Universit degli Studi di Parma (Italy)

Corals, pearls and shells in museum collections:

micro-Raman spectroscopy for their authentication
L. Bergamonti1,2, P.P. Lottici3
1 Industrial Engineering Department, University of Parma, Parco Area delle Scienze 181/a, 43124 Parma, Italy laura.bergamonti@unipr.it
2 Chemistry Department, University of Parma, Parco Area delle Scienze 17/a, 43124 Parma, Italy
3 Physics and Earth Sciences Department, University of Parma, Parco Area delle Scienze 7/A, 43124 Parma (Italy)

Corals, shells and pearls are used since Neolithic as jewelry and ornaments and are by themselves objects exposed in museum collections. The nature of the pigments
responsible for the different colors and even a deep understanding of the intricate biomineralization processes in marine and terrestrial biogenic carbonates found in corals,
shells or pearls are still debated and are of interest for a better conservation in museum collections. Raman microscopy in resonance conditions is a powerful technique to
investigate both the spatial distribution of the inorganic phases (calcite, aragonite or vaterite) and to define the nature of the organic pigments. Mixtures of methylated
(carotenoids) or non-methylated polyenes with different UV-VIS absorption spectra and chain lengths are responsible for the color and its changes in mineralized organisms.
Carotenoid pigments are found in Stylaster sp. corals whereas mixtures of unmethylated or partially methylated polyenes are found in Corallium rubrum and terrestrial
(Liguus virgineus ) and marine shells (Bractechlamys vexillum).
The resonance spectra in red Corallium rubrum (calcite skeleton) show the
pigment features (overtones and combination) up to >5000 cm-1. The peaks 1
and 2 at 1131 and 1522 cm-1 correspond to C-C and C=C stretching
motion in polyenic (partially demethylated or unmethylated) structures.

The Stylaster sp. coral has aragonite based skeleton (702-706 cm-1
characteristic Raman double peak). The pigments belongs to carotenoid
family: the C-C and C=C stretching modes at 1159 cm-1 and at 1516 cm-1 are
shifted with respect to the corresponding features in (calcite based) Corallium
rubrum. In resonance (473.1 nm) overtones and combination modes are
observed up to > 5000 cm-1.

Raman spectra of white, pink, black freshwater

pearls and white seawater pearls (aragonite). Arrows
indicate the polyenic pigment main bands

Raman spectra of different color lines in juvenile (b)

and adult (a) Liguus shell: the 1 peak shifts to lower
wavenumbers for darker colours and shows large
asymmetry. i are the fundamental frequencies and A
indicates the aragonite features.

1550
1540

Raman spectra of yellow pigments outside and

inside the Liguus shell.

Raman spectra of a shell cameo: the authenticity is guaranteed by the

presence of polyenic dyes in the white carved figure.

Liguus
SHELLS+CORA
LS

v1 frequency (cm-1)

1530

v1 = 1.3454*v2
R = 0.91

1520
1510
1500
1490
1110

1120

1130

v2 frequency

1140

(cm-1)

1150

1160

a) Raman spectra from a

map on the black hinge
(taken out resonance at
632.8 nm).
b) Spectra from a map on a
yellow-orange outer zone
(at 632.8 nm).

Raman spectra on more than one hundred corals (calcitic) and marine shells with non-carotenoid (i.e. polyenic) pigments
suggest a linear relationship between 1 and 2 and a simple approximate rule for their dependence on N:
1 = 254*103/(N+157); 2 = 189*103/(N+157)
Contributions from N=7 to N=14 may be found by peak decomposition in marine shells according to different colours.
Selective resonance may apparently blue-shift the pigment peaks. The effect is less pronounced in Corallium r. coral and in
Stylaster sp. coral where the pigments seem due to single (or a few) molecular species [2].
The Liguus virgineus (terrestrial shell) shows contributions from shorter polyenic chains with respect to Bractechlamys vexillum
(in 1 vs. 2 graph the asterisk indicates the light yellow color of Liguus).

The calcite-aragonite distribution in Bractechlamys vexillum (Reeve,1853) shells

has been determined by Raman maps in the interior of the valve: calcite is
found in the body region, just below the umbo, up to the adductor muscle
scar. Below this area, above and in the adductor muscle scar, up to about half
the valve midline height, only aragonite is detected. At the bottom of the
midline of valve, calcite and aragonite phases are found together. In the
dorsal of shell aragonite is found only close to the umbo, whereas in the rest
only calcite is found.

Distribution of calcite and

aragonite phases in the
interior of the valve.

Raman spectra taken with 473.1 nm and 632.8 nm excitation lines in marine and terrestrial shells and corals are useful to assess the nature of the pigments involved in their coloration and are
important tests for calculations of the vibrational properties of the polyenic/carotenoid molecules and their interaction with the mineralized structure. In the shells investigated the Raman results
suggest a mixture of polyenic pigments with different chain lengths. Apparent blue shift of the main Raman features at 473.1 nm excitation may be due to a selective resonance mechanism. The
effect is observed also in stylaster corals, where the pigment has a definite carotenoid nature. The mapping capability of the micro-Raman allows an easy identification of the carbonate phases.
1) L. Bergamonti, D. Bersani, D. Csermely, P.P. Lottici, The nature of the pigments in corals and pearls: a contribution from Raman spectroscopy, Spectroscopy Letters 44, 453-458 (2011)
2) L. Bergamonti, D. Bersani, S. Mantovan, P.P. Lottici, Micro-Raman investigation of pigments and carbonate phases in corals and molluscan shells, European Journal of Mineralogy 25, 845-853 (2013)