Chapter Three:

Geochemistry of Igneous and Sedimentary rocks

3.1. Geochemistry of magmatic processes

3.1.1. Chemical composition of magmas
3.1.2. Physical properties of magma
3.1.3. Genesis of magma
3.1.4. Magma evolution
3.1.5. Behavior of major- and trace elements during fractional crystallization
3.1.6. Trace element geochemistry: enrichment, depletion, and spider diagram
3.1.7. Modeling of trace element processes in igneous rocks
3.1.8. Discrimination diagrams for basaltic to andesitic and granitic
composition
3.2. Geochemistry of sedimentary process
3.2.1. Weathering, transportation, deposition, digenesis
3.2.2. Sequence of silicate mineral weathering
3.2.3. Discrimination diagrams for sedimentary rocks
 Geochemistry of magmatic processes
• Magmas
 Molten rock which originates deep within the earth
 Are generated inside the earth by partial melting of mantle
material or crustal material (anatexis),
 Mostly have silicate composition, known as silicate magma.
 Other varieties like sulfide, oxide, carbonatite are also
possible, but rare and mainly originate from mantle.
 Are the mixture of elements in gaseous, liquid and solid state.
 Chemical Composition Magma

 Oxygen is invariably the most abundant element about 50

% of the weight of the total mass of magmas.
 Other major elements like Si, Al, Fe, Mg, Ca, Na, K, Ti, P
vary from 1 to 30%.
 Since, oxygen dominate the composition, it is common to
express the composition of magmas or igneous rocks as
weight percentage of oxides of major elements.
 In most cases SiO2 is most abundant major oxide, followed
by Al2O3, Fe2O3, FeO, MgO, CaO, Na2O, K2O, TiO2, P2O5.
 On the basis of silica abundance, the igneous rocks are classified into
Ultrabasic (SiO2 < 46 w%),
Basic (SiO2, 46-52 w%),
Intermediate (SiO2, 52-65 w%) and
Acidic (SiO2 >65w%).
 There is regularity in the variation of the major oxides in magmas.
 Fe2O3, FeO, MgO, CaO, TiO2 are more abundant in the basic magmas and
decrease as silica content increases.
 Magmas also contain all other elements in the periodic table but in trace
quantities either in ppm or ppb (trace elements).
 Volatiles present in the melt are mainly H2O and CO2 and followed by F,
Cl, SO2, SO3 etc.
Water is highly soluble in the magmas at moderate and
high pressure, whereas CO2 is soluble only at high
pressure (> 10 kb).
 Physical Properties of Magma
 Three important parameters are used to explain the physical properties of magmas,
1) Temprature:
 Magmas vary in temperature from about 700O C
(acidic) to about 1250O C (basic).
2) Viscosity:
 It varies by several orders of magnitude in natural magmas, as high as 108- 109
poises (acidic) to 103- 105 poises (basic).
– Magmas rich in silica and depleted in Fe, Mg, Ca will
have high quantity of polymers (acidic) compared to the
melts with low silica and high content of Fe, Mg, Ca
(basic) (less polymerised).
– Viscosity may decrease when there is an increase in
temperature and
high Viscosity = low temp.addition
= high silica=of
slowwater
flow low and other volatile
Viscosity = high temp. = low silica = easy flow
components to magma.
3) Density:

 Also depends on the composition of the melt

 Basic magma will vary between 2.5-2.6 at ambient temperatures but will
be about 2.9-3.0 at upper mantle pressures,
 Acidic magmas on the other hand will be about 2.0 at ambient and
increases up to about 2.7 with increasing pressures in the subsurface
conditions.

 One of the reasons for the lower density of acidic magmas may be the high
amount of dissolved volatile components in it compared to the basic ones.
3) Density:

 Also depends on the composition of the melt

 Basic magma will vary between 2.5-2.6 at ambient temperatures but will
be about 2.9-3.0 at upper mantle pressures,
 Acidic magmas on the other hand will be about 2.0 at ambient and
increases up to about 2.7 with increasing pressures in the subsurface
conditions.

 One of the reasons for the lower density of acidic magmas may be the high
amount of dissolved volatile components in it compared to the basic ones.
 Magma Genesis
 Magmas are formed or generated in the lower crust or upper mantle.
 As they are forming under high pressure conditions, tend to move
upward, due to lower density than the surrounding rocks, towards the
surface producing either
 Intrusive or extrusive rocks.
 There are two important stages in the magmatic process,
 Magma generation and
 Magma evolution.
 Magma Generation in the Upper Mantle conditions

