Banaras Hindu University

Department of Geology
Presentation on
Mineral formulae recalculation using
EPMA Data
Pyroxenes EPMA Analysis
Presented by:- Priyanshu Kumar
Exam roll no.:-22220GLG025
Date:- 29-May-2025
Submitted to
Dr. Amiya Kumar Samal
 INTRODUCTION
Pyroxenes are a group of inosilicate
minerals common in igneous(basalts,
gabbro) and metamorphic(eclogites)
rocks.

They are important rock forming

mineral stable almost under every
condition and may also form during
metamorphism.

Forming in mantle pyroxenes are key to

understanding petrogenesis, mantle
processes, and planetary geology.
 Basic Chemical Formula
General Formulae :- W1-p(X,Y)1+pZ2O6

X= Mg,Fe2+,Mn
Y = Al,Fe3+,Ti
Z = Si, Al
W = Na, Ca

Here the element in the place of X and Y are octahedrally

coordinated and occupy the M1 sites while those in place of Z
occupy Tetrahedral site and those in the place of W occupy the M2
sites in the pyroxene structure.
Fig.1: Ternary Composition Diagram for Pyroxenes, ALEX STREKEISEN

 Example :-  End Member :-

• Enstatite: Mg₂Si₂O₆ • Enstatite: Mg₂Si₂O₆
• • Ferrosilite: Fe₂Si₂O₆
Ferrosilite: Fe₂Si₂O₆
• Wollastonite: CaSiO3
• Diopside: CaMgSi₂O₆
• Augite : NaAlSi₂O₆
 Crystal Structure of Pyroxenes
Pyroxenes crystallizes in Single-chain inosilicate
structure.

In this structure one SiO₄ tetrahedra shares its two

oxygen with two other SiO₄ tetrahedra

The SiO₄ tetrahedra form chains along the c-axis Fig.2: Inosilicate single Chain Structure,
Tulane University

Pyroxenes crystallize in two crystal system

Orthorhombic and Monoclinic and hence named
orthopyroxene and clinopyroxene respectively.

Fig.3: Pyroxenes Structure, Doubtnut

 Site Occupation
There are three cation sites in which are occupied by various cations
• M1 (regular octahedral) : Smaller cations, (Mg2+, Fe2+,
Fe3+, Al3+, Ti4+)
• M2 ( distorted octahedral) : Larger cations (Ca2+, Na+, Fe2+,
Mg2+, Mn2+,Sr2+).
• T (tetrahedral) : Si4+, Al3+ forming silicate chains.

Fig. 4: M1, M2 Octahedral Site distribution in Pyroxenes, Geology Is The way

 Pyroxene Quadrilateral

Fig.5: Pyroxene Quadrilateral, The Planetary Society

Pyroxene quadrilateral is solid solution diagram showing

the various field in which the various minerals of the
pyroxene group exist.
Example:-
Enstatite (Mg) ↔ Ferrosilite (Fe)
Diopside (CaMg) ↔ Hedenbergite (CaFe)
It is important for classifying pyroxenes in igneous rocks.
 Electron Probe Micro-Analyzer
EPMA, or Electron Probe Micro-Analyzer, is an analytical device that employs a
concentrated stream of electrons to examine the elemental makeup of solid materials at a
microscale. This non-destructive method enables both qualitative and quantitative
assessments of the elements found within a sample.
EPMA operates by directing a
concentrated electron beam onto a small
region of a solid sample. This
engagement with the atoms in the
sample produces distinctive X-rays that
are subsequently sensed and examined.
The X-rays that are emitted are utilized to
recognize the elements within the sample
and assess their concentrations.
Fig.6: EPMA Laboratory View,
Fig.7: EOMA Working Method, JEOL
 Mineral Formulae Recalculation
The process of converting chemical analysis data—usually weight percentages of
oxides—into a chemical formula that expresses a mineral's composition in terms
of atoms per formula unit (a.p.f.u.) is known as mineral formula recalculation. For
figuring out the ratios of elements in each crystallographic site inside the
structure of a mineral, this computation is essential.
The steps involved are:-
We will take example of Diopside with SiO2 54.38 MgO 18.61 CaO 27.01 by wt.% to
understand the steps involved.
• Convert weight % of each oxide to
molar proportion. This is done by
dividing given wt.% with formula
weight of the oxide.

