Spectra of Minerals and Rocks

Objects can be marked by following types

of spectral behaviour-

1. Selective absorption-
relative weak reflection

2. Selective Reflection

3. Selective higher or lower emission

Basic Arrangement for Laboratory Spectroscopy
Three types of laboratory spectroscopic
arrangements can be conceived-

1. Reflection

2. Emission

3. Absorption (or transmission)

1. Reflection arrangement- Most extensively used arrangement
in the optical Region

EMR impinges upon the object-sample and is reflected onto a

detector. It is customary to express the spectral reflectance as
a percentage of the reflectance of MgO, in order to provide a
calibration.

S D
High reflectivity
Reflection

Object

λ
2. Emission Arrangement

All objects above zero kelvin emits radiation.

Due to practical problems of non-uniform heating

In general, emission spectra is computed from
Reflection or transmission spectral measurement.
3. Transmission Arrangement-
Most suited for gases and liquids...
Fine particulate solids suspended in air or embeded
In suitable transparent pellets can also be studied under this
arrangement....

Since it involves spectral absorption, it is also called an absorption

arrangement.

Low absorptivity

S Object D Absorption

λ
Energy State and Transition-

Total energy of a atomic-molecular system can be expressed as

the sum of four different types of energy
States –
Translational
Rotational
Vibrational and
Electronic

Different amount of energy is required for each of these

transition,,,hence it appears in different part of the EM spectrum
Translational energy- unquantized nature, not considered here..

Rotational energy- not considered here due to physical

Properties of solid substances...

Vibrational energy state is involved with the movement of atoms

relative to each other, about a fixed position. Such changes are
caused by thermal IR and SWIR...

Electronic energy state is related to the configuration of electrons

surrounding the nucleus or to the bonds; their transitions require
even a greater amount of energy. Caused by Photons of near IR,
visible, UV and X-ray...
Electronic Processes
1. Charge-transfer effect- Incident energy absorbed, raising the
energy level of electrons so that they migrate between
adjacent ions, but do not become completely mobile.
mainly caused by UV and visible region photons

Typically exhibited by Fe-O, widespread constituent of rocks,

absorbs radiation of shorter wavelength such that there is
steep fall-off in reflectance towards blue, and so it has a red
colour in the visible range.

Another example- uranyl ion(UO2)2+ in

carnotite absorbs all energy <0.5 μm, resulting
in yellow colour of the mineral.
A steep fall off in UV and blue region of the minerals mainly having Fe-O
Also, it shows a marked absorption feature 870 nm.
2. Conduction band absorption effect-

In some semi-conductors such as sulphides,

Nearly all the photons of energy greater than a
Certain threshold value are absorbed, raising the
Energy of the electrons to conduction band level.
3. Electronic transition in transition metals-
The presence of these elements leads to
Absorption bands at the appropriate wavelengths.

Ferrous ion- 1.0, 1.8-2.0, 0.55-0.57 micron

Ferric ion- 0.87, 0.35, sub-ordinate bands ~0.5
Manganese- 0.34, 0.37, 0.41, 0.45 and 0.55
Copper- 0.8
Nickel- 0.4, 0.74 and 1.25
Chromium- 0.35, 0.45, 0.55
4. Crystal Field Effect-
The energy level for the same ion may be different in different
Crystal fields. This effect is seen in some transition elements
Having unshielded electrons (3d shell electrons). The energy
Level is greatly influenced by the external field of crystal and thus
They assume a new energy level.
It depends on-
Valence state of the ion, site symmetry, type of ligand formed

For example-
Ferrous ion located in different crystal field produce absorption
Peaks at different wavelengths.
Vibrational Processes-
Most of the rock forming minerals (including silicates,
Oxides, hydroxyl, carbonates, phosphates, sulphates, etc)
are marked by atomic-molecular vibrational processes
In the SWIR, TIR of the EM spectrum.

These are the result of bending and stretching molecular

Motions and can be distinguished as fundamentals,
Overtones and combinations. The fundamental tones
Mainly occur in the thermal-infrared region (>3.5 micron)
And their combinations and overtones in the SWIR region
(1-3 micron)
Spectral Features of Mineralogical Constituents-

This is divided in three parts-

1. VNIR region
2. SWIR region
3. TIR region

1. VNIR region (0.4-1.0 micron)- dominated by electronic

processes in Transition metals (i.e. Fe, Mn, Cu, Ni, Cr etc.)
Si, Al and various anion groups silicates, oxides, hydroxides
Lack spectral features in this region.

Fe-O, a ubiquitous constituent in rocks exhibit strong absorption

In this region.
2. SWIR region (1-3 micron)-
Important as marked by spectral features of hydroxyls
and carbonates, commonly occurring in earth’s crust.

Hydroxyl ion-
Mainly occurring in clays, mica, chlorite,,,,
Vibrational fundamental absorption band at about 2.74-2.77
And and overtone (1.44). It also interfere with water molecule.

