Gemstone Identification

Using Raman Spectroscopy

Raman microspectroscopy is an ideal method for the examination
of marketable gemstones because of the lack of sample preparation involved
and the nondestructive nature of Raman analysis.

Amanda L. Jenkins and Richard A. Larsen

I
n recent years, the gemstone market has been flooded with
stones of questionable origin. Frequently, even thorough
analysis by a qualified jeweler cannot reveal unequivocal-
ly whether the gemstone is genuine or fake. In the worst
case, sophisticated analytical methods struggle to differentiate
modified diamonds, causing considerable concern to the
international gemstone trade. Raman microspectroscopy is an
ideal method for the examination of marketable gemstones
because of the lack of sample preparation involved and the
nondestructive nature of Raman analysis. The micro-Raman
study of a stone also provides a unique record for identifica-
tion purposes. This article discusses the variety of Raman
spectra that can be obtained from different families of gem-
stones, comparing and contrasting spectra from genuine and
artificial minerals. refracting from very thin layers of a gemstone material such
Color in gemstones is caused by light of specific wave- as fir agate or ammonite. Orient is another interference phe-
lengths being absorbed inside the stone. Such absorption is nomenon that occurs in pearls and is caused by the thin
a characteristic of the gemstone material, the molecular layer structure of the outer pearl and by undulations in non-
structure, and extraneous impurities or inclusions within spherical pearls. Asterism is caused by needle inclusions
the crystalline structure (1). The human eye perceives the along crystallographic lines. This effect is seen in star rubies,
different light wavelengths as colors. As white light enters a sapphires, and some other stones. Chatoyancy is similar to
stone, the wavelengths are affected by the chemical and asterism, but produces a single band of light caused by the
structural properties of the stone, some wavelengths being needle inclusions creating the phenomena known as a cats-
absorbed, others reflected. A combination of different eye effect. Aventurescence is a sparkle effect caused by small
wavelengths radiate from the stone, changing the white plate-like inclusions and is common in aventurine quartz,
light that entered into emitted light of various colors (2). sunstone feldspar, and Goldstone glass (4, 5).
Materials formed in different configurations can have very
few similarities. For example, both diamond and graphite Gemstone Modification and Enhancement
are essentially pure carbon but the crystal structure of the Gemstones and semiprecious stones have been modified for
carbon in diamond is completely different. For colored centuries to make them more colorful, more eye-catching, and
gemstones the quality of the color is worth at least 50% of easier to work with. One such technique is heat-treating (the
the valuation of the gemstone (3). most common) to enhance, clarify or create color in a stone.
Color also comes from sources other than absorption of Amethyst is heated to obtain citrine. Zircon is heated to clarify
bands of light. Structural properties can cause various types the stone to clear white. Sapphires are heated to get amazing
of phenomena. The first is play of color, an effect caused by pinks and blues. Rubies lose a purplish tint while iolite might
diffraction of light. In opal, which is made up of regularly be turned a deep blue. Heat-treating also can be used to
stacked small spheres of silica, these layers of spheres act enhance the “color change” of gems such as tanzanite. Dying of
similar to a diffraction grating producing colors from the stones also is a very common practice. Agate is dyed to get
refracted light. The colors are determined by the sphere size pinks, purples, oranges, and blues. Although chalcedony is
and spacing. Iridescence is somewhat similar to a play of often dyed, black chalcedony usually is sold as onyx. Irradiation
color in that the interference colors are created by light with UV light is another common treatment. Topaz currently is

