Mineral Chemistry Analysis

Dr. Arifudin Idrus

Department of Geological Engineering
Gadjah Mada University – INDONESIA
E-mail address: arifidrus@ugm.ac.id
 Introduction
• The common minerals are made up mostly of
the abundant elements in the crust.
• We can express the chemical composition of
such minerals by a simple (and sometimes not
so simple) chemical formula, all minerals
exhibit some chemical variation.
• Pure minerals (those with a chemical
composition exactly the same as the chemical
formula) are rarely found in nature.
• if we had a technique for measuring even
the smallest concentrations of elements, we
would see that any given mineral probably
contains every stable element in the
periodic table.
• Most of these elements would occur in very
low concentrations (parts per trillion or
less), nevertheless they are present.
• Analysis of minerals is quite different from
analysis of rocks.
• Chemical analysis of rocks involves
analyzing an aggregate of minerals.
• So, in most case the rock can be grounded
to a fine powder and subjected to one of the
methods.
 Mineral chemical analysis
• Analysis of a mineral is more complicated
because:
– Individual minerals are much smaller than rocks
and it is therefore difficult to obtain enough
sample of a mineral to perform the chemical
analysis.
– In cases where a single mineral is too small to
provide enough sample, several grains of the
same mineral can be separated from a rock and
analyzed as a single sample.
– Individual minerals may be chemically zoned.
• Electron Probe is a powerful tool.
 METHODS OF CHEMICAL ANALYSIS

1. Wet Chemical Analysis

2. Inductively Coupled Plasma-Mass
Plasma
Spectrometry (ICP-MS)
MS)
3. X-Ray
Ray Fluorescence (XRF)
4. Electron Microprobe
obe (EMP) Analysis
 1. Wet Chemical Analyses
• Prior to about 1960 classical wet chemical
analysis was the only means of determining
the chemical composition of minerals.
• Wet chemical analyses always involves
dissolving the mineral into an acidic
solution.
 1. Wet chemical analysis
• Gravimetric Analyses- the element of interest is precipitated as a
compound. The precipitate is then weighted to determine its
proportion in the original sample.
• Volumetric Analyses - In this type of analysis titration is used to
determine the amount of reagent that is added in order for a
specific chemical reaction to occur that involves the element of
interest. From the volume of reagent added, the concentration of
the element can be calculated.
• Colorometric Analyses - A reagent is added to the solution that
reacts with the element of interest to produce a color change in
the solution. The intensity of the color is proportional to the
concentration of the element of interest, and thus when
compared to standard solutions in which the concentration is
known, the concentration of the element in the unknown solution
can be determined.
 1. Wet chemical analysis

• Generally all elements cannot be

determined by the same wet chemical
methods and different methods are more
sensitive for different elements.

• Complete wet chemical analysis usually

involves a combination of methods.
2. Inductively Coupled Plasma - Mass
Spectrometry (ICP-
(ICP-MS)

• ICP-MS
MS combines two instruments, an
inductively coupled plasma spectrometer
and a mass spectrometer to simultaneously
measure most elements in the periodic
table and determine concentration down
to the sub part-per
per trillion (ppt) level.
 ICP--MS
ICP
• The sample of mineral or rock must first be
powdered and put into solution in acid.
• This solution is then injected into a plasma as an
aerosol where the atoms in the sample are
ionized.
• The plasma is produced by passing Ar gas into an
energy field induced by a radiofrequency (RF)
generating coil.
 ICP--MS
ICP

• The RF energy field causes collisions between the

Ar atoms, generating a high energy plasma.
• The sample aerosol is instantly decomposed in the
plasma (temperature of 6,000 - 10,000 K) to form
analyte atoms which are simultaneously ionized.
• The ions produced are extracted from the plasma
into a mass spectrometer which is held at high
vacuum.
 ICP-MS
MS
• The mass analyzer then separates the ions based
on their mass/charge ratio.
• The mass analyzer is essentially four parallel
molybdenum rods to which a combination of RF
and DC voltages are applied.
• The combination of these voltages allows the
analyzer to transmit only ions of a specific
mass/charge ratio.
• Finally, the ions are measured using an electron
multiplier, and are collected by a counter for
each mass number.
 ICP--MS
ICP