 The low velocity zone is generally considered to be the site for the
generation of the magma.
 At the same time this zone seems to contain only small amounts of melt
i.e. <1%.
 In such a case, how to account for the enormous quantities of magma that
has produced the thick earth’s crust?
 Available experimental data on the behavior of pyrolite which is a
common rock type in the upper mantle provide answer to this question.
 Pyrolite (lower pyrolite zone in the upper mantle) when exposed to
melting temperatures with varying pressures and dry and/or water
saturated condition, it starts melting at 1100oC at low pressures; with
increasing pressures, in dry condition, the solidus temperature increases
from 1200 to 15000C and in water saturation condition the same solidus
temperature decreases to about 10000C.
 Thus, the experiment data suggests that the excess amount water
facilitates melting even at much lower temperatures.
 However, the amount of water present in the upper
mantle is quite low less than 0.1% because the
upper mantle is mainly solid.
 Apart from this, the studies also indicate that the
presence of CO2 can also lower the melting
temperature of pyrolite particularly at pressure
conditions of the asthenosphere,
 Thus the conditions that are to be fulfilled for the
generation of magma in the upper mantle seems to be
a) Availability of water:
 Occur along active converging plate margins where subducting
oceanic crust carries water to upper mantle, in addition to the release
of water from the hydrated minerals (amphiboles, clay minerals etc),
present in altered sea- floor basalts and deep sea sediments;
b) Localized high temperatures:
 Occur beneath oceanic islands (e.g. Hawaii or Helena) or
intercontinental areas (e.g. Danakil depression), where hot diapers
 Magmas produced in upper mantle are basaltic in character and basic in
composition with high amounts of FeO, MgO, and CaO.
 Alkalis, Na2O and K2O contents on the other hand are quite variable and
hence are used to classify basalts as alkaline, transitional and Sub-
alkaline
1) Alkali basalts characterized by
 Very high alkali content,
 Undersaturated in silica and contain nepheline and
 Undersaturated in potassic minerals like leucite and kalsilite.
• Alkali basalts are divided into
a) K- alkaline (K2O > Na2O) and
b) Na- alkaline (Na2O > K2O).
• Na-alkali basalts which show strong undersaturation in silica with high amount
of nepheline are known as basanites.
2) Transitional basalts are characterized by
 Slightly oversaturated to undersaturated in silica and
 Named as

a) potassic if K2O/Na2O is >1 and b) sodic if K2O/Na2O is <1.

Figure. Classification of basaltic magmas based on alkali and silica
3) Sub-alkaline basalts are
a) Tholeiitic basalts are characterized by
Low alkali content and
Slightly oversaturated in silica and
Contain orthopyroxene and olivine (olivine tholeiites,
quartz tholeiites etc).

b) Calc-alkaline basalts characterized by

 Contain high content of alkalis
(especially, K) than tholeiites
 Oversaturated in silica and
 Contain orthopyroxene and quartz.
 Volcanic rock classifications

Undersaturated

Saturated

Basic Acid
 MODAL ANALYSIS Vs. NORMATIVE ANALYSIS (NORM)

MODAL ANALYSIS

 Produces an accurate representation of the distribution and volume

percent of the mineral within a thin section.
 Requires only a thin section .

NORMATIVE ANALYSIS

 Normative analysis is defined as the calculation of a theoretical

assemblage of standard minerals for a rock based on the whole rock
chemical composition as determined by analytical techniques.
 Requires a chemical analysis.
 Various types of NORMs have been proposed – e.g. CIPW norm,
Niggli, Barth.
 Volcanic rock classifications

Undersaturated

Saturated

Basic
Acid
• Generation of basalts depends on many factors,
important among them are-
• Experimental studies have also suggested that
a) The degree of partial melting of the mantle rocks;
high degree of partial melting (>15-20%) and low
pressures favor the formation of tholeiitic basalts
b) The pressure at which the melting occurs; low
degree of partial melting (<5-10%), high pressure
and CO2 favor the formation of transitional and
alkaline basalts;
c) Abundance and type of fluid present during
melting; intermediate degrees of partial melting
(about 10-15%) in hydrated conditions generate calc-
alkaline basalts;
 Hence, calc-alkaline magmas are generated in subduction tectonics,
 Tholeiitic basalts at oceanic ridges due to the combined effects of
convecting hot material arising from deep mantle and of pressure release
due to crustal stretching (which produce extensive degrees of partial
melting of mantle rocks).
 However, some tholeiitic basalts can occur above subduction zones or
hotspots if the degree of partial melting is high.
 Various degrees of partial melting have strong bearing on the
concentrations of major and minor and trace elements.

 Due to this the content of some elements such as Ni, Cr will be more in
the mantle rock minerals (known as compatible elements) and will be
depleted in melt.

 In the case of elements like Th, Rb, Cs, Ba, La, Ce, Sr etc which will be
low in mantle rock minerals and high in the melt (known as
incompatible elements).

 The abundance of trace elements in the magma depends strongly on the

degree of the partial melting.

