GEMSTONE ANALYSIS AND THEIR

TREATMETS
Using Spectroscopy

Malaviya National Institute of Technology

By: Arpita Jain

Dept. of Chemistry
2012PCY7018

Introduction
Gemology is the science dealing with the study of natural and artificial gems and
gemstones. Identification of gemstone can be determine by taking the specific gravity of
stone, analyzing with microscope, taking refractive indices and absorption spectra of the

stones.
With advance methods in intimating and synthesizing gemstone as well as new gemstone
treatment, these methods proved not to be sufficient anymore.

However, today analytical methods became easily available mostly the spectroscopic
methods in different areas of electromagnetic spectrum enables to study about a gemstone
in much detail.

Good gemmological laboratories nowadays are equipped with much advanced

spectrometers like UV-Vis spectrometer, FT-IR spectrometers, Laser Raman spectrometers
and less frequently, ED-XRF spectrometers.

spectroscopy

Energy that is emitted from the sun is affected by electrical and magnetic fields
which are known as Electromagnetic Radiations'.
These radiations include the complete spectrum of rays from high frequency (short
wavelength) to low frequency (long wavelength) i.e. cosmic, gamma, X-rays, ultraviolet, visible, infrared, micro, radar, television and radio waves.
When a gemstone is exposed to light or excited by the energy of incoming waves or
radiation, mainly two reactions take place - absorption and emission (fluorescence),
which makes the base for any spectroscopic technique.
Further, the color of a gemstone, what we see, is also due to the absorption and
emission (fluorescence) of certain types of wavelengths.

The Electromagnetic Spectrum and

associated spectroscopic technique

Spectroscopic techniques are used to identify :

The constituents (elements, molecules, crystallographic properties) of
materials through the characteristic absorbance of visible, infrared and/or
ultraviolet light.
To separate natural from synthetic gem materials, as variations in chemical
composition can be revealed in the absorption spectrum of light transmitted
through the stone.

General schematic working of a spectrometer

All spectroscopic techniques are based on the

principle of transmission of energy through
sample which is absorbed by the electrons or
molecules.

 Amount of absorption and transmission depends on electrons, elements or

molecules present in the gemstone.
For example, absorption and emission in visible light or region in gemstones

and minerals are due to the presence of certain trace elements or defects,
responsible for the colour of gem.
Ruby showing absorptions in the visible range not necessarily display

absorptions in other regions; the electrons of chromium atom excited by the

visible light may not get affected by the infra red radiations. A ruby appears
red, because of the absorption of green and violet wavelengths, while
transmitting mainly the red with some orange, yellow and blue.
This is mainly dependant on the electronic and /or molecular configuration
of the material and the type of radiation.

Fourier Transform Infra-Red

Spectrometry (FT-IR)
Infrared spectrum gives a fingerprint of a sample with absorption peaks
corresponding to the vibrations between the bonds of the atoms.

Bonds in the molecules absorb infra red rays at one or more specific
frequencies and produce vibrational characteristic of molecules in one of the
three major parts of infra red region,

Near Infrared (NIR) and Mid Infrared (MIR) - Provide characteristic

information in this region of organic compounds like, H2O and CO2.

Far Infrared (FIR) - It display lattice vibrations, allowing identification of the

mineral group (such as silicate, carbonate, sulfide, etc).

To identify an unknown gem material, i.e. separating out similar looking gem
and separate natural from synthetic gemstone.

For e.g. in case of Diamonds FT-IR spectroscopy can easily

distinguish from its simulants. However much sharper peaks are

obtained by Raman Spectroscopy.

Diamond mainly composed of Carbon atom.
Minor quantities of natural Silicon Carbide, known as Luthenite were
replicated in a material to produce a synthetic gemstone with similar
properties of Diamond called Moissanite

Cubic Zirconia primarily consists of Zirconium Dioxide.

The FTIR Spectra shows the broad absorption between 1800 cm1 and 2700 cm1 is
due to the carbon in case of diamonds (blue trace). Mossianite (red trace) and Cubic
Zirconium (green trace) does not shows sharp peaks due to presence of different
elements

 FTIR spectroscopy used to identify gemstones like Rubies and sapphires are
both varieties of the corundum group and have same chemical structure
(Aluminum Oxide). FT-IR spectroscopy can confirm that a stone is corundum
and not a simulant.
Red stones are classified as ruby (the red color comes from chrome and iron),
while the other remaining colors are classified as sapphires even though the
name sapphire was originally reserved for blue stones (the blue color comes
from titanium and iron).
Most natural rubies and sapphires have a small peak in the infrared spectrum
near 3310 cm1 that corresponds to the OH stretching mode of water.

Using FTIR spectroscopy, it is possible to verify the presence of trapped water

in ruby or sapphire. FTIR provides a rapid, nondestructive technique to identify
stones.

The spectrum of a sapphire in Figure shows the strong absorption from the AlO
bonds below 1500 cm1 and a lack of other major features in the spectrum. The
unique spectrum of corundum makes it very easy to differentiate ruby and
sapphire from most of the simulants or other similarly colored gemstones.