• The mass spectrum generated is extremely

simple.
• Each elemental isotope appears at a different
mass (i.e.. 27Al would appear at 27 amu) with a
peak intensity directly proportional to the initial
concentration of that isotope.
• The proportionality is determined using standard
solutions with known concentrations of elements.
 LA-
LA-ICP-
ICP-MS
• Small parts of solid mineral samples can also be
analyzed using the ICP-MS MS with an attached laser.
• The laser is focused on the part of the sample of
interest and the power is increased to cause
melting of that small part of the sample (this is
called laser ablation).
• The melt is then injected into the plasma and the
rest of the analysis is similar to that described
above.
• This is a relatively new technique that is continually
improving in terms of detection limit and
reproducibility.
 3. X-
X-ray Fluorescence (XRF)
Spectrometry
• It is a technique now used mainly for the
analysis of rocks because it requires relatively
large amounts of sample (about 1 gram).
• It can be used to measure all of the major
elements in a rock or mineral as well as a wide
variety of trace elements.
• Sample preparation involves grinding the rock
or mineral to find powder and either pressing
the powder into a pill or melting and
quenching the sample to make a glass disk.
 • when an electron is
XRF be dislodged from
an inner electron
shell, outer shell
electrons fall in to
take its place
resulting in the
production of X-rays
with a wavelength
that is characteristic
of the element
involved.
 • Inner shell electrons that are
XRF dislodged from atoms in the unknown
sample result in the production of X-
X
rays of characteristic wavelength for
each of the different atoms in the
sample.
• For each atom in the sample, the
intensity of the characteristic X-rays
X
will be proportional to the number of
atoms in the sample.
• If we can measure the intensity of
characteristic X-rays
X for each
element, we can compare the
intensity to that of a standard with
known concentration, and determine
the concentration of the element in
the unknown.
 • The instrument used for such
XRF spectrometer measurements is called an X-ray
X
Fluorescence Spectrometer.
• It consists of an X-ray
X tube to
produce X-rays
X capable of dislodging
inner shell electrons of all elements
of interest in the sample.
• These have to be high energy X- X
rays, so Cr, Mo, W, and Au targets
are used as the anode.
• The X-rays
X that are produced in the
sample are then sent through a
collimator to produce a coherent
beam.
• These are then diffracted through a
crystal of known d-spacing.
d Using
the Bragg equation (n‫=ג‬
(n 2d.sinθ) we
can determine the θ angle that X-
rays of known wavelength will be
diffracted through the crystal.
• Thus, the crystal and detector are
set up to diffract only X-rays
X of the
particular wavelength of interest
into the detector.
 XRF spectrometer

• Intensities of characteristic X-rays

X for each
element of interest are determined by
rotating the crystal and detector to the angle
θ required for diffraction of the characteristic
X-ray wavelength.

• X-ray
ray intensities are then measured for each
element in the unknown and for each element
in a standard that has known concentrations.
 XRF Concentration calculation
Cistd = kIistd (1)

Ciunk = kIiunk (2)

where:
Cistd = the concentration of element i in the standard,
Iistd = the intensity of X-rays
rays of element i in the standard,
Ciunk = the concentration of element i in the unknown,
Iiunk = the intensity of X-rays
rays of element i in the unknown
k = a proportionality constant.

The proportionality constant, k, can be determined from the first

equation:
k = Cistd/Iistd (3)

This can then be substituted into the second equation to solve for the
concentration of element i in the unknown:

Ciunk = (Cistd/Iistd) Iiunk (4)

 XRF calibration

• In practice, this is only true if all elements in

the standard and the unknown occur in about
the same concentration.

• This is often difficult to attain, so a wide variety

of standards are used to figure out all of the
interfering effects and make a calibration curve
which relates concentration in the unknown to a
more complex equation involving the
concentration and intensities in the standard.
 4. Electron Microprobe Analysis (EMPA)
• The electron microprobe is an instrument that
uses principles similar to XRF. The main
difference is that instead of using X-rays
X to
dislodge inner shell electrons of elements in
the unknown, an electron beam is used.
• The electron beam can be focused down to a
spot size of about 1 µmm (1 µm = 10-6m), and
thus the X-rays
rays in the sample will only be
generated within a very small volume of the
sample.
 EMPA samples
• Thus, one can measure the concentrations in
small parts of single mineral grains, and
chemical zoning patterns or changes in the
concentration of elements through an
individual grain can be determined.