20 Spectroscopy 19(4) April 2004 w w w. s p e c t r o s c o p y o n l i n e . c o m

the most commonly irradiated gemstone tant issue with these simulants is proper sample stone and the hemicylinder.
(to get various shades and tones of blue). disclosure (7–9). Observation through a calibrated scale
This also is how fabulously colored dia- allows the observer to see a partially
monds are obtained. In fact, diamond Gem Examination and shaded scale where the boundary defines
was the first gemstone to be color treated Identification the refractive index of the stone. If a yel-
by UV radiation (1, 3–6). Gems often are examined by trained low sodium light source is used, the
Another gemstone enhancement personnel using a variety of methods. observer can move the stone around to
technique is stabilization. Stabilization The most common instrument in gem view different facets and determine both
traditionally was accomplished by filling identification is the eye. Vision alone can the upper and lower limits of the refrac-
the stone with natural oils; however, be used to observe color, transparency, tive index on doubly refractive stones
modern synthetic resins such as Opticon cut, phenomena, polish luster, disper- and therefore the birefringence. Careful
(Hughes Associates, Wayzata, MN) are sion, heft, fractures, and cleavage. use of the refractometer with the stone
being used now. Resin filling often is However, a variety of analytical instru- in many positions also will allow deter-
more permanent than the use of natural ments also is available and some are mination of the optical characteristics
oils. Opals often are stabilized and emer- explained here. (doubly or singly refractive) and the
alds have a long history of fracture filling The refractometer probably is the optical sign (positive or negative). These
due to the popularity of the gem and a most common instrument in gemstone tests must be done with a well-polished,
tendency for the stones to be highly identification. A special light source is clean stone and great care must be
included or fractured. Another com- used to project a beam of light into the taken so as not to scratch the hemicylin-
monly used technique is diffusion, refractometer and into a hemicylinder of der (3, 10).
which embeds a very thin layer of an ele- very soft, highly leaded glass. A small A thermal impedance tester is used to
ment into the surface to improve color. drop of a special liquid with a high measure the thermal conductivity of a
Laser drilling also is done to obtain refractive index is used to form an opti- stone. It is of little value except for sepa-
access to enclosed crystal inclusions and cal bond (not physical) between the rating diamond from other stones.
remove them with acid. Stones also are
bleached, dyed, waxed, coated, and
painted (4–6). 15 Figure 1. Citrine
One of the most controversial modi- (bottom), a yellow-
fication techniques is the so-called cre- colored natural
quartz, can be
ation of gemstones. Synthetic gems are
passed off as the
made on an industrial scale like chemi- 10 more expensive
Intensity

cals and have been around since the late topaz (top) by
1800s when ruby first was synthesized. unscrupulous gem
Laboratory grown crystals of ruby, sap- dealers.
phire, diamond, emerald, and star sap-
5
phire bear the name of the mineral
species they resemble because they have
an identical appearance, atomic struc- 2
ture, and a similar (not always identical) 1220 1000 500 55

chemical composition. Simulants or Wavenumber (cm-1)

imitations are gemstones or other mate-
rials that alone or in combination with
others are made to look like more valu- 5
Figure 2. The nor-
able gemstones. Assembled stones are malized Raman
made by gluing layers of different gem spectra of peridot
4
materials together to create an appar- from a necklace,
ently colored composite or to increase (solid) ring,
stone size. Glass and plastics, manufac- 3 (dots/dashes) and
Intensity

tured with a wide range of color, specif- the fake peridot

ic gravity and index of refraction can be from a bracelet (dot-
2
used to simulate natural stones. Cubic ted).
zirconia, synthetic rutile, strontium
titanate, zircon, and white sapphire 1

include both synthetic and natural gem-

stones that are used to simulate natural 0
gemstones, usually diamonds (3). From 1500 1000 500 90
Raman shift (cm-1)
a buyer’s point of view, the most impor-

April 2004 19(4) Spectroscopy 21

Gemstone Identification

However, even a positive test using ther- 8

mal impedance must be augmented by Figure 3. The
other gemological observations to dif- Raman spectra of
ferentiate diamond from moissanite. A several cuts of gar-
6 net: square cut
UV cabinet uses both short- and long-
(top), oval (middle),
wave UV light bulbs to illuminate the and round (bottom).
samples. Testing for UV fluorescence is

