IDENTIFICATION OF CULTURED PEARLS AND PEARL IMITATIONS

USING SPECTROSCOPIC TECHNIQUES

Ms Siti Juliana Binte Khairoman

Supervisor: Assoc Prof Augustine Tan T.L.

Natural Sciences Academic Group
National Institute of Education
1 Nanyang Walk, Singapore 637616

tltan@nie.edu.sg

Keywords: Pearl, composition, FTIR, EDXRF, SEM

Abstract
Pearl is a popular organic gemstone basically due to the beauty of its natural lustrous and
iridescent surface. For superior quality pearls, it may take up to two years or more to
harvest and the yield is usually low. Theses account for their high price and the
proliferation of pearl imitations. In this investigation, the surface structure of the cultured
pearls and its imitations are studied using scanning electron microscope (SEM) at
magnification of up to 2,000 times. Energy-dispersive x-ray fluorescence (EDXRF) and
Fourier transform infrared (FTIR) spectroscopy are employed to study the chemical
composition of the pearl layer and the bead for naturally-coloured cultured pearls, dyed
cultured pearls and pearl imitations. In EDXRF experiments, elemental detections of Ca,
C and O in the cultured pearls and their beads show that they are basically CaCO3, while
the detection of only C and O in pearl imitations reveals that they are polymeric in
composition. Detections of Si and O in the bead of pearl imitation show the presence of
glass substances in it. In FTIR experiments, the absorption peaks of 700 cm-1, 713 cm-1,
862 cm-1 and 1083 cm-1 are observed in both naturally-coloured and dyed cultured peaks,
which confirm that they are CaCO3 with aragonite structure. However, the infrared
spectrums of pearl imitations are very different and are typical of polymers.

1. Introduction
Many studies on pearls have been done and are recorded in journals. For instance, studies
on Chinese cultured pearls in relation to their production and colour-treatment were made
recently using Raman spectroscopy. Formation and quality of pearls were also
investigated in detail using optical and scanning electron microscope. These structural
studies were useful in understanding the formation of cultured pearls. The history,
production and yield of Australian pearls had also been studied. The internal structure of
pearls and Bangladesh pearls had also been studied.
In this research, studies on cultured pearls and pearl imitations using spectroscopic
technique such as Fourier transform infrared (FTIR) spectroscopy and energy-dispersive

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x-ray fluorescence (EDXRF) were applied. These techniques will be useful for the
identification of the chemical composition of the pearls. The usefulness of these
techniques was also discussed.
Spectroscopic studies on them were also very limited as these imitations are rampant in
the pearl market and may not be easily distinguished by visual observations. Hence, it is
useful to study their chemical composition using FTIR and EDXRF techniques. Results
showed that imitation pearls could be effectively differentiated from the cultured ones.
Therefore, it is worthwhile to make a systematic study of cultured pearls and its
imitations using these scientific methods.

2. Materials and Experimental Methods

Five samples of naturally-coloured cultured pearls (Samples 1-5), three samples of dyed
cultured pearls (Samples 6-8), one sample of shellfish bead for all cultured pearls
(Sample 9), four samples of imitation pearls (Samples 10-13) and one sample of bead for
imitation pearls (Sample 14) were used in this research project as shown in the
photograph.

Photograph of all the 14 samples of both cultured and imitation pearls

Row 1: Cultured Pearls (Samples 1-5)
Row 2: Dyed Cultured Pearls (Samples 6-8) and Cultured Bead (Sample 9)
Row 3: Imitation Pearls (Samples 10-13) and Imitation Pearl Bead (Sample 14)

All the cultured pearls samples were freshwater cultured pearls from China. The imitation
ones were easily available in shops and were produced in Japan. Scanning electron
microscope (SEM) observations, ultraviolet fluorescence, Fourier transform infrared
(FTIR) spectroscopy and energy dispersive x-ray fluorescence (EDXRF) were carried out
for these samples and the results are summarized in Table 1.
Ultraviolet (UV) fluorescence was the initial test carried out to distinguish the pearls
from one another. The UV lamp used is a model of UVGL-58, Mineral Light, USA. It
has a short wave of wavelength 254nm and long wave of 365nm. The pearl samples were
cleaned with ethanol to remove organic impurities on the surfaces. Cultured pearls