Based on this write a general formulae for the

diopside.
Ca0.553Mg0.462(SiO2)0.838
 Normalization :-

• Obtain oxygen number by multiplying mole of each

oxide by number of oxygen atoms in it and sum it.
Obtain normalization constant by dividing total
number of oxygen in formulae by oxygen number.

• Each oxide's "oxygen number" should be multiplied

by a normalization constant, which is calculated by
dividing the total number of oxygens in the
required formula by the sum of the "oxygen
numbers.“
This will give “normalized oxygen value”

• The number of cations per oxygen in the oxide

formula is multiplied by the "normalized oxygen
numbers" of each oxide.
The mineral formulae hence calculated is :- CaMgSi2O6
 Dataset Overview
 After analyzing 22 pyroxene samples for oxide weight percentages, cation
distributions, site occupancies, and end-member composition the
observation recorded are :-

 Major Oxides :-
 SiO2: 49.22%–51.18% (silicate framework).
 CaO: 17.79%–20.58% (M2 site).
 MgO: 14.24%–15.76% (M1/M2 sites).
 FeO: 7.95%–12.74% (M1/M2 sites).
 Al2O3: 2.50%–3.56% (T/M1 sites).

 Minor Oxides: TiO2 (0–0.77%), MnO (0–0.34%), Na2O

(0.26%–0.34%), SrO (0.43%–0.52%), Cr2O3, NiO, P2O5,
K2O
(negligible).
• Mineral Chemical Data.

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 Analytical Methods

 Oxide Analysis :- Weight % were measured for chemical analysis using the
Electron Microprobe analyzer.

 Cation Normalization :- Cations and Oxides were calculated to 4 and 6 per

formulae unit respectively to determine the site occupancy.

 End Member Calculation :- Wollastonite (XWo), Enstatite (XEn), Ferrosillite

(XFe) compositions have been derived from the oxide proportions .

 Assumptions:- Fe has been assumed as Fe2+ (FeO); Fe2+/Mg

ratio assumed to be same in both M1 & M2 sites.

 Oxide ratios (e.g., MgO/FeO, Al₂O₃/TiO₂) used to infer magma source.

 Oxide Relationship

 CaO v/s MgO :- There is an inverse

relationship , this is due to Ca2+
↔ Mg2+ substitution in M2
site.
A high CaO implies Wollastonite
component, hence reducing the
Enstatite component.

 Feo v/s Cao :- Weak

inverse relationship due
to Fe2+ ↔ Ca2+
substitution in the M2
site.
A high FeO component implies
increased Ferrosilite/hedenbergite
component
 SiO2 v/s Al2O3 :- Weak inverse
relation due to substitution
of Al3+ ↔ Si4+ in the
tetrahedral (T) site.
High Al3+ substitution is suggesting an
elevated pressure-temperature conditions as
high pressure is unfavourable for silica
tetrahedra linkage and hence the
substitution.

 MgO v/s TiO2 :- Weak inverse

relation, suggesting Ti decrease
with Mg increase and vice versa.
High TiO2 indicates high temperature
conditions(>800°C) which is an
indicator of evolved magma.
 CaO v/s SrO :- Weak positive correlation:
because of their similar ionic radii, Sr2+
replaces Ca2+ in M2 (0.43%–0.52%).

The availability of trace elements in the

magma is reflected in Sr2+ substitution.

 Na2O v/s CaO :- There is no strong

correlation; Na+ in M2 site.
A low alkali level in the source is indicated by a
low Na+, which also suggests a little
jadeite/aegirine component.
 In most of the samples, Cr2O3, NiO, P2O5, and K2O
are either negligible or nonexistent (usually less
than 0.01%).

 Due to low concentration there is not any significant

relation between major and minor oxides.

 This significantly low amount of trace element in the

sample indicates a simple geochemical system with
a minimal influence on the pyroxene composition.
 Site Occupancy
 Tetrahedral (T) :- Forms the silicate chain backbone, which is
critical for pyroxene structure.
• Si4+ (1.854–1.909) apfu, is dominant cation while There
is minor substitution of Al3+ (0.091–0.120) apfu.
• This indicate that the structure is well maintained while
with temperature pressure increase there is minor Al 3+
substitution in T site.
 M1 Site :- It is key for Mg-Fe solid solution and is site for
smaller cations in structure.
• Mg2+: 0.655–0.757 apfu, is primary cation.
• Fe2+:0.214–0.315 apfu, shows notable substitution with
Mg.
• Al3+: 0–0.048 apfu, minor Tschermak component.
• Ti4+: 0–0.022 apfu, is high-T indicator
 M2 Site:- Ca dominating in cpx. And is host site for large
cations.
• Ca2+: 0.710–0.820 apfu, is dominant cation.
• Mg2+: 0.106–0.173 apfu, significant in enstatite
component.
• Fe2+: 0.033–0.083 apfu, hedenbergite
component.
• Na+, Sr2+: 0.019–0.028 apfu, 0.009–0.011 apfu,
minor substitutions.
Clinopyroxene structure is confirmed by Ca2+ dominance; low
alkali/trace element content is indicated by minor Na+ and Sr2+.
 End Members Compositions