Intensity
5
useful in separating several gemstone
types and is particularly useful in sepa-
rating some synthetic materials from
2
natural counterparts. Occasionally a
gemstone will have phosphorescence, a
persistent release of light for a short time
after exposure to ultraviolet light. This is 0
50 500 1000 1200
caused by a slower return of electrons Raman shift (cm-1)
from their excited state to the normal, or
ground, state. In adequate darkness,
such phosphorescence can be observed 9 Figure 4. The
easily. A spectroscope is used to reflect a Raman spectra of
8
strong light source off the surface of a emerald (solid) and
gemstone or project it through the two tanzanites (dot-
stone. Either way, the gemstone will 6
ted and dashed).
leave its spectral fingerprint on the light
Intensity

beam, which is spread into the visible

spectrum for observation. The gemolo- 4

gist notes the wavelengths (spectral

position) of the absorption line and 2
bands, and compares them to known
materials. Microscopes are used for
close-up examination of the external 0
and internal characteristics of gem- 1250 1000 500 120
Raman shift (cm-1)
stones (3, 10).
In some well-studied cases such as
diamond, these techniques usually will source-induced change in the polariz- Laser Technologies AVS, Skodsborg,
suffice. However, imperfections can be ability of the molecular bond during the Denmark); two gratings and an Andor
filled readily with synthetic materials or vibrational motion. With the ability to (South Windsor, CT) air-cooled, front-
the stone can be processed to alter the microscopically examine both loose and illuminated CCD detector. The integra-
color and increase market value, with mounted stones, Raman can distinguish tion time for spectral collection was 20 s
the unsuspecting consumer convinced not only real versus artificial gemstones, per acquisition. The confocal aperture of
that he has purchased a stone of greater but also can discriminate those that have 50 mm gives an approximate 1 mm (x, y)
value (7, 11). With lesser gemstones the been adulterated in addition to provid- × 2 mm (z) sample volume. The laser
analytical techniques are much less ing details of the alteration. power at the sample was approximately
established and more reliant on long 10 mW or less.
experience with mineralogical identifi- Experimental
cation methods. Raman spectroscopy Loose and mounted gemstones in differ- Results and Discussion
provides an ideal method for the exami- ent types of platinum gold jewelry set- Citrine, Topaz, and Amethyst. The most
nation of gemstones and semiprecious tings (rings and pendants) were bor- commonly occurring form of silica
stones. Raman spectroscopy is a meas- rowed or purchased from various deal- (SiO2) is quartz, which appears in
urement of the reemission of light from ers. In several instances these gemstones impure form as amethyst, citrine, onyx
interaction with an incident light source, had professional appraisals. Each gem- and jasper (12). Citrine is the most valu-
usually a laser. Raman spectra result stone then was placed into the sample able quartz gem. Almost all citrine on
from vibrational motions of the molec- compartment of a Jasco Ventuno, a the market is heat-treated amethyst (13).
ular bonds in the material. As opposed benchtop-mounted fully integrated con- Natural citrine is yellow to orange, and
to infrared spectra, which are a result of focal micro-Raman spectrometer. The occurs in much lighter hues than the
a change in the molecular dipole instrument was equipped with a 488-nm heat-treated material. Amethyst tradi-
moment during the molecular vibra- argon ion laser (Melles Griot, Carlsbad, tionally is purple. The color in both
tion, Raman spectra result from a CA) and a 532-nm diode laser (Torsana amethyst and citrine is due to impurities