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normally have a weak whitish fluorescence under short wave and strong bluish white
fluorescence under long wave (Matlins, 1999).
Following the UV fluorescence tests, SEM observations and EDXRF tests were carried
out using JEOL JSM–5600LV SEM/EDX microscopy with a working voltage of 20kV.
Surface analysis by EDXRF is accomplished by bombarding a sample with high-energy
electrons and detecting and analyzing the energy of the emitted x-rays (Riddle, 1993).
These electrons have penetrating power in a solid extending 1 to 5 µm depending on their
energy and the nature of substance. EDXRF is a surface-sensitive technique of chemical
characterization of the surface of a solid. For this, the surfaces of all samples were
cleaned using ethanol solution in order to remove any contaminant present due to
handling. Since EDXRF helps to identify the elements in the samples, SEM observations
of the samples were also taken into consideration to learn more about the surface
structure of the samples in the identification of the cultured pearls from the imitations.
All the samples were further tested using the FTIR spectroscopy method. A Perkin Elmer
Instruments, Model Spectrum One– Fourier Transform Infrared Spectrometer was used to
record the spectra of all samples in the wavelength range of 400 cm-1 to 4000 cm-1. The
accuracy of the absorption peaks was ±1 cm-1.
Since pearls are opaque, the samples were wiped cleaned with ethanol before the surface
of the samples were scraped off, ground to a fine powder and mixed with potassium
bromide (KBr) to make circular pellets. These pellets are translucent and allow infrared
light to pass through it and be absorbed. The infrared transmission spectra were recorded
to give absorption peaks for identification of materials.

3. Results and Discussions

The results of SEM observations, UV fluorescence, FTIR spectra and EDXRF elemental
analysis are summarized in Table 1 for all 14 samples. The individual tests and results
will be further described in the next few paragraphs.

3.1 Ultraviolet (UV) Fluorescence

For naturally-coloured cultured pearls (Sample 1-5), there was no clear distinction
between fluorescence in the short and long wavelengths. Samples 3, 4 and 5 all being
white cultured pearl, showed very strong bluish white in the long-wave and weak bluish
white in the short wave. However samples 1 and 2 did not show such strong fluorescence.
The results of samples 3, 4 and 5 agree with the data of Matlins et al, 1995 which states
that cultured white pearls have weak whitish in short wave and strong bluish white in the
long wave. Similarly, the shellfish bead (sample 9) used in the cultured pearls has weak
whitish in short wave and strong bluish white in the long wave.
However, for dyed cultured pearls (samples 6-8) there are no obvious trends in their UV
fluorescence. All pearl imitations (samples 10-13) were inert in the short wave and weak
dark purple fluorescent in the long wave. The bead used in pearl imitations (Sample14)
was inert in the long wave and weak yellowish white in the short wave. Since the results
were not conclusive enough, comparison between cultured and imitation pearls were not
accurate.

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Table 1 SEM observations, UV Fluorescence, FTIR absorption peaks and EDXRF
elemental peaks on Cultured Pearls (samples 1-5), Dyed Cultured Pearls
(samples 6-8), Cultured Shellfish Bead (sample 9), Imitation Pearls (samples
10-13) and Imitation Pearl Bead (sample 14)