 So, alkaline basalts, which are formed by low degree of partial melting
will have much higher concentrations of incompatible elements than
calc-alkaline and tholeiitic basalts.
Magma Genesis in the Lower and Intermediate Continental Crust

 Temperature within the continental crust is, in general, not sufficiently

high to produce melting.
 In fact, basaltic and intermediate rocks which make up lower and
intermediate crust, have solidus temperatures in dry conditions around
1100-1200 OC at pressure of few kilobars.
 In hydrous conditions, the solidus temperatures are somewhat lower,
around 800-9000C.
 These values are much higher than those believed to be typically present
in intermediate-lower crust.
 So, for magma generation within the crust, the temperature has to be
increased, which is possible by intrusions of basaltic magmas rising
from the mantle.
• Consequently, partial melting or anatexis of the crust is possible.
Anatexis is also possible due the subducting
material at subduction zones.
Experimental petrological studies have indicated
that melting of
 a basic-intermediate rock gives rise to acid granitic (rhyolitic) to
granodioritic magmas.
However, such a possibility is ruled out by the
extremely large amount of heat that is needed to
have degrees of crustal melting higher than 50-
60%.
 These conditions are never reached in nature.
Therefore, granitic, granodioritic and, in some
 Regarding the behavior of trace elements, the above
mentioned rules for mantle melting are also valid for
crustal melting.
 The only difference is that the mineral phases present
in the crust are not the same as in the mantle and,
accordingly, some elements that are incompatible in
the mantle become compatible in the crust.
 This is the case for Sr and Ba that are hosted in
plagioclases and alkali feldspars, the main crustal
feldspar minerals.
 Accordingly, these elements are more abundant in the
crustal rocks than in the magmas formed by melting
of these rocks.
 Magma Evolution
• The main processes
responsible for magma
evolution are:
1) Fractional
crystallization,
2) Mixing and
3) Assimilation of wall
rocks.
 1) Fractional Crystallization

 It is the removal of early formed crystals from an originally homogeneous magma

(for example, by gravity settling) so that these crystals are prevented from further
reaction with the residual melt
 Fractional crystallization plays an important role and is the most important factor
in the magma evolution.
 In this process, crystallization of mineral phases and their separation from the
parent magma takes place due to the density contrast between the solid and
liquid phases.
 This causes a change in the composition of the residual liquid.
 Fractional crystallization mostly occurs when magma stops in the bodies of
variable size called magma chambers in which it undergoes cooling and
fractional crystallization before eventually reaching the surface as an extrusive.
 These chambers can be developed either in the crust or at the interface between
upper mantle and crust.
 The compositional modifications that the magmas suffer during fractional
crystallization however depend on the original composition of the magmas and the
separating minerals phases.
 So, it is convenient to state as a rule, evolved magmas formed by fractional -
crystallization become depleted, with respect to parental liquids, in those elements
that preferentially enter into the solid phases and are enriched in those elements
that do not preferentially enter into the solid phases.
 In other words, if a mineral contains - concentrations of a given element than
coexisting magmatic liquid, the abundance of this element decreases in the residual
magma.
 On the contrary, the elements that are not incorporated preferentially into the
crystallizing minerals increase in concentration in the residual liquids.
 If the ratio of the concentrations of a given element between minerals and magma,
known as partition coefficient, is higher than unity, the concentration of that
element decreases in the residual melt during fractional crystallization.
 Major element chemistry during FC
 With regard to major elements, fractionation of olivine mineral from a basaltic
magma causes decrease in MgO content and an increase in SiO2, alkalis and
other oxides in the residual melt.
 This is because olivine with Mg2SiO4 (forsterite, the first forming mineral)
composition, utilizes higher MgO compared to silica (of lower amount) and other
oxides.
 Different minerals will be formed and separated from the melt irrespective of the
nature of the magma either tholeiitic or calc-alkaline.
 The final stages of the fractional crystallization result in the acidic melts very
similar to those which are formed by crustal melting.
 The overall process produces a series of magmas ranging from basalt, andesite,
dacite to rhyolite.
These together make up the well-known calc-alkaline
magmatic series.
 In the case of K-rich alkaline magmas, early forming minerals like olivine and
clinopyroxene will be followed by leucite (feldspathoid mineral) and K-feldspar.
 As a consequence the K-alkaline basaltic liquids initially become enriched in
alkalis and silica but depleted in CaO and MgO.
 However, separation of alkali feldspars produces depletion in silica in the
residual liquids.
 In fact, these minerals have higher SiO2 than the magmas from which they
crystallize.
 As a result, the K-rich alkaline magmas never evolve toward acidic composition
and the resulting magmatic series will consist only of K-alkaline basalts,
phonolites, and tephrites.
 The most evolved magmas in this case will have a maximum SiO2 content slightly
higher than 60%.
 A similar evolutionary path is followed by Na-alkaline basalts, even though
nepheline and Na-feldspar are the main crystallizing minerals in those magmas.
 Changes in composition and variation of magmatic series
formed by fractional crystallization are better
explained/shown by plotting the concentration of major
oxides against silica for various rocks, which are formed by
magmas of different degrees of evolution.
 Such diagrams are called as variation diagrams or Harker
diagrams.
 Since silica increases with fractional crystallization in most
of the cases, its content is used as an index of the degree of
magma evolution especially for sub-alkaline rocks. An
alternative fractionation index for basaltic compositions is
MgO
 The shape is typical of fractional crystallization and is related
to the fact that the mineral assemblages crystallizing from
magmas change with ongoing evolution.
 This causes a modification in the rate of increase or decrease
of the elements, and whose variation trends result in the
curved lines.
 Variation (x-y)
diagrams