22 Spectroscopy 19(4) April 2004 w w w. s p e c t r o s c o p y o n l i n e . c o m

of iron at parts per million levels. The color (12). The ancient Egyptians called teristic silicon bands from 900–1150 cm-
1
iron substitutes for silica in the quartz peridot “the Gem of the Sun” because it , which indicated that these stones were
structure. The iron is trivalent and gives supposedly was too bright to be visible merely green glass. Thus Raman analysis
the yellow color seen in citrine. If it is in the sunny Egyptian desert. Legend proved the peridot in this bracelet to be
irradiated, most of it will turn purple, also suggests that peridot can glow at a fake.
but not all citrine will change color (11). night which made it easier for the Another orthosilicate gemstone is
In some amethyst deposits, the amethyst Egyptians to see (and mine it) after sun- garnet, which is a group of compounds
has been partially or fully changed to set (11–15). We analyzed several peridot with the structure, M23M32(SiO4)3 where
brown citrine by geothermal heating. stones in various shapes and settings. M2 are eight-coordinate (Ca, Mg, Fe)
Citrine also can be produced by heat- The first two stones were trillion cut, one and M3 are six-coordinate (Al, Cr, Fe)
treating smoky quartz from certain mounted in a ring and the other in a a (12). The name garnet can be applied to
localities. Citrine also closely resembles pendant. Two oval peridot stones from a six similar mineral species, namely
topaz (14). Unfortunately, unscrupulous ring and a pendant also were evaluated. almandine, pyrope, spessartine, grossu-
dealers label citrine in such a way that Finally a series of peridot stones from a lar, andradite, and uvarovite. To further
unassuming buyers think they are buy- tennis bracelet were examined by Raman complicate matters, many garnets actu-
ing the more valuable topaz. It should be spectroscopy. The Raman spectra from ally are a combination of these minerals.
understood that any “topaz” labeled each of the first four stones were almost Rhodolite, for instance, is a combination
with a prefix (such as gold topaz, identical, independent of stone cut. of almandine and pyrope (13). There
Brazilian topaz, and citrine topaz) is Figure 2 shows the Raman spectra from also are many trade names and other
heat-treated citrine. The Raman spectra the oval peridot pendant and the trian- commonly used names which only adds
in Figure 1 clearly indicate the differ- gular peridot ring. Some minor varia- to the confusion, such as Rhodolite,
ences between citrine and topaz. tions in some of the weaker bands are Tsavorite, Malaya, Mozambique,
Peridot, Emerald, Garnet, and Tanzanite. indicative of the stone cut. The peridot Mandarin, Melanite, Topazolite, and
Peridot is the well-known gem variety of spectra from the tennis bracelet, howev- Thai (2, 15). The most common forms
olivine ([Mg,Fe]2SiO4), a species name er, had a large fluorescence and were of garnet all contain iron and adopt one
for a series of magnesium-iron rich sili- missing the peridot bands. Instead, these of the spinel structures (12). We evaluat-
cate minerals known for their green so-called peridot exhibited the charac- ed several different garnets, including

Circle 18 March 2004 19(3) Spectroscopy 23

Gemstone Identification

two oval shaped garnets mounted as

10
pendants, two square garnets mounted Figure 5. Three
as earrings, and several small round gar- rubies: maternal
nets in an earring cluster. Figure 3 illus- stone (dot/dash),
8
paternal stone
trates the Raman spectra from each gar-
(solid), and ruby
net shape. The top square garnet was 6 ring (dashed). All
identified as being spessartine-zz. The

Intensity
have the same
middle spectrum of the round stone was characteristic ruby
determined to be an alamandine-xx, 4 peaks.
while the bottom spectrum of the oval
garnet is an example of the pyrope-zz. 2
Tanzanite is a unique gemstone as it
occurs in only one specific location in the
east African state of Tanzania. It has a 0
4450 4450 4350 4325
characteristic blue color that shimmers in Raman shift (cm-1)
a slightly purplish hue. Tanzanite is a blue
variety of zoisite gemstone. However, this
hydrated calcium aluminum silicate min- 4 Figure 6. The 1332
eral Ca2Al3Si3O12(OH) achieves only cm-1 diamond
hardness 6.5 – 7 on the Mohs’ scale, and Raman band (bot-
is thus not very resistant to abrasions (16, 3 tom) is clearly dis-
17). Tanzanite is a natural gemstone tinguishable from
whose color is enhanced by heat-treating. the luminescence of
Intensity

