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Universit degli Studi di Parma (Italy)

RAMAN SPECTROSCOPY IN CORALS AND PEARLS


L. Bergamontia, D. Bersania, D. Csermely b, P. P. Lotticia
a bDipartimento di

Dipartimento di Fisica, Universit degli Studi, Viale G.P. Usberti 7/a, 43100 Parma (Italy), +39 0521906212, lottici@fis.unipr.it Biologia Evolutiva e Funzionale, Sezione Museo di Storia Naturale, Universit di Parma, via Farini, 90, 43121 Parma, Italy

Corals and pearls consist mainly of calcium carbonate in calcite, aragonite or vaterite forms. The nature of the pigments responsible for the different colors and even the structure of carbonate matrix in coral and pearls is still debated: to get more information, Raman spectroscopy in resonance conditions has been applied to different colored and white corals and pearls, from private collections and from the Natural History Museum of the University of Parma.

The Stylaster sp. coral (class Hydrozoa) has aragonite based skeleton (703-707 cm-1 characteristic Raman double peak). The pigment 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 (class Anthozoa). Overtones and combination modes are observed up to > 5000 cm-1.

1 2

Resonance Raman spectra of red and pink Corallium rubrum

Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. The four main modes i are indicated Overtones and combination modes are evident.

Pigments are carotenoids (methylated polyenes as cantahaxanthin) OR unmethylated polyenes ?? Freshwater cultured pink pearls, show the characteristic polyenic 1130-1530 cm-1 bands, large and asymmetric. No trace of dyes are found in freshwater white cultured pearls, while the resonance Raman spectrum of saltwater white pearls evidences the polyenic pigment. A dyed black pearl shows the characteristic features of (amorphous) carbon at about 1350 and 1600 cm-1.
Raman spectra of white, pink, black freshwater pearls and white seawater pearls (aragonite). Arrows indicate the main bands of the polyenic pigment.

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 1133 and 1531 cm-1 correspond to C-C and C=C stretching motion in polyenic (unmethylated ?) structures.
v1 v2 v3 v4 Exp Obs Exp Obs Exp
Pearl

Obs
Pearl

Stylaster sp. Stylaster sp. Corallium r. Corallium r.

The aragonite/calcite nature of the skeleton in some corals is still debated. The Raman spectra of different white museum corals unambiguously characterize the skeleton nature and exclude the presence of natural pigments of polyenic nature. . Lazurite and celestine in Pocillopora !?

0 0 0 1 0 0 0 0 0 1 1 1 2 0 0 0 0 1 1 1 1 1 2 0 2 0 2 0

0 1 0 0 0 1 2 0 1 0 1 0 0 0 1 2 3 0 1 2 0 1 0 0 1 2 0 3

1 0 0 0 2 1 0 1 0 1 0 0 0 3 2 1 0 2 1 0 1 0 1 4 0 2 0 1

0 0 1 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 0 1 1 0 0 0 0 1 0

1014 1159 1279 1516 2028 2173 2318 2293 2438 2530 2675 2795 3032 3042 3187 3332 3477 3544 3689 3834 3809 3954 4046 4056 4191 4346 4311 4491

1014 1159 1279 1516 2018 2168 2312 2433 2521 2665 2790 3022 3044 3159 3318 3461 3525 3674 3837 3809 3945 4030 4179 4342 4306 4482

1017 1133 1296 1531 2034 2150 2266 2313 2429 2548 2664 2827 3062 3051 3167 3283 3399 3565 3681 3797 3844 3960 4079 4068 4195 4300 4358 4416

1017 1133 1296 1531 2028 2148 2263 2315 2428 2542 2650 2816 3040 3040 3142 3273 3381 3550 3659 3753 3930 4095 4048 4151

1020 1135 1297 1528 2040 2155 2270 2317 2432 2548 2663 2825 3056 3060 3175 3290 3405 3568 3683 3798 3845 3960 4076 4080 4191 4310 4353 4425

1020 1135 1297 1528 2140 2265 2305 2433 2539 2655 2822 3048 3142 3278 3393 3631 3767

Raman frequencies observed in aragonite corals (Stylaster Bamboo corals are generally sp.), calcitic corals (Corallium r.), freshwater cultured pink artificially colored as evidenced by pearls. The combinations and overtones of the four main i a comparison with natural Isididae. frequencies of the pigment are indicated by the integers in the first four columns. Resonance Raman spectra with the 473.1 nm excitation line are useful to assess the nature of the pigments involved in coral or pearl coloration and are important tests for calculations of the vibrational properties of the polyenic/carotenoid molecules and their interaction with the mineralized structure. The question on the relative importance of methylated or unmethylated polyenes in calcite or aragonite based organisms asks for careful chromatographic measurements. The resonance allows to reveal small quantities of pigments and to immediately distinguish artificially colored corals and pearls.