Figure. Harker variation diagram

for 310 analyzed volcanic rocks
from Crater Lake (Mt. Mazama),
Oregon Cascades.
 Trace element chemistry during FC

 Minor and trace elements also behave in a similar way as

major elements.
 The elements preferentially enter into the lattices of the
fractionating minerals (compatible elements) decrease
in abundance in the residual liquid.
 Instead, those elements that prefer to remain in the liquid
phase (incompatible elements) and become concentrated in
the residual melts.
 For instance, Ni, Co and Sc, which enter preferentially
into the lattices of olivine and pyroxenes, and Cr, which
is hosted by spinel and pyroxene, decrease during
fractional crystallization.
 Instead, U, Th, Rb and La which do not enter easily into
these phases are concentrated in the residual liquids.
 However, in some highly evolved magmas accessory
In other words, the crystallization of accessory
phases makes some elements, which are typically
incompatible for the main rock minerals, to
become compatible for the separating mineral
assemblage and, thus, to decrease with fractional
crystallization.

Fractional crystallization of accessory phases rich

in incompatible elements is more likely to occur
in sub-alkaline than in alkaline and transitional
magmas, because these phases are more soluble
in alkali-rich melts.
Harker diagrams for trace elements of calc-alkaline (in circles) and
Na-transitional series (in triangles).
 2) Mixing and Assimilation
 Mixing is a process by which magmas with different compositions blend
in a magma chamber or in a conduit to give a hybrid magma whose
composition is intermediate between the starting end-members.
 The composition of the hybrid magma depends on the weight fraction (i.e.
relative amounts) of each of the starting liquids.
 For instance, mixing between rhyolitic and basaltic magmas gives
either dacitic or andesitic or basaltic andesitic liquids depending on the
proportion of mixing (high, moderate or low) of the participating
acidic magma.
 Assimilation is the process of dissolution and incorporation of solid wall
rocks by magmas.
 Assimilation may be total or selective, depending on whether the entire
wall rock or only some minerals are assimilated.
 The magmas that have suffered assimilation of wall rocks are called
syntetic.
 The composition of the syntetic magmas depends on
 the composition of the starting magma, type and amount of the assimilated
rocks, on the style of assimilation, i.e. total or selective.
 Assimilation can be considered as a mixing between a liquid magma and solid
rocks or minerals.
 However, during assimilation magmas lose heat that is consumed to dissolve solid
material.
 This produces cooling of the magma with consequent crystallization and
fractionation of mineral phases.
 Accordingly, in most cases assimilation will be accompanied by fractional
crystallization.

 Magmas formed by different degrees of mixing or assimilation between two end-

members give linear trends between end-members on binary variation diagrams of
element vs. element.

 These trends contrast with that formed by fractional crystallization, which are
typically curved. between a mixing (between acidic & basic magmas) and a
fractional crystallization trend).
 Behavior of major, minor, and trace elements

