The Geochemistry of Gems

and Its Relevance to Gemology:

Different Traces, Different Prices
George R. Rossman1

1811-5209/09/0005-0159$2.50 DOI: 10.2113/gselements.5.3.159

I
n colored gems, minor and trace chemical components commonly Green color can also occur in
determine the difference between a common mineral specimen and andradite garnet, Ca 3Fe 2 (SiO 4 ) 3.
Andradite is pale yellow-green when
a gemstone. Also, these components are often responsible for the it has exactly the end member
color, and may provide a fingerprint for determining the provenance composition, but commonly, minor
of the gemstone. The minor elements that are incorporated will depend amounts of Ti4+ coupled with Fe2+
turn andradite to brown or black.
on local geologic conditions such as temperature, redox conditions, and, A beautiful green variety of andra-
particularly, chemistry. dite occurs when minor amounts
of Cr3+ enter the garnet (Mattice
KEYWORDS : gemstone, provenance, color, geochemistry
1998). These stones, known as the
variety demantoid, are highly
COLOR IN GEMSTONES valued (FIG. 1B).
Metal ions from the fi rst row of transition elements in the The stoichiometric components of garnets also depend on
periodic table, especially Ti, V, Cr, Mn, Fe, and Cu, are the the geologic setting. In lithium pegmatites, minerals that
most important causes of color in oxide and silicate crystallize late in the formation of the gem pockets in the
gemstones. V3+, Cr3+, Mn3+, and Cu 2+ can produce strong pegmatites can be nearly devoid of iron. In this setting,
coloration when present at concentrations of tenths of a nearly pure end member spessartine garnet, Mn3Al2 (SiO4) 3,
weight percent. Color comes from electronic transitions can occur. This garnet has a beautiful orange color due to
involving only the electrons in the d-orbitals (referred to Mn2+ in a cation site of eight-coordination (FIG. 2). If the
as ligand-field transitions or crystal-field transitions). When garnet grows while some iron is still present in the pegma-
present by themselves, Fe2+, Fe3+, and Mn2+ typically require titic fluids, the color becomes a much less valuable brown-orange
higher concentrations to cause significant color. Intervalence due to solid solution with the almandine end member,
charge transfer (IVCT) interactions, which involve an Fe3Al2 (SiO4) 3.
exchange of an electron between two cations with different
valences (for example, between Fe2+ and Fe3+ or between A
Fe 2+ and Ti4+) are a major source of color in gems and
require only a small amount of the interacting couple to
produce intense color. In some systems, charge transfer
from oxygen to the metal ion also contributes to the color.

Garnets
Good examples of the compositional dependence of color
are provided by the garnet group. When grossular garnet,
Ca3Al2 (SiO4) 3, is composed of just the end member compo-
nents, it is colorless. Ca 2+, Al3+, Si4+, and O2- ions do not
absorb light in the range of the visible spectrum. However,
low concentrations of minor elements can dramatically B
modify the color. Small amounts of V3+ with some Cr3+
turn grossular into the green tsavorite variety (FIG. 1A).
Spectacular examples of these garnets occur in marble
seams in graphitic gneisses of the Mozambique belt in
northeastern Tanzania and southeastern Kenya. There,
metamorphic fluids were able to mobilize traces of vana-
dium and chromium from the host rock and incorporate
them in the grossular garnets. The unusual beauty of these
garnets was recognized after their discovery in 1967 and
they were given the trade name tsavorite, in honor of the
nearby Tsavo National Park in Kenya (Bancroft 1984). (A) The tsavorite variety of grossular garnet owes its color
FIGURE 1
to the substitution in the Al site of about a percent level
3+ usually
of V accompanied by a lesser amount of Cr3+. This stone
weighs 7.4 carats. (B) The color of the demantoid variety of andradite
1 Division of Geological and Planetary Sciences is due to a minor amount of Cr3+ but is somewhat modified by the
California Institute of Technology presence of the stoichiometric constituent Fe3+. This highly valued
Pasadena, CA 91125-2500, USA variety of andradite has classically come from the southern Ural
E-mail: grr@gps.caltech.edu Mountains of Russia. PHOTOS : WIMON MANOROTKUL, PALAGEMS.COM