Laser Raman Spectrometry (LRS)

Raman spectroscopy complements IR spectroscopy where FTIR fails for e.g. in
addition to HO or CO content of sample, it identifies the chemical groups
irrespective of thickness of the sample.
It proves to be very useful in case of large specimens or gems set in a jewellery,
or when the size of stones are too small (very small surfaces of micron sizes) ,
or if the sample is in rough form.
Besides providing information about the host mineral, it shows inclusions
present in it, or the various layers within in case of composites, or colour
zoning, and much more.
It is to identify an unknown gem material, especially when other properties
closely overlap

Raman spectra of diamond and its simulants are distinctly different. The spectrum of
diamond shows only one very strong and sharp Raman band at around 1332 cm1, which
corresponds to C-C stretching mode. However spectrum of zircon shows multiple Raman
bands at around 200 - 650 cm1. Synthetic Moissanite shows peaks at 766 cm1, 789 cm1 and
966 cm1 due to Si-C stretching mode.

Ultra Violet- Visible- Near Infrared

Spectrometer (UV-Vis-NIR)
Absorption features in the UV-Vis region are caused due to electron defects or
presence of chromophoric elements (coloring elements).
This technique gives detailed information about the cause of color in a
sample, thereby assisting in determination of a gem material, separating
natural from synthetic gem materials, identifying treatments, etc.
It not only determines the trace element, but also its type , for example,
whether Fe is present as Feor Fe.

UV-Vis spectra also assist in origin determination, by studying the type of

trace element present, such as separating sapphires from basaltic (e.g.
Thailand) and metamorphic (e.g. Burma) environments.

Natural sapphires, from basaltic environment display strong iron-band at around 450 nm
with associated weaker bands at 460 and 470 nm (red trace) those from metamorphic
environment show single band at 450nm; these features are not present in a synthetic
counterpart (blue race).

Energy Dispersive X-Ray Fluorescence

Spectrometer (ED-XRF)
When a substance is exposed to x-rays, the electron of the atoms get excited to the higher
energy level and on falling back to the ground state, emit radiations in the form of
fluorescence. The emitted light is thus, recorded by the detectors and hence, the method
known as x-ray fluorescence spectrometry.
It provides a quick chemical composition of a sample and identify gemstone species /
variety, especially in case of look-alikes.
It is used to determine the bulk chemical composition of the samples' surface. Due to the
sensitivity levels of the spectrometers used, elements with atomic number 11 i.e. Sodium
(Na) or higher can be detected, while those falling below atm. no. 11 (such as H, C, O, B, Be,
Li) cannot be detected due to their very low levels of emitted energies.
Identify treatments, especially glass fillings in rubies, sapphires or diamonds, coatings in
spinel, tanzanite, topaz or any other gem, diffusion in corundum or topaz, etc.

Flux -grown synthetic ruby (red trace) may show the presence of lead, which is
present in the flux used to grow crystals, while natural ruby (blue trace) does not
have lead content, unless it is glass filled.

Spectroscopic Techniques in Gemstone Enhancement

Gemstone Enhancement is a treatment process other than cutting and
polishing that improves the appearance (color / clarity), durability or
availability of a gemstone.
This treatment covers heating, oiling, irradiation, waxing, dyeing,
bleaching etc.
These spectroscopic techniques are helpful in analyzing internal features,
such as exact nature of the mineral or fluid inclusions.
Thus assisting in determination of origin and separating natural and
synthetic rubies and sapphires or emeralds.

Treatment Techniques

Fracture Filling- Filling surface-reaching fractures or cavities with a glass,

resin, wax or oil to conceal their visibility and to improve the apparent
clarity of gem materials, appearance, stability.

Heat Treatment- The exposure of a gem to high temperatures for the

purpose of altering its color and/or clarity.

Dyeing- Introducing colored dyes into porous or fractured gems to

change their color. Such fractures are sometimes purposely induced by

heating the gem so that an otherwise non-porous material can more

readily accept the dye.

FTIR analysis shows clean fracture in emerald showing iridescence

(top, left), oiled fracture (top, centre & right) showing dendritic
patches and uneven filling and resin-filled fractures showing blue and
golden flashes (bottom).

The FTIR spectra of natural and treated emerald. The wavenumber range between
3200 cm1 and 2800 cm1 clearly shows absorption bands that originate from resin.
Since oil and resin show absorption in the MID-IR spectrum, FTIR can be used to
determine whether emeralds have been treated.

A zircon crystal in a natural unheated

sapphire with a radiation-induced stress
crack (left) appear transparent, but on
heating at elevated temperatures, zircon
crystal gets damaged and appear white and
frosty, often forming a highly reflecting
discoid fracture (centre) and / or atoll-like
halo (right).

Zircon crystals, which are one of the most common inclusions present in rubies and
sapphires, provide very useful information regarding heating. Zircon crystal when present
in nature are usually in metamict state (almost amorphous), hence do not display sharp peaks.
However, on heating, zircon restores its crystalline state, and as a result, the intensity of
absorption peaks also increases (blue and red traces), assisting in detection of even lowtemperature heating of below 800-1000C.

Many pearls seen in the

market are dyed, as the
bottle of dye-soaked pearls
(left) shows, and the single
pearl demonstrates (right).

Natural red colouration in corals is due to the presence of

carotenoids and parrodines which can be detected in
Raman spectra (red trace). These are missing in dyed
counterparts (blue trace); hence, separation becomes quite
conclusive with Raman spectra.