SCIENCE CHINA

Physics, Mechanics & Astronomy

• Letter • August 2013 Vol.56 No.8: 1598–1602
doi: 10.1007/s11433-013-5144-z

Natural amber, copal resin and colophony investigated by UV-VIS,

infrared and Raman spectrum
RAO ZhiFan1*, DONG Kun1, YANG XiaoYun1, LIN JinChang1, CUI XiaoYing1,
ZHOU RongFeng1 & DENG Qing2
1
Analysis and Testing Center of Yunnan, Kunming University of Science and Technology, Kunming 650093, China;
2
School of Engineering and Applied Science, Harvard University, Cambridge 02138, USA

Received September 9, 2012; accepted January 30, 2013; published online June 25, 2013

Natural amber, copal resin and colophony are have investigated by UV-VIS, infrared and Raman spectrum. In order to distin-
guish the natural amber, copal resin and colophony, we have successfully used the nondestructive examination (NDE) tech-
nology. The results show that UV-VIS could not distinguish these compositions. The infrared spectra can distinguish them, but
the technology may destroy the specimen. The Raman spectra show three characteristic peaks of vibration near position 932
cm–1 and position 1179 cm–1 of copal resin, which confirm the existence of terpenes compounds in it. In the Raman spectra of
colophony, the vibration characteristic peak at position 1589 cm–1, caused by the conjugate double bond of internal unsaturated
resin acid, is the basis of the characteristic difference between colophony and natural amber. The advantages of the distin-
guished technology by Raman spectroscopy are convenient and nondestructive examination for natural amber, copal resin and
colophony.

gemology, nondestructive examination, spectrum, rosin

PACS number(s): 36.20.-r, 36.20.Ng, 33.20.Ni

Citation: Rao Z F, Dong K, Yang X Y, et al. Natural amber, copal resin and colophony investigated by UV-VIS, infrared and Raman spectrum. Sci Chi-
na-Phys Mech Astron, 2013, 56: 15981602, doi: 10.1007/s11433-013-5144-z

Natural amber is fossilized tree colophony, which has been matures over the years, more polymerization takes place as
appreciated for its color and natural beauty since Neolithic well as isomerization reactions, crosslinking and cyclization
times. Amber (general formula C10H16O) is used as an in- [3,5,6]. Copal resin is a general term used for the descrip-
gredient in perfumes, as a healing agent in folk medicine, tion of some terpenoid resins [7–9]. Copal resin is some-
and as jewelry [1]. Natural amber is heterogeneous in com- times quoted as immature amber, as amber is a fossilised
position, but consists of several resinous bodies more or less resin [4,10–13]. The resin produced by most plants is a vis-
soluble in alcohol, ether and chloroform, associated with an cous liquid, composed mainly of volatile fluid terpenes,
insoluble bituminous substance [2–4]. Natural amber is a with lesser components of dissolved non-volatile solids
macromolecule by free radical polymerization of several which make resin thick and sticky. The most common ter-
precursors in the labdane family, e.g. communic acid, penes in resin are the bicyclic terpenes alpha-pinene, beta-
cummunol, and biformene. These labdanes are diterpenes pinene, delta-3 carene and sabinene, the monocyclic ter-
(C20H32) and trienes, equipping the organic skeleton with penes limonene and terpinolene, and smaller amounts of the
three alkene groups for polymerization. As natural amber tricyclic sesquiterpenes, longifolene, caryophyllene and
delta-cadinene. Colophonys consist of a complex mixture of
*Corresponding author (email: [email protected]) waterinsoluble, organic compounds, which are mostly of

© Science China Press and Springer-Verlag Berlin Heidelberg 2013 phys.scichina.com www.springerlink.com
 Rao Z F, et al. Sci China-Phys Mech Astron August (2013) Vol. 56 No. 8 1599