The element can be taken up by the crystal

structures of the major silicates, either as
 isomorphous replacements
 random inclusions in the holes of a crystal lattice.
How much of a given element can be
accommodated in the silicate structures depends
 Charge & Radius
Rules formulated on the basis of the isomorphous
replacement of one ion by another:
1) A minor element may substitute extensively for a
major element if the ionic radii do not differ by more
than about 15%.
2) Ions whose charges differ by one unit may substitute for one
another, provided their radii are similar and the charge difference can
be compensated by another substitution.
• Example, in plagioclase feldspar Na+ readily substitutes for Ca2+ and the
charge difference is compensated by substitution of Si4+ for Al3+.
3) The rare alkali metal rubidium, for example, is so similar to
potassium that several tenths of a percent can be accommodated as
replacements of Rb for K in micas and feldspars.
4) The rare metal zirconium cannot fit easily into common silicate
structures, and even very small amounts of it go into separate
crystals of the accessory mineral zircon.
5) Some elements, like beryllium, boron, copper, and uranium, are
capable neither of forming their own high-temperature minerals nor
of substituting appreciably for common ions in silicate structures and
so are concentrated in the residual solutions that give rise to
pegmatites and sulphide-bearing quartz veins.
 Distributions of Elements in Igneous rocks
Following are some general patterns suggested on the basis many
analyses of igneous rock series:
1) Cations with large radii and low electric charges tend to
substitute for potassium (radius of K+= 1.38 Å),
 Are concentrated in felsic rather than in mafic rocks.
 These elements (Rb, Cs, Ba, Pb, Tl) are often called the large-ion
lithophile group (LILE).
2) Several cations with smaller radii and mostly with higher charges
(U4+,Th4+, B3+, Mo6+, W6+, Nb5+,Ta5+, Sn4+, Zr4) also are
concentrated at the felsic end of the series.
 Because of the small size and high charge, the electric field associated
with these ions is unusually strong, and they are often designated high
field-strength elements (HFSE).
 Differentiation segregates them into the late residual solutions, and
present in appreciable amounts they may form minerals of their own
like uraninite, beryl, columbite, zircon etc.
3) Many elements whose ions have intermediate radii, especially metals of
the transition groups, substitute readily for iron and magnesium, hence
are abundant in the earlier members of the differentiation sequence.
4) Some Cr, Ni, Co are strongly enriched within ultramafic rocks and others
like Mn, V, Ti have maximum abundance in gabbros and basalts.
5) Among the chalcophile elements, a few substitute to some extent for
major cations in silicate structures (Zn2+ for Fe2+ and Mg2+, Bi3 for Ca2+),
but majority of these metals get accumulated in the residual solutions that
may eventually form sulphide ores.
6) Some minor elements are so similar in size and chemical properties to
major elements that normal differentiation cannot separate them
effectively from their major relatives.
– Closely related pairs are Ga and Al, Rb and K, Hf and Zr, Cd and
Zn.
 The Rare Earth Elements (REE) Geochemistry
Rare earth elements (REE)
 Is a group of elements with atomic numbers between 57
(La) and 72 (Lu)
 Characterized by relatively large ionic radii, and valences
of either +2 or +3.
 Because of their high charge and large radii, the rare
earths are incompatible elements.
 Can be classified into:
• Light rare earth elements (LREE)are La - Gd, and
• Heavy rare earth elements (HREE) are Tb - Lu.
The distribution of REE, as is evident from the
simple rules of substitution, leads readily to
speculation about the
 Genesis and history of particular igneous rocks and rock
associations.
From REE abundance data, it is evident that all of
this group, with the single exception of
europium, are more concentrated in granite than
in basalt.
The simple facts about abundances tell us that the
REE are to some extent incompatible with the
igneous magmas.
 REE are remarkable for the similarity in their chemical and
physical properties, with a principal oxidation number of 3+.
 Ionic radius shrinks steadily from La (the lightest rare earth)
to Lu (the heaviest rare earth); filling f-orbitals; called the
“Lanthanide Contraction”.
 The slight decrease in size means slight differences in
properties, which are reflected in differences in the
distribution of these elements in geologic materials.
Contrasts and similarities in the D values:
All are incompatible
Table 9-1. Partition Coefficients (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks

Also Note: Olivine Opx Cpx Garnet Plag Amph Magnetite

Rb 0.01 0.022 0.031 0.042 0.071 0.29
Sr 0.014 0.04 0.06 0.012 1.83 0.46
HREE are less Ba 0.01 0.013 0.026 0.023 0.23 0.42
incompatible Ni 14.0 5.0 7.0 0.955 0.01 6.8 29.
Cr 0.7 10.0 34.0 1.345 0.01 2.0 7.4
Especially in garnet La 0.007 0.03 0.056 0.001 0.148 0.544 2.
Rare Earth Elements

Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.

Eu can  2+ which Nd
Sm
0.006
0.007
0.03
0.05
0.23
0.445
0.026
0.102
0.055
0.039
1.34
1.804
2.
1.
conc. in Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1.
Dy 0.013 0.15 0.582 3.17 0.023 2.024 1.
plagioclase Er 0.026 0.23 0.583 6.56 0.02 1.74 1.5
Yb 0.049 0.34 0.542 11.5 0.023 1.642 1.4
Lu 0.045 0.42 0.506 11.9 0.019 1.563
Data from Rollinson (1993). * Eu3+/Eu2+ Italics are estimated
The REE plots "normalized” to chondritic concentrations

Figure.4.6. Chondrite- normalised REE

diagram for six rock samples (Krauskopf
and Bird, 1995)
A. Peridotite xenolith; B. Basalt (MORB); C.
Rhyolite; D. Granite; E. Anorthosite; F.
North American Shale (Rock that represent
material formed by repeated
differentiation by both igneous and
sedimentary processes over long geologic
times)].

• Two dominant LREE patterns relative to HREE

1) LREE-depleted.
Example: Peridotite xenolith
2) LREE-enriched
Example: Rhyolite, Granite
 Europium anomaly when plagioclase is
 A fractionating phenocryst
 A residual solid in source

Figure REE diagram for 10%

batch melting of a hypothetical
lherzolite with 20% plagioclase,
resulting in a pronounced
negative Europium anomaly.
From Winter (2001) An
Introduction to Igneous and
Metamorphic Petrology.
Prentice Hall.
 Normalized Multielement (Spider) Diagrams

 An extension of the normalized REE technique to a broader

spectrum of elements

Chondrite-normalized spider
diagrams are commonly
organized by (the author’s
estimate) of increasing
incompatibility L  R

Different estimates 
different ordering (poor
standardization)

Fig. 9.6. Spider diagram for an alkaline basalt from Gough Island, southern Atlantic. After
Sun and MacDonough (1989). In A. D. Saunders and M. J. Norry (eds.), Magmatism in the
Ocean Basins. Geol. Soc. London Spec. Publ., 42. pp. 313-345.
 Application of Trace Elements to Igneous Systems
1) Determination of the depth of generation of a primary magma.
 Because different trace elements have different chemical
characteristics, their concentrations in a magma produced by
partial melting of a source rock will depend on the phases
occurring in this source rock and the abundance of these phases.