• The sample can either be a highly polished thin

section of a rock or mineral or can be grain
mounts wherein individual grains are mounted
in epoxy and polished to a smooth surface.
 EMPA equipment & measurement
• The instrument consists of a large tank that is evacuated
to produce a vacuum.
• At the top is an electron gun that has a filament, similar
to that in an X-ray
ray tube, that generates electrons.
• The electron beam is accelerated down to a sample stage
that is moveable. The electron beam is focused to a
diameter of about 1 mm by a series of magnets along its
path.
• Most electron microprobes have at least 3 X-ray
X
spectrometers inside, so that more than one element can
be measured at once.
• A microscope with binocular viewfinders allows the user to
focus the electron beam anywhere on the sample, as
shown in the inset. This can be accomplished by moving
the sample stage.
Schematic of EMPA measurement
 EMPA equipment & measurement
• Electrons striking the small area of the sample
produce X-rays
rays with wavelengths characteristic of
the elements in the sample.

• The spectrometers consist of curved crystals of

known d-spacing.

• These crystals diffract X--rays of each element into

the detectors at the diffraction angle θ. Several
elements can be measured at once, then the
spectrometers are set to new angles to measure
the X-ray
ray intensities of several more elements.
 EMPA concentration calculation
• Just like in XRF analyses, standards have to
measured to determine the proportionality
constants or calibration curves, and equations
similar to those used in the XRF method are
used to determine element concentrations in
the unknowns.

• Electron microprobe analysis is useful for

determining the major element concentration
in small parts of minerals. But, it is much less
sensitive than the XRF in terms of trace
element concentrations.
EMPA (EPMA) JEOL JXA-
JXA-8900R
In action...-)
 DETECTION LIMIT
Mineral Amphibole Biotite Calcite Chlorite Epidote Garnet Plagioclase1 Pyrophyllite Pyroxene Sericite

Program Amp BioN Calcite Chlorite Ep, Epi Grt PlA Prl Px Sericite

Acc. V (kV) 15 15 15 15 15 15 15 15 15 15

Diffusion (µm) 3 3 10 3 3 3 3 3 3 10

Current (nA) 2.305 2.358 2.357 2.345 2.352 2.358 2.364 2.014 2.355 2.348

Accum. points 1 10 1 1 1 1 1 1 1-5

Si 0.02 0.004 0.01 0.02 0.01 0.01 0.01 0.02 0.01

Ti 0.02 0.008 0.03 0.02 0.03 0.02 0.02 0.03 0.02

Al 0.009 0.003 0.009 0.01 0.01 0.01 0.01 0.009 0.009

Fe 0.02 0.006 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02

Mn 0.02 0.005 0.02 0.02 0.01 0.02 0.01 0.02 0.02 0.02

Mg 0.01 0.004 0.007 0.01 0.007 0.008 0.008 0.008 0.007

Ca 0.01 0.004 0.01 0.01 0.01 0.02 0.01 0.01 0.02 0.01

Na 0.01 0.003 0.009 0.008 0.009 0.01 0.01 0.008 0.009 0.008

K 0.01 0.003 0.01 0.01 0.01 0.01 0.01 0.01 0.009

Cr 0.02

Pb 0.05

Ba 0.03 0.03

Sr 0.02 0.02 0.01

F 0.02 0.1 0.05

Cl 0.003 0.009 0.009 0.01 0.008

 MEASUREMENT CONDITIONS-
CONDITIONS-Silicate
Silicate--Carbonate
Mineral Amphibole Apatite Biotite Calcite Chlorite Epidote Garnet Plagioclase1 Pyroxene Sericite