terpenoid origin [8,14,15]. photometer (GENERAL TU-1221, wavelength resolution 1

Hitherto has been used infrared spectroscopy [2] discov- nm, China). The infrared spectrums (IR) are characterized
ered that amber from the Baltic region the characteristic by the FT-infrared spectrometer (EQUINOX55 type, Ger-
feature of a broad should are in the wavenumber region many). The IR region is from 400 cm–1 to 4000 cm–1 and the
1250–1175 cm–1 on the band at 1150 cm–1 [4], 1250 cm–1 energy resolution is 0.5 cm–1. By using this method, the
and 1110 cm–1 [16]. Raman spectroscopy is a molecular species are destroyed in the test. Raman spectra were ac-
spectroscopic technique that during recent years often has quired using an spectrophotometer (Raman Systems RM-
been used for the non-destructive analysis of historical and 200 model, energy detection from 250 cm–1 to 2400 cm–1;
artistic materials [16–18]. Edwards et al. [18] addressed the energy resolution 4 cm–1, OpotoTrace, USA) which incor-
provision of preliminary spectroscopic assignments and porates a 785 nm pump laser (250 mW).
concentrated principally on the spectroscopic differentiation Table 1 shows the physical properties of natural amber,
between real and imitation ambers, e.g. plastics. The ratio of copal resin and colophony, such as color, and density and
the intensity of bands at 1646 and 1450 cm–1, I1646/I1450, refractive index. By observing from the appearance of these
Winkler et al. [9,10] confirmed that the intensity ratio was samples, they are pale yellow and translucent shape. The
for immature fossil resins (copal) and for mature fossil res- nuanced color is difficult to characterize expression, and
ins (ambers). Moreno et al. [19,20] report values for the therefore while use this method still difficult to distinguish
ratio in a range of amber samples predominantly from the each other. From the density point of view, they are very
Baltic region and suggest spectral differences exist between similar to each other. In addition, while the selected samples
ambers from different geographical locations [4]. However, may come from different regions, the difference of density
the distinguishing technology among the amber, copal resin is very obvious in different samples. Hence, the measure-
and colophony are still a difficult problem in modern analy- ment process can not be used as a precise distinction meth-
sis technology. In this paper, natural amber, copal resin and od. The refractive index is very similar among of them.
colophony have been investigated by UV-VIS, infrared and When measured by UV fluorometer, they are all appeared
Raman spectrum. By using the nondestructive examination the Blue-white color light, regardless of the short or long
technology of Raman spectra, we can well distinguish these wave meter. In a word, while used the UV fluorometer, we
gems. can not distinguish the natural amber, copal resin and co-
The natural amber, copal resin and colophony was se- lophony.
lected in market of Yunnan Mizhina. The density was Figure 1 shows the UV-Vis spectra of natural amber, co-
measured according to Archimedes principle, where the pal resin and colophony, respectively. It can be seen the
weight of a volume of distilled water equivalent to that of spectrum region of wave length from 200 nm to 900 nm,
the colophony sample was obtained to a precision of 0.0001 and no obvious UV absorbed peak are appeared in these
g. Color was detected by UV fluorometer. Linear refractive samples. The absorbance curve inflection point of the natu-
index measurements (0.001 precision) were carried out us- ral amber and copal resin are near in 450 nm wavelength,
ing a prism coupler (Metricon 2010 model). The linear re- but there is no obvious inflection point in the colophony.
fractive index of the samples was measured at wavelengths The results are not in agreement with some of the literatures
632.8 nm, 1305.4 nm and 1536 nm. UV-VIS transmittance [6,12,17]; hence, the method should be processed in the
spectra (200 nm to 900 nm) were acquired using a spectro- future.

Table 1 The physical property of natural amber, copal resin and colophony

UV fluorescence
Species Color Transparency Density Refractive index
Short wave Long wave
Natural amber Pale yellow Translucent 1.075 1.54 Pale blue-white Dark blue-white
Copal resin Pale yellow Translucent 1.050 1.54 Pale blue-white Dark blue-white
Cplophony Pale yellow Translucent 1.045 1.53 Pale blue-white Dark blue-white

Table 2 The vibrational peaks of infrared and Raman spectra of natural amber, copal resin and colophony, respectively

Spectra Species Position (cm–1)

Infrared colophony 827, 885, 1041, 1166, 1385, 1464, 1708, 2867, 2955, 3435
Infrared copal resin 637, 700, 887, 1039, 1176, 1268, 1386, 1446, 1647, 1700, 2864, 3079, 3436
Infrared natural amber 887, 1015, 1154, 1378, 1447, 1742, 2870, 2930, 3448
Raman colophony 1412, 1589, 1628
Raman copal resin 683, 732, 932, 964, 989, 1179, 1226, 1417, 1624
Raman natural amber 1417, 1630
1600 Rao Z F, et al. Sci China-Phys Mech Astron August (2013) Vol. 56 No. 8