 End Member Ranges :-

• Wollastonite (XWo): 36.69–42.25%, high Ca2+ in

M2.
• Enstatite (XEn): 41.43–45.14%, dominant Mg2+
in M1/M2.
• Ferrosilite (XFs): 12.75–20.51%, Fe2+
substitution in M1/M2.
It is evident from the given two ternary
plot that the compositions cluster in the
diopside field (CaMgSi2O6) with a little
clustering in the Augite field as well.
 Geochemical Interpretation

• TiO2 – MgO system :-

 Ti4+ inclusion indicates high-temperature crystallization (>800°C), which is
typical of mafic magmas or early fractional crystallization (e.g., 0.77% TiO2
at 14.60% MgO, page 11 of pdf ).
 TiO2 in certain samples (such as tholeiitic basalts) suggests hotter,
potentially more advanced magmatic settings.
 Low TiO2 in High Mg samples is indicator of primitive magma source.
• Al2O3 - CaO system :-

 Higher Al2O3 indicates conditions for the Tschermark substitution which

is favored in deep mantle/crustal setting with pressure > 5kbar.
 This indicates mineral crystallization in lower part of crust or in mantle,
and also in high grade metamorphic rocks such as granulite.
• Mg2+/Fe2+ in M1 and high Ca2+ in M2 , hence the
sample is classified as diopsides with hedenbergite and
enstatite-ferrosilite constituents.

• Na+, Sr2+ in M2; Ti4+, Al3+ in M1 indicate

high-T or high-P condition.

• Low TiO2, Na2O, SrO: Suggests primitive or

depleted source, minimal alkali/trace element
enrichment.
 Conclusion

 Geological Environment :- The mineral is likely to

have crystallized in high P-T conditions or in regions
of high grade metamorphism thus indicating mafic
rocks, granulite or amphibolites.
 Geochemical Insights :-
• TiO2-MgO indicating high-T, evolved magmas), CaO-Al2O3
suggests high-P, deep settings, low minor oxides suggests a
primitive source.

• The clinopyroxene is silica saturated and shows a limited Al

substitution indicating calc-alkaline basalts and tholeiitic
basalts.

• The clinopyroxene is characterized by high M1Al concentrations (0–0.048 apfu),

possibly responding to a high pressure crystallization conditions like lower
crust, mantle or high-grade metamorphic environments such as amphibolites,
granulite.
• The scatter plot and table confirm that most pyroxene analyses have Si + Al values slightly above 2,
indicating unavailability of Si at M1 site and silica saturated nature of the magma.
this suggests a sub-alkaline basal

• The low Na concentration (0.26%–0.34%) is also indicating towards a sub-alkaline

basalt host.
  Predicted Tectonic Setting:- Mid-Ocean Ridge Basalt (MORB) or Back-Arc
Basin

Evidences:
• Low Ti, Na: Typical of tholeiitic basalts
• Fe/(Fe+Mg) = 0.22–0.32:Primitive to moderately evolved magma
• High Ca (Wo), Mg (En): Augite/diopside, common in MORB

 Structural Insights :- Stable T site, Ca2+-dominant M2,

Mg2+-Fe2+ in M1 however there are minor vacancies in M1.

The pyroxenes are excellent petrogenic indicator, the chemical composition of clinopyroxene can reveal
the host basalts' tectonic setting. The pyroxene mineral data are thus widely used in finding tectonic
settings of various igneous rocks such as ophiolitic basalts, gabbro, metabasalts, etc.
 References :-

• Rock Forming Minerals, Deer Howie Zussman

• Mineralogical constraints on petrogenesis and tectonic affiliation

of Karnaprayag-Rudraprayag metamafics, Garhwal Lesser
Himalaya, Pandey_et_al

• Leterrier et al. (1982)

Thanks..!!