Sample Description and (SEM) Ultraviolet fluorescence FTIR EDXRF

observations Short wave Long wave Absorption Elemental
(254 nm) (365 nm) peaks (cm-1) peaks
1 Pink, baroque cultured pearl. Inert Weak Blue 700, 713, 862, C, O, Ca
Layered, flaky surface. 1083, 1469,
1788, 2499,
2522, 2547, 2920
2 Orange, baroque cultured Inert Inert 700, 713, 863, C, O, Ca
pearl. 1083, 1472,
Layered, flaky surface. 1788, 2499,
2522, 2547, 2919
3 White, oval-shaped cultured Weak bluish Very strong 700, 713, 862, C, O, Ca
pearl. white bluish white 1083, 1463,
Layered, flaky surface. 1788, 2500,
2522, 2547, 2918
4 White, strong iridescent, Weak bluish Very strong 700, 713, 862, C, O, Ca
baroque cultured pearl. white bluish white 1083, 1462,
Layered, flaky surface. 1788, 2500,
2522, 2547, 2918
5 White, spherical cultured Weak bluish Very strong 700, 713, 862, C, O, Ca
pearl. white bluish white 1083, 1463,
Layered, flaky surface. 1788, 2500,
2522, 2547, 2918
6 Green-dyed, round cultured Inert Green 700, 713, 863, C, O, Ca
pearl. Layered, contoured 1083, 1469,
surface. 1788, 2500,
2522, 2547, 2918
7 Blue-dyed, round cultured Weak Purple Very strong 700, 713, 862, C, O, Ca
pearl. Layered, contoured bluish white 1083, 1469,
surface. 1788, 2499,
2522, 2546, 2917
8 Gold-dyed, round cultured Inert Inert 700, 713, 861, C, O, Ca
pearl. Layered, contoured 1083, 1469,
surface. 1788, 2499,
2522, 2547, 2918
9 Shellfish bead for cultured Weak bluish Strong bluish 700, 713, 861, C, O, Ca
pearls. white white 1083, 1424,
Layered, flakes surface. 1788, 2499,
2522, 2546, 2918
10 Cream-white imitation pearl. Inert Weak dark 751, 840, 1068, C, O
Cubes-like structures on purple 1161, 1280,
surface. 1376, 1654,
1732, 2554,
2929, 2964, 3466
11 Cream-white imitation pearl. Inert Weak dark 751, 840, 1068, C, O
Cubes-like structures on purple 1161, 1280,
surface. 1376, 1654,
1732, 2554,
2929, 2964, 3466
12 Gold imitation pearl. Inert Weak dark 751, 840, 1068, C, O
Cubes-like structures on purple 1161, 1280,
surface. Cracks and lines are 1376, 1654,
also visible. 1732, 2554,
2929, 2964, 3466

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 13 Gold imitation pearl. Inert Weak dark 751, 840, 1068, C, O
Cubes-like structures on purple 1161, 1280,
surface. Cracks and lines are 1376, 1654,
also visible. 1732, 2554,
2929, 2964, 3466
14 Bead for imitation pearl. Weak Inert 3511, Highly O, Na, Al, Si,
Cubes-like structures on yellowish absorptive Ca
surface white material.

3.2 Fourier Transform Infrared (FTIR) Spectroscopy

All naturally coloured and dyed cultured pearls (samples 1-8) and the shellfish bead used
in cultured pearls (sample 9) have strong infrared absorption peaks at 700 cm-1, 713 cm-1,
862 cm-1, 1083 cm-1, 1469 cm-1, 1788 cm-1, 2499 cm-1, 2522 cm-1, 2547 cm-1 and 2920
cm-1 as shown in Figures 3 to 7. These are typical peaks for calcium carbonate, CaCO3
structure as given in Smith, 1999. The peaks at 700 cm-1, 713 cm-1, 862 cm-1, 1083 cm-1
showed that CaCO3 is of aragonite structure, similar to those of turtle eggshell research
paper recorded by Baird, 1979.
The infrared spectra of pearl imitations (samples 10-13) and the bead used in pearl
imitations (sample 14) are very different. Figure 6 shows the various absorption peaks of
the pearl imitations at 751 cm-1, 840 cm-1, 1068 cm-1, 1161 cm-1, 1280 cm-1, 1376 cm-1,
1654 cm-1, 1732 cm-1, 2554 cm-1, 2929 cm-1, 2964 cm-1 and 3466 cm-1 showed that they
have polymeric content. The peaks at 2929 cm-1 and 2964 cm-1 were the of C-H
vibrations while 1654 cm-1 and 1732 cm-1 was due to C=O stretch (Smith, 1999). The
presence of C, H and O indicates that the pearl layer is polymeric. The bead for pearl
imitations is opaque to infrared below 2500 cm-1 and has a broad peak at 3500 cm-1 as
seen in Figure 7. This shows that the bead is of different material from the pearl
imitations.
The measurements of the various absorption peaks as given in Table 1 are useful and
effective in differentiating naturally coloured and dyed cultured pearls from the
imitations. The beads used in cultured pearls and the pearl imitations are also different.
However, naturally coloured and dyed cultured pearls cannot be differentiated in using
the FTIR absorption peaks.