wave number in copal resin, which is the stretching vibra-

tion of the exocyclic non-conjugated C==C bond. When
compared the peaks at 1154 wave number in amber and
1268 and 1176 wave number, we found the opposite vibra-
tional peak intensity contrast between them. The peak at
887 cm–1 in copal resin is much clearer than natural amber,
which is the terpenes cyclic skeleton surface of the bending
vibration. The main difference is the peaks at 700 cm–1 and
637 cm–1 in copal resin except natural amber, which is the
stretching vibration of the linear molecule of the C—C bond.
Due to the natural amber evolved by the copal resin, but
the copal resin structure have a lower degree of polymeriza-
tion while compared with amber. So the vibrational peaks of
copal resin are more obvious than amber’s. With the in-
creasing age and the gradually incremented maturity of co-
pal resin, it with the natural amber differences vibration
Figure 1 (Color online) The UV-VIS spectra of natural amber, copal and peak intensity will be relatively weakened, or even disap-
colophony. pear.
When compared with colophony, we found that the co-
Figure 2 shows the infrared spectra of natural amber, co- lophony’s vibrational peaks are at 3435, 2955, 2867, 1708,
pal resin and colophony, respectively. It can be seen the 1464, 1385, 1166, 1041, 885, and 827 cm–1. The main ob-
obvious vibrational peaks at 3448, 2930, 2870, 1742, 1447, vious differences of vibrational peaks between amber is at
1378, 1154, 1015, and 887 cm–1. Due to the formation rea- 1166, 1041, 885, and 827 cm–1, which can be distinguished
son between the copal resin and amber are similar, except the amber and colophony. In a word, the Infrared spectra is
the age and composition. So the spectrums of them are very a useful tool in distinguishing the natural amber, copal resin
similar and have only a little difference. Table 2 shows the and colophony. However, in the infrared spectra testing
positions of vibrational peaks of IR spectra. It can been seen process, the samples should be destroyed as powder, which
the vibrational peaks at 3436, 3079, 2928, 2864, 1700, 1647, is not suitable for nondestructive examination (NDE) tech-
1446, 1386, 1268, 1176, 1039, 887, 700, and 637 cm–1 in nology in the gems.
copal resin. While compared these spectrums of samples, Raman spectra have a demonstrable advantage over
we found the main differences of vibrational peaks at 3079, conventional, visible excitation methods chiefly because
1647, 1268, 1176, 887, 700, and 637 cm–1. The peak at 3079 problems associated with sample fluorescence are mini-
wave number is the hydrogen atom attached to the terminal mized [21–25]. Figure 3 shows the Raman spectra of natural
carbon atom on the rocking terpenes in copal resin except in amber, copal resin and colophony, respectively. Table 2
natural amber. Another obvious vibrational peak is at 1647 shows the positions of vibrational peaks of Raman spectra.

Figure 2 (Color online) The infrared spectra of natural amber, copal and Figure 3 (Color online) The Raman spectra of natural amber, copal and
colophony. colophony.
 Rao Z F, et al. Sci China-Phys Mech Astron August (2013) Vol. 56 No. 8 1601

It can be seen the obvious difference of vibrational peaks to istic difference between colophony and natural amber. In
each other samples. In the natural amber, the vibrational the natural amber, the vibrational peaks are located at 1417
peaks are located at 1417 cm–1 and 1630 cm–1, which is cm–1 and 1630 cm–1, which is represented the asymmetric
represented the asymmetric rocking vibration of H—C—H rocking vibration of H—C—H bond and the telescopic vi-
bond and the telescopic vibrations of C==O double bond in brations of C==O double bond in carboxyl groups, respec-
carboxyl groups, respectively. The obvious vibrational tively. The obvious vibrational peaks are at 683, 732, 932,
peaks are at 683, 732, 932, 964, 989, 1179, 1226, and 1266 964, 989, 1179, 1226, and 1266 cm–1 between the copal
cm–1 between the copal resin and amber. Because the lower resin and amber. The large difference among colophony
degree of polymerization in the copal resin than amber, the with the natural amber and copal resin is the vibrational
vibration peak at 683 and 732 wave numbers are the peak at 1589 cm–1.
stretching vibration of C—C bond in the carbon chain of
polymer. The vibrational peaks at 932, 964 and 989 cm–1
This work was supported by the National Natural Science Foundation of
are closely related with the breathing vibrational mode of China (Grant No. 51261011), and the Science and Technology Program of
the ring structures. The three vibrational peaks at 932, 964, Yunnan (Grant No. 2010DH025).
and 989 cm–1 are the in or out C-H plane of the rocking vi-
brational of the cyclic molecular structure. The above evi-
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