When found in nature, tanzanite crystals 2 the glass imposters

are a muddy reddish-brown color. The (top solid and
dashed).
crystals then are heated to approximately
650–700 °F to bring out the permanent 1
rich blue, purple, and violet colors.
Tanzanite is one of the few gemstones
that are pleochroic, meaning it exhibits 0
two or more separate colors when viewed 2000 1500 1000 500 60
Raman shift (cm-1)
at different angles. The more common
colors are blues and purples but one
might also see flashes of red, green, yel- from about 50 to 2000 cm-1 (Figure 4). glued on top of a colored glass bottom
low, orange, or brown. The color that All four tanzanite examined had spec- to form a large composite emerald.
gemologists predominantly speak of is tra with identical peak locations, but Soude emeralds are false emerald dou-
the “deep royal blue” (18–21). Tanzanites, the individual spectra exhibited differ- blets that consist of a colorless spinel
which are more blue than purple, usually ent peak height ratios. These slight top and bottom pieces fused together
are more expensive because the crystals intensity differences are attributed to with a green bonding agent. Emerald
tend to form with the blue color axis ori- the alignment of the crystals along the triplets can be detected by immersing
ented along the width of the crystal color axis. the stone in a liquid such as alcohol —
instead of the length (22). Emerald is in the beryl family (beryl- the top and bottom pieces seem to dis-
Several synthetic gemstones and lium aluminum metasilicate) with a appear and all that is visible is the
nongem materials have been offered as chemical formula of Be3Al2Si6O18. The green bonder at the girdle. Another
substitutes for tanzanite. For example, emerald differs from other beryls in its common emerald imitator is green
synthetic fosterite simulates the color deep green color (7). Its intense green glass (19). We examined emeralds in an
and look of tanzanite but is signifi- coloring is due to a trace of chromium antique platinum ring consisting of 10
cantly less expensive. Synthetic sap- or vanadium replacing the aluminum square cut emeralds surrounding a
phires also have been offered as imita- in the beryl structure. Because of the round diamond. The emerald Raman
tors of the bluer varieties of tanzanite nature of this replacement, almost no spectra are shown in Figure 4 along
(18). We evaluated several tanzanite emeralds with intense color are free with the tanzanite.
stones and compared them with a ref- from inclusions. Imitation emeralds A Tale of Two Rubies. We examined
erence database (21). One stone was a are found most commonly as compos- two large blue–purple gemstones
triangular shaped stone, two others ite stones, which are jewelry pieces mounted in separate rings. The
were oval, and one was round. The comprising more than one stone bond- amethyst from the first ring was a large
Raman spectrum of tanzanite has a ed together. False emerald doublets teardrop shape and mounted in 14-
characteristically complex spectrum consist of a thin slab of emerald that is karat yellow gold. It was purchased at