Program Amp Ap BioN Calcite Chlorite Ep, Epi Grt PlA Px Sericite

Acc. V (kV) 15 15 15 15 15 15 15 15 15 15

Diffusion (µm) 3 10 3 10 3 3 3 3 3 10

Current (nA) 2.305 2.37 2.358 2.357 2.345 2.352 2.358 2.364 2.355 2.348

Accum. points 1 10 10 1 1 1 1 1 1-5

Si Pl64 Pl64 Pl64 Pl64 Am130 Or79 Pl64 Pl64

Ti Ru83 Ru83 Ru83 Ru83 Ru83 Ru83 Ru83 Ru83

Al Pl64 Or79 Pl64 Pl64 Am130 Pl64 Pl64 Pl64

Fe Fa66 Fa66 Fa66 Fa66 Fa66 Fa66 Fa66 Fa66 Fa66 Fa66

Mn Mn133 Fa66 Mn133 Mn133 Mn133 Mn133 Mn133 Mn133 Fa66

Mg Sp761 Sp761 Sp76 Sp761 Sp761 Sp167 Sp761 Sp76

Ca Pl64 Ap44 Pl64 Ap70 Pl64 Pl64 Di60 Pl64 Pl64 Pl64

Na J107 J107 J107 Jl07 J107 J107 J107 J107 J107 J107

K Or79 Or79 Or79 Or79 Or79 Or79 Or79 Or79

P Ap44

Cr Cr54

Pb PbS2

Ba Ba89 Ba89

Sr Coel1062 Coel1062 Coel1061 Coel106

F Ap44 Ap44 Fl80

Cl Tug34 Tug34 Tug34 Tug34 Tug34

MEASUREMENT CONDITIONS
MEASUREMENT RESULTS
MEASUREMENT RESULT
MEASUREMENT RESULT
 HORNBLENDE CHEMISTRY
Analysis 176-01a 176-01b 176-01c 176-01d 176-01e 176-01g 176-01h

SiO2 48.64 48.90 48.68 48.63 49.41 47.70 49.12

TiO2 0.96 0.88 0.89 0.89 0.84 0.88 0.84
Al2O3 6.89 6.92 6.82 7.05 6.68 7.08 6.43
FeO 13.07 13.19 12.69 11.84 11.73 11.79 11.41
MnO 0.59 0.58 0.76 0.59 0.61 0.63 0.69
MgO 15.91 15.81 16.10 15.58 15.95 15.81 16.42
CaO 10.16 10.28 10.70 10.34 10.28 10.29 10.18
Na2O 1.45 1.50 1.11 1.45 1.44 1.33 1.22
K2O 0.14 0.17 0.14 0.15 0.14 0.13 0.12
Total 97.83 98.23 97.88 96.53 97.05 95.63 96.42
Structural formula based on 23 Oxygens, using 15-NK calculation method (after Robinson et al., 1981)
IV
Si 7.05 7.07 7.01 7.13 7.20 7.04 7.17
IV
Al 0.95 0.94 0.99 0.87 0.81 0.96 0.84
AlVI 0.22 0.24 0.17 0.35 0.34 0.27 0.27
Fe+3 0.08 0.05 0.29 0.00 0.00 0.10 0.01
Ti 0.11 0.10 0.10 0.10 0.09 0.10 0.09
Mg 3.44 3.41 3.46 3.40 3.46 3.48 3.57
Fe+2 1.50 1.55 1.24 1.45 1.43 1.36 1.38
Mn 0.07 0.07 0.09 0.07 0.08 0.08 0.09
Ca 1.58 1.59 1.65 1.63 1.60 1.63 1.59
Na 0.41 0.42 0.31 0.41 0.41 0.38 0.35
K 0.03 0.03 0.03 0.03 0.03 0.02 0.02
∑ cations 15.44 15.45 15.33 15.44 15.43 15.40 15.37
X Fe+2 0.30 0.31 0.26 0.30 0.29 0.28 0.28
X Fe+3 0.05 0.03 0.19 0.00 0.00 0.07 0.01
XA b 56.90 55.30 54.90 58.10 56.70 57.00 56.00
Notes:
X Fe+3 = Fe+3/(Fe+3 + Fe+2); X Fe+2 = Fe+2/(Mg+Fe+2)
XA b = albite proportion of rim of plagioclase phenocrysts in contact or in near contact with an amphibole rim.
 HORNBLENDE CHEMISTRY-
CHEMISTRY-Classification
1
Tremolite Tr Hb

Magnesio-Hbl
Tsch
Hbl Tschermakite
Actinolite Act
Hbl
Mg/((Mg+Fe2 )

Fe- Fe-
Ferro- Ferro-Hbl Tsch Ferro-
Actinolite Act Hbl Tschermakite
Hbl

0
8.0 7.5 7.0 6.5 6.0 5.5

TSi
EPMA BACKSCATTER IMAGE
 MINERAL CLASSIFICATION

Biotite classification
Eas to n ite Sid e r o p h yllite
3.0
2.9 magmatic
hy drothermal
2.8
2.7
2.6
Al IV