3.3 Scanning Electron Microscopy (SEM)

The surface of naturally-coloured cultured pearls (samples 1-5) was observed at
magnification of 2000 times as shown in Figure 8. The pattern showed was layered and
flaky. Similar pattern was observed for dyed cultured pearls (samples 6-8) that is layered
but in contoured manner as shown in Figure 9. However, the surface morphology of the
pearl imitations was different as shown in Figure 10. Small cubical particles were seen
randomly distributed. These could probably be polymeric cubes suspended in the layer to
provide iridescence effect. The difference in the SEM observations is again useful for
differentiating cultured pearls from the imitations.

3.4 Energy Dispersive X-Ray Fluorescence (EDXRF)

The EDXRF spectrum typical of naturally-coloured cultured pearl is shown in Figure 11.
The strong x-ray energy peaks of carbon, C Kα1, at 0.277 keV; oxygen, O Kα1 at 0.525

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keV; calcium, Ca Kα1 at 3.69 keV and Ca Kα2 at 4.00 keV, and gold, Au Mβ at 2.205 keV
were identified. These elemental x-ray peak energy values for different elements were
obtained from Blake, 1990. The spectrum recorded in the x-ray energy range of 0 to 9
keV was able to provide identification of all elements present on the surface of the pearls.
The presence of gold, Au detected in the sample surface can be explained by a thin layer
of gold, which is coated prior to the EDXRF scan. The gold coating is to allow the
electrons to be drained off from the surface and prevent charging up on the surface. The
detection of Ca, C and O is consistent with the composition of cultured pearls, which is
calcium carbonate, CaCO3.
A similar EDXRF spectrum as in Figure 12 was recorded for dyed cultured pearls.
Elements other than Ca, C and O and Au were not identified. This indicated that the
elements used for dyeing were not easily detected by EDXRF. Therefore, EDXRF cannot
differentiate naturally coloured cultured pearls from the dyed cultured pearls. This is
proven so by Liping 2001 in her research in differentiating naturally coloured cultured
pearls from the dyed cultured pearls. Likewise, the shellfish bead used in cultured pearls
also had similar EDXRF spectrum as in Figure 13, which indicated that the shellfish bead
has similar elements as in the cultured pearls.
On the other hand, the EDXRF spectrum of pearl imitations as shown in Figure 14
showed the presence of C and O only. Such detections, signifies the polymeric content of
the pearl imitation. For the bead used in pearl imitations, oxygen O, silicon Si, aluminium
Al and sodium Na were detected, as seen in Figure 14. This proves that the bead used for
pearl imitations has glass composite of SiO2 and metals, i.e. Al and Na as mentioned in
Landman, 2001.
The elemental analysis of the samples using EDXRF provides useful information of the
chemical composition on the surface of the sample. These data can be effectively used to
identify cultured pearls from their imitations. Such non-destructive analysis like EDXRF
is beneficial for pearls set in close-set jewellery.

4. Conclusion
The present investigations of the cultured pearls, imitation pearls and the respective beads
using EDXRF method showed that this method provides accurate identification by the
detection of the various elements in the samples. Since shells of mollusks are mainly
made of calcium carbonate, the main elements present are carbon, oxygen and calcium
for the cultured pearls. However, carbon and oxygen are more prominent in the imitation
pearls, which indicate that imitation pearls were made of polymers. Also, the bead used
in cultured pearls is made of calcium carbonate while the bead in the imitation pearls is a
glass composite material.
From the results obtained using accurate techniques like FTIR, SEM and EDXRF,
identifications of cultured and imitation pearls were proven to be constructive in this
research.