 For example, elements such as Sr are strongly fractionated in

plagioclase feldspars. In the absence of Plag from the source
rock, Sr will be incompatible, and will be highly enriched in a
magma formed by small degrees of partial melting.

 If the source rock is Plag - bearing, the magma will be less

enriched in Sr until Plag melts completely.
 Primary basalts are produced by partial melting at different depths in
the mantle.

 At shallow depths, the mantle consists of Plagioclase Lherzolites,

 At depths between 40 and 80 km, it consists of spinel Lherzolites,
 whereas at depths > 80 km, it consists of garnet Lherzolites.

Because Plag, Spinel and garnet concentrate Sr, V + Cr, and heavy
rare earth elements (HREE), respectively, magmas produced by
small degrees of partial melting at shallow depths will be depleted in
Sr, those from intermediate depths will be depleted in V and Cr,
whereas those from depths > 80 km will be depleted in HREE.
 Identification of the source rock or a particular mineral involved
in either partial melting or fractional crystallization processes
 •Garnet concentrates the HREE and fractionates among them
Thus if garnet is in equilibrium with the partial melt (a residual phase in the source left
behind) expect a steep (-) slope in REE and HREE

Table 9-1. Partition Coefficients (CS/CL) for Some Commonly Used Trace
Elements in Basaltic and Andesitic Rocks

Olivine Opx Cpx Garnet Plag Amph Magnetite

Rb 0.01 0.022 0.031 0.042 0.071 0.29
Shallow (< 40 km) Sr 0.014 0.04 0.06 0.012 1.83 0.46
Ba 0.01 0.013 0.026 0.023 0.23 0.42
partial melting of the
Ni 14.0 5.0 7.0 0.955 0.01 6.8 29.
mantle will have Cr 0.7 10.0 34.0 1.345 0.01 2.0 7.4
plagioclase in the La 0.007 0.03 0.056 0.001 0.148 0.544 2.
Rare Earth Elements

resuduum and a Eu Ce 0.006 0.02 0.092 0.007 0.082 0.843 2.

anomaly will result Nd 0.006 0.03 0.23 0.026 0.055 1.34 2.
Sm 0.007 0.05 0.445 0.102 0.039 1.804 1.
Eu 0.007 0.05 0.474 0.243 0.1/1.5* 1.557 1.
Dy 0.013 0.15 0.582 3.17 0.023 2.024 1.
Er 0.026 0.23 0.583 6.56 0.02 1.74 1.5
Yb 0.049 0.34 0.542 11.5 0.023 1.642 1.4
Lu 0.045 0.42 0.506 11.9 0.019 1.563
Data from Rollinson (1993). * Eu3+/Eu2+ Italics are estimated
 10.00

8.00 67% Ol 17% Opx 17% Cpx

sample/chondrite

6.00 Garnet and Plagioclase

4.00
effect on HREE
2.00

0.00
56 58 Ce 60 Nd 62Sm Eu
La 64 Tb66 68
Er 70 Lu 72
Yb

10.00
10.00

60% Ol 15% Opx 15% Cpx 10%Plag 8.00 57% Ol 14% Opx 14% Cpx 14% Grt
8.00 sample/chondrite
sample/chondrite

6.00
6.00

4.00
4.00

2.00
2.00

0.00
0.00
56 58
La Ce60 Nd 62Sm Eu
64 Tb66 68
Er 70 Lu
Yb 72
La Ce Nd Sm Eu Tb Er Yb Lu
2) Prediction of the phases fractionating from a magma.
 Separation of:
(a) Plag depletes the remaining melt in Sr and Eu,
(b) Ol depletes it in Ni and Co,
(c) spinels deplete it in V, Cr and possibly Zn,
(d) K-spar in Ba and Rb, ... etc.

3) Discriminant diagrams
 Trace elements can also be used to identify the paleotectonic setting of
some igneous rocks (i.e. to determine where they were erupted).
 In this case, rather than use the absolute concentrations of trace elements
(which may have been affected by such post-magmatic processes as
weathering, alteration or metamorphism), ratios of relatively immobile
trace elements (as these are least affected by post magmatic processes).
 Table 9.6 A Brief Summary of Some Particularly Useful Trace Elements in Igneous Petrology

Element Use as a Petrogenetic Indicator

Ni, Co, Cr Highly compatible elements. Ni and Co are concentrated in olivine, and Cr in spinel and clinopyroxene. High concentrations

indicate a mantle source, limited fractionation, or crystal accumulation.