Hydroxyl ions occur in combination with Aluminium (Al-OH)and

Magnesium (Mg-OH), which happens to be very common in
Clays and hydrated silicates, several sharp absorption features
Are seen in 2.1-2.4 micron region.
Reflectance spectra of some Common clay minerals

Strong absorption phenomenon within

the 2.1-2.4 due to Al-OH (2.2) and Mg-
OH (2.3) leads to sharp decreasing
Spectral reflectance beyond 1.6, if clay
present.
Kaolinite has doublet while
Montmorillonite and muscovite has 2.3
due to Mg-OH.
Ratio of broad bands
1.55-1.75/2.2-2.24 is very useful
Parameter in identifying clay mineral
assemblages.

Also useful in identifying hydrothermal

Alteration zones as many clay minerals
Are associated with such zones.
Water molecules-
Important absorption bands due to water molecules occur
At 1.4 and 1.9 micron. Sharp peaks imply that water
Molecules occur in well defined sites.
Carbonates-
Calcite (CaCO3), Magnesite (MgCO3), Dolomite [(Ca-Mg)CO3],
Siderite (FeCO3).
Important carbonate absorption bands in the SWIR occur at
1.9 micron, 2.35 and 2.55 micron.

1.9 may interfere with water

2.35 may interfere with clay

However, a combination of 1.9 and 2.35 and also an extra feature

At 2.5 micron is considered diagnostic of carbonates.

Presence of siderite is accompanied by an electronic absorption

Band due to iron, occuring near 1.1 micron.
3. Thermal IR Region
Characterized by spectral features by many rock forming
Minerals groups- silicates, carbonates, oxides...many

Typical emission is shown by many groups...

Carbonates show a prominent absorption feature at 7..

However, this is outside the atmospheric window (8-14),
It cannot be used for remote sensing, instead the weak
Feature around 11.3 can possibly be detected.

Sulphate show a band around 9 and 16.

Phosphate at around 9.25 and 10.3
Silicates, form the most
Abundant group of minerals
Display in this region due to
SiO4 tetrahedron.
In the region- 7-9 micron, there occur a maximum peak called
Christiansen peak migrates systematically with the composition
Being near 7 micron for felsic mineral and near 9 for ultramafic
Minerals.

Region 8.5-12, a strong peak centered around 10 is designated

As Si-O vibration absorption.
However, exact position is sensitive to silicate structure....
9 micron- framework silicates
11.5 micron- chain silicates

Region 12-15 micron, sensitive to silicate and aluminium silicate

Structure of tectosilicate type.
Hence, from a geological point of view, TIR is the most
Important spectral region for remote sensing.
 Spectra of Rocks

Aggregates of minerals,
Hence diagnostic spectral curve of rocks is difficult.
Based on constituent Minerals, divided in 2 parts-
1. Solar Reflection region
2. Thermal IR region
 1. Igneous Rocks- Graphic granites shows absorption at
1.4, 1.9 and 2.2 corresponding to absorption band of OH
and H2O. Biotite granites and granites have less water
and hence the absorption peak is weaker..

Ultramafic rocks contain

Larger amounts Fe2+,
bearing
Minerals and therefore the
Ferrous bands become still
More prominent e.g. In
Pyroxenite.
2. Sedimentary Rocks- All sedimentary rocks generally have water
absorption band at 1.4 and 1.9 μm. Clay has additional around 2.1-2.3 μm.
Carbonaceous shales are featureless.
Pure siliceous sandstone is also featureless.

Limestone and calcareous

Rocks are characterized
by absorption band of
Carbonates (1.9 and 2.35).
In Dolomites, the ferrous ion
Bands at 1.0 μm due to
Substitution of Mg2+ by Fe2+.
Metamorphic rocks- The broad absorption due to ferrous ion is prominent
In rocks such as tremolite schists. Water and hydroxyl bands (at 1.4 μm
1.9 μm) are found in schists, marbles and quartzites.

Carbonate bands (1.9 and 2.35)

Mark the marbles.
 Thermal IR Region
In TIR, mineral spectra are additive in nature. Hence can easily be interpretable
In terms of relative mineral abundances.
See the selected igneous rocks
Arranged in decreasing silica content
from top to bottom.

-Gradual shift of center of the

Minimum emission band from 9
In granite to 11 in olivine-peridotite.
A large part of earth surface is covered with vegetation and
therefore vegetation spectra have drawn greater attention.
In general, in the visible region, leaf pigments govern the leaf spectrum.
The normal chlorophyll-pigmented leaf has a minor but characteristic
Green reflection peak....

In Anthocyanin, green reflection is absent.

Spectrum of white leaf has a nearly constant level in visible region.
Spectral reflectance curves of different level of pigmentation
In the near IR region, the spectral reflectance depends on the
Type of foliage and cell structure.

Some leaves as Fir and Pine, reflect weakly in near IR, whereas
Grass reflects very strongly. This can therefore be used for
Identifying vegetation type.
Spectral reflectance curve for vegetation with different foliage and cell structure
Leaf pigments absorb most of the light in the visible region.
There is a minor peak at 0.55 leading to green color.

Absorption feature at 0.48 is due to electronic transition in

Carotenoid pigments works in photosynthetic process.

0.68 is due to electronic transition in the chlorophyll molecule

Centered around the Magnesium component of the photoactive site.

Ratio of near IR-visible reflectance provide information of the

Photosynthetic capacity of the canopy, and is used as a type of
Vegetation index.

The reflectance in the SWIR region is related to biochemical content

In the canopy, such as proteins (nitrogen concentration), lignin and
other leaf constituents.