E LEMENTS , V OL . 5, PP. 159162 159 J UNE 2009

PROVENANCE OF GEMS Minor and Trace Elements
Over time, gems from certain localities have been recog- Minor and trace elements are often different or incorporated
nized as having greater beauty, and thus greater value. Even differently in gems of the same species but from different
as new sources of gems are located, gems from the classic localities. Thus, they may provide a readily available tool for
localities may still be perceived to have a higher value than determining the locality of origin of gems. The following
more recently discovered stones of similar color and quality. examples illustrate this concept.
The geographical origin of gems, in a general sense, is
becoming an important commercial factor. More value is Tourmaline
ascribed to particular deposits of gems compared to others Most gem tourmalines owe their color to Fe2+ (most blue
with similar geology. tourmalines), Fe2+ plus Fe2+ Ti4+ IVCT (green), Mn3+ (pink),
Mn2+ Ti4+ IVCT (yellow), or a combination of these factors
One question that must be addressed is what can be done
(FIG. 3). At a few localities, such as in Kenya and Tanzania, Cr3+
with a faceted stone to determine its locality of origin. The
and V3+ are the minor components responsible for the color.
need to avoid visually destructive analytical methods
restricts the use of many standard geochemical methods In 1988, a new fi nd of gem-quality elbaite with unusually
and presents demanding analytical challenges. A variety saturated shades of green and blue was made in the
of tools are now available, including minimally or Brazilian state of Paraba. The unusual blue color comes
nondestructive chemical analysis for major and trace from the copper content, which can range up to 1.7 wt%
elements, luminescence, and isotopic analysis. Other CuO (Rossman et al. 1991). The stones became an instant
avenues of investigation, such as inclusions and growth success in the commercial market (FIG. 4, inset). Later, tour-
features, are discussed in Fritsch and Rondeau (2009 this malines were found in Nigeria and Mozambique that also
issue) and Devouard and Notari (2009 this issue). contained copper and had blue colors approaching those
of the tourmaline gems from Paraba. The question was
raised about the possibility of distinguishing the provenance
of copper-containing tourmalines once they had been
faceted and entered the market.

Quantitative laser ablationinductively coupled plasma

mass spectrometry (LAICPMS) analysis can be used to
differentiate tourmalines from the various localities by
comparing concentrations or proportions of selected minor
and trace elements such as Cu, Mn, Ga, Pb, Be, Mg, and Bi.
For example, the Brazilian stones generally have more Mg,
Zn, Bi, and Sb, while the Nigerian stones generally contain
elevated levels of Ga and Pb (Abduriyim et al. 2006). By
comparing the relative proportions of Bi, Pb, and Ga in such
tourmalines, one can, in most cases, distinguish between the
three main geographical provenances (FIG. 4). However, there
is still a small overlap between the compositions of tour-
malines from Mozambique and Brazil (Krzemnicki 2007).

Corundum
For many years, rubies from the Mogok region of Burma
were considered the fi nest in the world and commanded
a high price (Hughes 1997). Beginning in the early 1990s,
A crystal of orange spessartine and a faceted gem from rubies from a different source in Burma appeared in markets
FIGURE 2 in Bangkok. The Mng-Hsu rubies generally are unsaleable
the Little Three mine near Ramona, San Diego County,
California. The orange color is due to Mn2+ in the eight-coordinated as mined. They usually must be heated, often to high
cation site of the garnet. PHOTO: WIMON MANOROTKUL, WWW.PALAGEMS.com temperatures, to remove a naturally occurring dark blue
color that arises from a combination of Fe2+ Ti4+ and Fe2+
Fe3+ IVCT in the core of the stones. Heating oxidizes the
Fe2+ to Fe3+, which disrupts the IVCT couple. Furthermore,
the heating of rubies from Mng-Hsu introduces flux into
cracks in the stones (Peretti et al. 1995; Emmett 1999).
Although beautiful, the rubies from Mng-Hsu are gener-
ally valued less than rubies from Mogok because they have
been treated to enhance their appearance (Drucker 1999).