Zr, Hf Very incompatible elements that do not substitute into major silicate phases (although they may replace Ti in titanite or rutile).

High concentrations imply an enriched source or extensive liquid evolution.

Nb, Ta High field-strength elements that partition into Ti-rich phases (titanite, Ti-amphibole, Fe-Ti oxides. Typically low concentrations

in subduction-related melts.

Ru, Rh, Pd, Platinum group elements (PGEs) are siderophile and used mostly to study melting and crystallization in mafic-ultramafic

Re, Os, Ir, systems in which PGEs are typically hosted by sulfides. The Re/Os isotopic system is controlled by initial PGE differentiation

Pd and is applied to mantle evolution and mafic melt processes.

Sc Concentrates in pyroxenes and may be used as an indicator of pyroxene fractionation.

Sr Substitutes for Ca in plagioclase (but not in pyroxene), and, to a lesser extent, for K in K-feldspar. Behaves as a compatible

element at low pressure where plagioclase forms early, but as an incompatible element at higher pressure where plagioclase is

no longer stable.

REE Myriad uses in modeling source characteristics and liquid evolution. Garnet accommodates the HREE more than the LREE, and

orthopyroxene and hornblende do so to a lesser degree. Titanite and plagioclase accommodates more LREE. Eu2+ is strongly

partitioned into plagioclase.

 Geochemistry of Sedimentary Rocks

 Compared to the igneous process, sedimentary process operates

 In the surface conditions and under low temperature and
pressure conditions.
 Different stages mainly involved in the over all
sedimentary process are
a) Weathering and erosion of pre-existing rocks
b) Transportation of clastic particles (minerals) and dissolved
matter (including colloids and ions)
c) Deposition
d) Diagenesis (lithification- transformation of loose sediments
into sedimentary rocks).
 These activities are facilitated by different agents
like water, air and factors like pH, Eh etc.
 Sedimentary Process
a) Weathering
 Minerals that crystallize at higher temperature are
more unstable than minerals formed at lower
temperature.
 Accordingly, igneous minerals have the following
order of decreasing stability:
 Quartz> Alkali feldspar> Mica> Amphibole> Na-
plagioclases> Pyroxenes and Ca-plagioclases> Olivine
(Goldich series- the same minerals as the Bowen series, but
in an opposite order).
 Accessory minerals are mostly resistant to alteration
 Example: zircon, apatite, allanite, corundum, etc.
 b) Decomposition

The decomposition of minerals takes place by

water through a series of reactions that include
– Dissolution, hydrolysis, oxidation etc.
As a result of mineral decomposition some
components go into solution and are transported
as ions; others form new minerals that are
transported as colloids or remain in situ.
A common solution reaction is that of calcite in
water.
Calcite is very poorly soluble in pure water but it
is dissolved quite readily by acid rain water
 C) Transport

Material derived from weathering of rocks can be

transported as solid particles, colloids or ions.
 Solid particles are represented by mineral grains or rock
fragments that have resisted chemical weathering.
 They are transported for various distances depending on the
size and density of the particles and the energy of the
transporting agent.
Colloidal suspensions contain fine particles with a
size ranging from 10-2 to 10-5 mm.
 The most common materials transported as colloids are clay
minerals and oxide and hydroxides of Fe, Al, Cr, Mn and V.
 Colloidal particles are electrically charged and they aggregate
and precipitate (flocculation of colloids) when they come in
contact with electrolytes.
 Colloids have also the important characteristic property of
adsorbing certain substances.
 For instance, montmorillonite adsorbs potassium and is
transformed to illite.
 Moreover, natural colloids also adsorb heavy metals such as
arsenic and lead that are poisonous for life.
 The behavior of elements during transport and sedimentation
depends on their chemical characteristics and on the physical
conditions (essentially temperature, pH an Eh) of the water.
Ionic potential plays a crucial role in the behavior
of elements in aqueous solution.
Ionic potential is the ratio between charge (q)
and ionic radius (r): P = q/r.
 Ions with low ionic potential such as Cs, Rb, K and Na etc,
are highly soluble in water and are transported as ions.
 Elements with intermediate ionic potential such as Fe3+, A13+,
Ti4+, U4+ bind to hydroxyl groups and form insoluble
hydroxides.
 Ions with higher ionic potential such as C4+, N5+, P4+ bind to
oxygen to form carbonate, phosphate and nitrate ions that are
again soluble.
pH and Eh also play a key role during transport
and sedimentation.
 For instance low pH favors precipitation of silica, whereas
high pH facilitates solubility for SiO2.
 The opposite occurs for Al2O3 that is more soluble in acid than
in alkaline solutions.
Eh conditions of waters have important effects
on the behavior of elements that have different
oxidation states.
 For instance, high Eh conditions typically observed for waters
at intense and direct contact with atmosphere such as running
waters, favor the formation of ferric oxides and hydroxides
that are transported as colloids.
 On the contrary, low Eh stabilizes ferrous iron that is soluble.
Behavior of ions with respect to ionic potential
 D) Deposition

