoes branched decay to 40Ar
• half-life of 1.25 x 109 yr
• 8 = 5.81 x 10-11 yr-1
• 40Aro is small or can be corrected for
– System used to date rocks from historical time, 2 ka, to 4.5 Ga (meteorites)
1   λ ec + λ B −  40
Ar − 40Aro 
t= ln 1 +   
λ ec + λ B −   λ ec  40
K 
– The 40Ar/39Ar variant of K-Ar dating:
1  40
Ar 
t= ln 1 + J 
λ  39
ArK 
J is a constant including a factor for fraction of 39K atoms converted to 39Ar in the
neutron flux of a nuclear reactor
• More powerful than K-Ar dating:
– more precise; all measurements in single mass spectrometer
– smaller samples -- down to single phenocrysts
– incremental-heating; many ages from gas released over range of T in single
sample
– Thermally disturbed samples yield “discordant” release spectrum of ages

40Ar/39Arage
spectra and
isochrons