Thus it would be useful to be able to distinguish rubies

from different localities. Apart from specific microscopic
features, it has been shown that rubies from the Mogok
and Mng-Hsu localities can be differentiated on the basis
of their Ti/V ratio (Muhlmeister et al. 1998; Mittermayr et
al. 2008) as determined using X-ray fluorescence (XRF) or
LAICPMS. In other examples, key elements, such as V,
Ti, Ga, and Fe, have been used to separate rubies from
FIGURE 3 A suite of tourmalines illustrating the tremendous variety
of colors displayed by this mineral group. All the gems Vietnam/Burma versus Thailand or Tanzania. For a more
in this figure probably belong to the tourmaline species elbaite. End general distinction of ruby localities, the ratios of Fe, Ga,
member elbaites ideal composition is Na(Li1.5Al1.5)Al6(BO3)3Si6O18 (OH)4, and Cr have proven useful (Rankin et al. 2003; Peretti
a species that would be devoid of color if it were exactly the ideal
2008; Schwarz et al. 2008). Likewise, the source of blue
composition. The gems in this photo are colored by traces of iron,
manganese, and titanium. PHOTO: WIMON MANOROTKUL, WWW.PALAGEMS.COM sapphires can be determined using the trace element ratios

E LEMENTS 160 J UNE 2009

of Zn, Sn, Ba, Ta, and Pb as determined by LAICPMS wide use in commercial gem laboratories, but holds much
analysis of element concentrations down to levels promise for the future. As is the case with many analytical
approaching ppb (Guillong and Gnther 2001; Rankin et methods, the overlapping ranges of oxygen isotope ratios,
al. 2003; Abduriyim and Kitawaki 2006a). especially for the classical or commercially important
deposits such as Mogok, Kashmir, Sri Lanka, and Madagascar,
Isotopic Methods mean that no single analytical method will provide the
The provenance of gems has always been important to answers to all problems of provenance.
some degree. However, now that provenance has increased
in importance for commercial reasons, the tools to deter- SYNTHETIC CRYSTALS
mine origin have been refined. Chemical composition, inclu- Many of the same analytical methods used to differentiate
sions, growth features, luminescence, and trace elements the geographic or geologic source of a gem can also be
may all have a role in the determination of provenance. applied to distinguish synthetic from natural stones. Such
While stable isotopes have proven highly useful in distinctions will become increasingly important as the
geochemistry for studying the geological history of rocks quality of synthetic materials rises to nearly match that of
and minerals, they have, to date, found little practical their natural counterparts.
application in the determination of the provenance of
gemstones. In principle, isotopes should provide informa- Synthetic Amethyst
tion about the origin of gems, but the cost, time required,
Hydrogen is an important trace element in many natural
and destructive nature of these tests have, until now,
minerals. It is a common charge-balancing cation (in the
prevented isotopic methods from gaining wide application
form of an OH group). Its mode of incorporation can vary
in gemology. A few examples demonstrate the utility of
depending on the geologic conditions of formation of the
isotopic methods when applied to gem minerals.
host crystal. The intensity and shape of absorption bands
in the OH region of the electromagnetic spectrum provide
Emerald
a test for synthetic amethyst. A band at 3595 cm-1 is present
Emerald is a green variety of beryl, Be 3Al 2 Si6O18, that in the infrared spectrum of all natural amethysts but only
contains Cr3+ and, occasionally, some V3+ as the chromophore. rarely in synthetic ones. If present in synthetic amethyst,
It forms from hydrothermal fluids. The isotopic composi- its full width at half maximum (FWHM) is about 7 cm-1,
tion of these fluids varies with locality (Giuliani et al. 1998; whereas it is about 3 cm-1 in all natural samples. This
Zwaan et al. 2004). In an elegant study, Giuliani et al. absorption band difference provides a method to separate
(2000) used the isotopic composition of oxygen in emerald natural from synthetic amethysts (Karampelas et al. 2005).
to trace international trade routes since antiquity (FIG. 5).
Synthetic Ruby
Corundum
Minor and trace components commonly found in nature
Because both ruby and sapphire occupy an important place can be lacking in some synthetic gems. Such differences
in the gem market, the origin of corundum gems is a matter can be detected by some of the same testing methods previ-
of interest. In addition to the use of chemical element
ratios, as discussed above, to distinguish among localities,
certain classes of corundum show large isotopic differences
between different localities (Yui et al. 2003; Giuliani et al.
2005). Oxygen isotopes in carbonate-hosted corundum
show wide variations, whereas oxygen isotopes in mantle-
derived corundum vary much less. Because of the time
required for isotope analysis, its expense, and the destruc-
tive nature of the technique, the approach has not gained