2.5
2.4
2.3
2.2
2.1
2.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ph lo g o p ite A n n ite
+2 +2
Fe /(Fe +Mg)
EPMA BACKSCATTER IMAGE
EPMA BACKSCATTER IMAGE
TRAVERSE CHEMICAL ANALYSIS
 Clinopyroxene Garnet Anorthite
Sample no.* SBD287/794.7 Sample no.* SBD287/794.7 Sample no.* SBD287/794.7
Analysis no. 63-153f 181-60 Analysis no. 70-96c 49-119 Analysis no. 181-21 181-32
core rim core rim unzoned unzoned
CHEMICAL ANALYSIS SiO2
TiO2
53.33
bd
48.22
0.16
SiO2
TiO2
35.64
0.56
35.00
0.95
SiO2
TiO2
44.87
bd
44.14
bd
Al2O3 0.36 2.20 Al2O3 6.47 3.23 Al2O3 35.40 34.82
FeO 4.40 19.18 Cr2O3 bd 0.03 FeO 0.48 0.24
MnO 0.52 1.78 Fe2O3 22.14 26.14 MnO bd bd
MgO 15.32 5.58 FeO bd 1.40 CaO 18.41 19.27
CaO 25.71 23.40 MnO 0.44 2.24 Na2O 1.00 0.56
Na2O 0.10 0.33 MgO 0.05 0.12 K2 O 0.02 bd
K2 O 0.01 bd CaO 34.29 30.28 BaO bd bd
Total 99.75 100.85 Total 99.61 99.36 Total 100.17 99.03
Si 1.97 1.88 Si 5.84 5.90 Si 8.28 8.25
Al 0.02 0.10 Al 0.16 0.10 Al 7.69 7.66
Fe+3 0.02 0.02 AlVI 1.09 0.54 Ti 0.00 0.00
+3 +2
Ti 0.00 0.01 Fe 2.73 3.32 Fe 0.07 0.04
+3
Fe 0.04 0.13 Ti 0.07 0.12 Mn 0.00 0.00
+2
Fe 0.08 0.48 Cr 0.00 0.00 Ca 3.64 3.86
+2
Mg 0.84 0.33 Fe 0.00 0.20 Na 0.36 0.20
Mn 0.02 0.06 Mg 0.01 0.03 K 0.00 0.00
Ca 1.02 0.98 Mn 0.06 0.32 Ba 0.00 0.00
Na 0.01 0.03 Ca 6.02 5.47 Cations 20.04 20.01
K 0.00 0.00 X Ca 0.99 0.91 Ab 8.90 5.00
X Ca 0.52 0.53 X Fe 0.00 0.03 An 91.00 95.00
X Mg 0.43 0.18 X Mg 0.00 0.01 Or 0.10 0.00
X Fe 0.00 0.01 Alm 0.00 3.27 Plagioclase:
Q 1.94 1.78 And 70.12 83.28 Ab = albite
J 0.01 0.05 Gross 28.54 7.48 An = Anorthite
WO 50.54 49.22 Pyrope 0.20 0.50 Or = Orthoclase
EN 41.90 16.33 Spess 1.00 5.31
FS 7.56 34.45 Uvaro 0.03 0.10 bd = below detection limit

Pyroxene:
Q = Ca+Mg+Fe2; J = 2Na;
WO = 100*Ca/(Ca+Mg+Fe2+Fe3+Mn); EN = 100*(Fe2+Fe3+Mn)/(Ca+Mg+Fe2+Fe3+Mn) and
FS = 100*(Fe2+Fe3+Mn)/(Ca+Mg+Fe2+Fe3+Mn) (after Morimoto, 1989)
Garnet:
Alm = Almandine (Fe3Al2Si3O12); And = Andradite (Ca3Fe3+2Si3O12); Gross = Grossular (Ca3Al2Si3O12);
Pyrope = Pyrope (Mg3Al2Si3O12); Spess = Spessartine (Mn3Al2Si3O12); Uvaro = Uvarovite (Ca3Cr2Si3O12)
Structural formula
rmula calculation:
Pyroxene is based on 6 Oxygens, Fe+3 calculated with charge balance (after Yoder and Tilley, 1962)
Garnet is based on 24 Oxygens; Plagioclase is based on 24 Oxygens.
EPMA ELEMENTAL MAPPING-
MAPPING-Epidote
EPMA ELEMENTAL MAPPING
EPMA ELEMENTAL MAPPING
EPMA ELEMENTAL MAPPING-
MAPPING-Oxides
EPMA ELEMENTAL MAPPING-
MAPPING-Oxides