Minerals that are resistant to weathering are

partly left in situ and partly transported as
granular material and are deposited in zones of
low water energy, in suitable depressions to form
thick sand bodies.
Lithification of sand gives sandstones.
Argillaceous material, which is produced by the
reaction of several minerals especially feldspars
is partly left in situ and partly transported as clay
and colloids by waters.
 Concentration of ferric iron, manganese and Al-hydroxides can
give sedimentary deposits of economic importance.
 Moreover, since colloids attract impurities, these deposits may
be enriched in several metals such as Ni, Sb, W, Zn etc.
 Among the elements that remain in solution (e.g. Na, Cl, K, and
Ca), Ca is taken up by corals and by other organisms to form
skeletal material.
 However, calcium carbonate can also precipitate by purely
chemical processes by supersaturated solutions.
 The study of sea water has shown that at shallow depths there is
super saturation of calcium carbonate.
 At depth, the solubility of calcium carbonate increases.
 This is due to the decrease in temperature and increase in
pressure with increasing depth, which determines an increase of
CO2 solubility.
 This, in turn, causes an increase of CaCO3 solubility.
 As a consequence, sea water becomes undersaturated in CaCO3
at a depth of about hundred meters.
 Accordingly, calcite and aragonite can precipitate only from
shallow waters.
 Soil formation
 The nature of soil depends heavily on the
composition of the rocks, drainage and on the
climatic conditions.
 It has been demonstrated that in areas of high
rainfall and high relief characterized by high water
flow rates, gibbsite minerals are formed by
weathering of feldspars.
 In areas of low rainfall and low relief (low flow
rate) montmorillonite is preferentially formed.
 Kaolinite is formed in intermediate conditions.
 Concerning the composition of the original rocks,
presence of ferromagnesian minerals favor the
7/2/2022 66
  Each soil horizon represents a
different environment with
different conditions of redox
potential, acidity and other
properties.
 Elements can behave differently
in each soil horizon and can
have different background
(normal) concentrations.

7/2/2022 67
Soil Profiles and Geochemistry
 CHAPTER FOUR
Discriminating between tectonic environments using
geochemical data
 How can we classify granitic igneous rocks based on the
molecular proportions of Al2O3, Na2O, K2O and CaO.
 How can we plot Triangular Variation Diagrams( AFM)
 How can we do Bivarient (Harker diagrams).
 How can we do Rare Earth Elements Normalization
diagram
 Discrimination diagram
 Trace elements are used as a tool to determine paleotectonic
environment.
 Useful to suggest the former tectonic environment.
 Concentrated on elements that are immobile during low/medium
grade metamorphism.
 Useful for rocks in mobile belts that are no longer recognizable in
their original setting.
 Can trace elements be discriminators of igneous environment?
 Trace element discrimination diagrams for
basaltic to andesitic compositions.

 Useful to suggest the former tectonic environment

 Ti-Zr-Y diagrams proposed by Pearce and Cann (1973)-

tectono-magmatic discrimination diagram.

 Most effectively to discriminate between within plate

basalts i.e. ocean-island and other basalt types.
Fig: Ti/100-Zr-Yx3. Tectonic discrimination diagram for basaltic
rocks.(After pierce and Cann 1973.)
Fig: Zr/Y -Zr. Tectonic discrimination diagram for basaltic rocks.(After Pearce
and Norry 1979)
 Discrimination diagrams for rocks of granitic
composition.
 Granites can be divided according to their intrusive settings
into four groups:
 Ocean ridge granites (ORG),
 Volcanic arc granites (VAG),
 With in plate granites (WPG) and
 Collisional granites (COLG).
 Trace element system most widely used is that of Pearce et al
(1984), who divided granites into the above four tectonic
settings.
 This scheme is based on the relative abundance trace
elements, principally Rb, Nb and Y which characterize
different granites from known tectonic setting.
 The Rb Vs Y+Nb plot is used to differentiate the syn
collisional granites from the volcanic arc granites.
 Use of trace elements as tectonic discriminates
(granitoids)

Figure Examples of granitoid discrimination diagrams used by Pearce

et al. (1984
 Use of trace elements as
tectonic discriminates (basalts
and andesites)

Figure 9-8. (a) after Pearce and Cann (1973), Earth Planet, Sci. Lett., 19, 290-300. (b) after Pearce (1982)
in Thorpe (ed.), Andesites: Orogenic -andesites and related rocks. Wiley. Chichester. pp. 525-548, Coish
et al. (1986), Amer. J. Sci., 286, 1-28. (c) after Mullen (1983), Earth Planet. Sci. Lett., 62, 53-62.