FIGURE 5 The oxygen isotope composition of emeralds varies

among important gem-producing regions of historical
importance. The colored bands indicate the range of composition at
A plot of the relative proportions of Bi, Pb, and Ga, all each locality, and the white rectangles indicate the composition of
FIGURE 4 the ancient emeralds studied by Giuliani et al. (2000). 1: Gallo-Roman
present as trace elements in Cu-containing tourmalines
(inset), can in most cases distinguish the provenance of such earring; 2: Holy Crown of France; 3: Hays emeralds; 4: Spanish
tourmalines: Nigeria, Mozambique, or Brazil. These data were galleon wreck; 5: old mine emeralds. The isotopic variations allowed
obtained using LAICPMS. GRAPH MODIFIED FROM MICKAEL KRZEMNICKI these authors to trace the flow of emeralds in world commerce from
(2007); PHOTO (INSET): WIMON MANOROTKUL, WWW.PALAGEMS.COM antiquity to the late 18th century. GRAPH MODIFIED FROM GIULIANI ET AL. (2000)

E LEMENTS 161 J UNE 2009

ously discussed. For example, for several years, synthetic TREATED NATURAL GEMS
ruby was made from purified aluminum oxide from which
Many of the tests to determine the geological or geographic
most of the naturally occurring gallium had been removed
origin of a stone can also be used to find out if a stone has been
in the industrial purification process. Thus, natural rubies
subjected to laboratory processes to change its color or other
were readily distinguished by the presence of trace concen-
properties. As an example, consider the corundum gems,
trations of gallium. However, soon after the gallium test
which are commonly heated to clarify and modify their color.
became widely known, gallium began to appear in some
A recent development is the diffusion of beryllium, at the
synthetic stones.
level of 10 ppm or less, into the stones to change their color
to extents that range from subtle to dramatic. This treatment
Synthetic Emerald was initially difficult to detect, but now a variety of analyt-
For some time, a minor absorption band at 2293 cm-1 in ical methods have been developed. Laser-induced break-
the infrared spectrum of natural emeralds was found to be down spectroscopy (LIBS), LAICPMS, and secondary ion
absent in the spectrum of synthetic emeralds and could mass spectrometry (SIMS) now make it possible to detect
therefore be used as a test to distinguish between natural these low levels of beryllium in treated stones (Krzemnicki
and synthetic stones. However, such tests are not always et al. 2004; Abduriyim and Kitawaki 2006a, b).
long lasting. In the case of emeralds, Russian hydrothermal
synthetic emeralds now contain the 2293 cm-1 band (Duroc-
Danner 2006). Bands caused by water trapped in the c-axis
CONCLUSIONS
channels of beryl are present in natural emeralds and aqua- The examples cited illustrate just a few of the methods, both
marines (the blue variety of beryl) but are absent in flux- common and sophisticated, that are employed to determine
grown synthetic emeralds. Fortunately, other methods for the origin of gem materials. In many cases, rigorous tests
distinguishing natural from synthetic emeralds are available, prove to be too expensive compared to the value of the item
and these are based on trace element analysis using tested, or currently are too destructive for routine use. In
methods such as XRF and particle-induced X-ray emission several instances, the geochemical reasons for some of the
(PIXE) (Yu et al. 2000). observed differences are not fully understood. In other
cases, suitable tests are still lacking.

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