24 Spectroscopy 19(4) April 2004 w w w. s p e c t r o s c o p y o n l i n e . c o m

an antiques store in rural Maryland negative electron affinity (or work References
and had been appraised independently function) (22). 1. www.trappgem.com
twice by two separate lapidaries as All natural diamonds are flawed, 2. http://www.attawaygems.com/NMFG
amethyst. The stone from the second often by color or impurities. Most dia- /causes_of_color.html
ring was a large round stone with the monds have some yellow or brown 3. Richard T. Liddicoat, Handbook of Gem
same blue–purple color mounted in color. Defects mark the diamond as Identification (The Gemological
18-karat rose gold. It was purchased in unique. Color centers in diamond pho- Institute of America, Los Angeles,
Egypt and was sold as alexandrite. This toluminesce when excited by laser light. 1951).
ring also was appraised due to the rari- A Raman spectrometer used to measure 4. Robert M. Shipley, Dictionary of Gems
ty of the alexandrite. This stone was photoluminescence is a powerful char- and Gemology (The Gemological
determined to be amethyst. This acterization tool to identify artificially Institute of America, Los Angeles,
seemed reasonable because the other reprocessed, so-called exotic colored 1948).
ring with the similar stone was also diamonds. The diamond grading sys- 5. http://www.jewelrymall.com/stones/
appraised as amethyst. tem is as follows: D and F are colorless, 6. http://www.emporia.edu/earthsci/
Raman analysis of both stones pro- G through J are near colorless, K amber/go340/treat.htm
vided an interesting discovery. Neither through M are faint yellow or brown, N 7. http://www.professionaljeweler.com/
stone had the characteristic amethyst through Z are light yellow, brown or archives/articles/1998/jun98/0698gg1.
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display the strong bands at 4392 and Cubic zirconia is now one of the 8. http://www.palagems.com/
4360 cm -1, characteristic of ruby. most common substitutes for diamond. quality_4cs.htm
Comparison of the spectra of these The original manufacturing process 9. http://www.gemshopper.com/fraud.html
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oring (Figure 5). In this instance three different colors due to the addition of raman/raman/spettri.htm
separate lapidaries gave three incorrect other minerals, but only the clear white 12. N.N. Greenwood and A. Earnshaw,
appraisals of the stones. We also evalu- is preferred as a substitute for diamond. Chemistry of the Elements (Pergamon
ated two synthetic rubies and and With a distinctly different Raman spec- Press, New York, 1989).
found them to be indistinguishable trum, cubic zirconia gemstones can be 13. http://minerals.gps.caltech.edu/data
from their natural counterparts. distinguished easily from diamond. 14. Charles W. Chesterman, Field Guide to
Throughout history, ruby has been Common glass also is a cheap substitute Rocks and Minerals (published for the
considered the most prized of red gem- for diamond. Glass is distinguished eas- National Audubon Society by Alfred A.
stones and is considered to be the ily from the diamond in the Raman Knopf, New York, 1979).
medium-to-dark orangey red to pur- spectra because glass has a large photo- 15. http://www.mindat.org/min-1651.html
plish red variety of corundum, a min- luminescence. Diamond is character- 16. http://www.aist.go.jp/RIODB/rasmin/
eral composed of aluminum oxide ized readily by a sharp Raman band at E_index.htm, Ceramics Institute, AIST,
(Al2O3) (20). Colored metal ion impu- 1332 cm-1 (Figure 6). JAPAN
rities create the gemstone color, such as 17. http://www.gemstone.org/gem-by-
Cr3-ruby, and Fe2/3, Ti4-sapphire (12). Conclusions gem/english/tanzanite.html
The sapphires that we evaluated had Raman spectroscopy has been demon- 18. http://www.jewelryexpert.com/arti-
spectra virtually indistinguishable strated as an ideal method for the analy- cles/Tanzanite-Article.htm
from the ruby (11). sis of gemstones, both real and fake. 19. http://www.diamonds-gemstones-jew-
Diamonds. Diamond has been prized With the ability to examine both loose elry.com/emerald-grading/imitation-
for centuries as a gemstone of excep- and mounted stones of any size or con- emeralds.aspx
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exceptional chemical properties. When ly distinguish various gemstones that do com.htm
compared with almost any other mate- not readily lend themselves to identifi- 21. http://cwjewelers.com/stonetanz.htm
rial, diamond is almost always the cation by other, more traditional gemo- 22. http://www.bris.ac.uk/
most valuable. As well as being the logical identification methods. Raman Depts/Chemistry/MOTM/diamond/
hardest known material, it is also the spectra also can provide a unique fin- diamond.htm. ■
least compressible, the stiffest, the best gerprint of the gemstone with the abili-
thermal conductor with an extremely ty to distinguish any future alteration of Amanda L. Jenkins
low thermal expansion, chemically the gemstone. The photoluminescence is a senior applications specialist at
Jasco, Inc. (Easton, MD). E-mail:
inert to most acids and alkalis, and of colored diamonds offers a method
[email protected].
transparent from the deep UV through for the determination of the color of
the visible to the far infrared, and it is diamonds and provide a further dis- Richard A. Larsen
one of the few materials known with a crimination of the diamond color scale. is an applications chemist at Jasco.

April 2004 19(4) Spectroscopy 25