Universit degli Studi di Parma (Italy)

RAMAN SPECTROSCOPY IN CORALS AND PEARLS


L. Bergamontia, D. Bersania, D. Csermely b, P. P. Lotticia
a bDipartimento di

Dipartimento di Fisica, Universit degli Studi, Viale G.P. Usberti 7/a, 43100 Parma (Italy), +39 0521906212, lottici@fis.unipr.it Biologia Evolutiva e Funzionale, Sezione Museo di Storia Naturale, Universit di Parma, via Farini, 90, 43121 Parma, Italy

Corals and pearls consist mainly of calcium carbonate in calcite, aragonite or vaterite forms. The nature of the pigments responsible for the different colors and even the structure of carbonate matrix in coral and pearls is still debated: to get more information, Raman spectroscopy in resonance conditions has been applied to different colored and white corals and pearls, from private collections and from the Natural History Museum of the University of Parma.

1 2

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 1133 and 1531 cm-1 correspond to C-C and C=C stretching motion in polyenic (unmethylated ?). structures.

Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. The four main modes i are indicated Overtones and combination modes are evident.

Bamboo corals are generally artificially colored as evidenced by a comparison with natural Isididae. The Stylaster sp. coral (class Hydrozoa) has aragonite based skeleton (703-707 cm-1 characteristic Raman double peak). The pigment 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 (class Anthozoa). Overtones and combination modes are observed up to > 5000 cm-1.

v1 v2 v3 v4

Exp

Obs

Exp

Obs

Exp
Pearl

Obs
Pearl

Stylaster sp. Stylaster sp. Corallium r. Corallium r.

0 0 0 1 0 0 0 0 0 1 1 1 2 0 0 0 0 1 1 1 1 1 2 0 2 0 2 0

0 1 0 0 0 1 2 0 1 0 1 0 0 0 1 2 3 0 1 2 0 1 0 0 1 2 0 3

1 0 0 0 2 1 0 1 0 1 0 0 0 3 2 1 0 2 1 0 1 0 1 4 0 2 0 1

0 0 1 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 0 1 1 0 0 0 0 1 0

1014 1159 1279 1516 2028 2173 2318 2293 2438 2530 2675 2795 3032 3042 3187 3332 3477 3544 3689 3834 3809 3954 4046 4056 4191 4346 4311 4491

1014 1159 1279 1516 2018 2168 2312 2433 2521 2665 2790 3022 3044 3159 3318 3461 3525 3674 3837 3809 3945 4030 4179 4342 4306 4482

1017 1133 1296 1531 2034 2150 2266 2313 2429 2548 2664 2827 3062 3051 3167 3283 3399 3565 3681 3797 3844 3960 4079 4068 4195 4300 4358 4416

1017 1133 1296 1531 2028 2148 2263 2315 2428 2542 2650 2816 3040 3040 3142 3273 3381 3550 3659 3753 3930 4095 4048 4151

1020 1135 1297 1528 2040 2155 2270 2317 2432 2548 2663 2825 3056 3060 3175 3290 3405 3568 3683 3798 3845 3960 4076 4080 4191 4310 4353 4425

1020 1135 1297 1528 2140 2265 2305 2433 2539 2655 2822 3048 3142 3278 3393 3631 3767
Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. Overtone and combination modes are evident

Raman frequencies observed in aragonite corals (Stylaster sp.), calcitic corals (Corallium r.), freshwater cultured pink pearls. The combinations and overtones of the four main i frequencies of the pigment are indicated by the integers in the first four columns.

Pigments are carotenoids (methylated polyenes as cantahaxanthin) OR unmethylated polyenes ??

Raman spectra of white, pink, black freshwater pearls and white seawater pearls (aragonite). Arrows indicate the main bands of the polyenic pigment.

Lazurite and celestine in Pocillopora .

!?
The aragonite/calcite nature of the skeleton in some corals is still debated. The Raman spectra of different white museum corals unambiguously characterize the skeleton nature and exclude the presence of natural pigments of polyenic nature.

Freshwater cultured pink pearls, show the characteristic polyenic 1130-1530 cm-1 bands, large and asymmetric. No trace of dyes are found in freshwater white cultured pearls, while the resonance Raman spectrum of saltwater white pearls evidences the polyenic pigment. A dyed black pearl shows the characteristic features of (amorphous) carbon at about 1350 and 1600 cm-1.

Resonance Raman spectra with the 473.1 nm excitation line are useful to assess the nature of the pigments involved in coral or pearl coloration and are important tests for calculations of the vibrational properties of the polyenic/carotenoid molecules and their interaction with the mineralized structure. The question on the relative importance of methylated or unmethylated polyenes in calcite or aragonite based organisms asks for careful chromatographic measurements. The resonance allows to reveal small quantities of pigments and to immediately distinguish artificially colored corals and pearls.

Universit degli Studi di Parma (Italy)

RAMAN SPECTROSCOPY IN CORALS AND PEARLS


L. Bergamontia, D. Bersania, D. Csermely b, P. P. Lotticia
a bDipartimento di

Dipartimento di Fisica, Universit degli Studi, Viale G.P. Usberti 7/a, 43100 Parma (Italy), +39 0521906212, lottici@fis.unipr.it Biologia Evolutiva e Funzionale, Sezione Museo di Storia Naturale, Universit di Parma, via Farini, 90, 43121 Parma, Italy

Corals and pearls consist mainly of calcium carbonate in calcite, aragonite or vaterite forms. The nature of the pigments responsible for the different colors and even the structure of carbonate matrix in coral and pearls is still debated: to get more information, Raman spectroscopy in resonance conditions has been applied to different colored and white corals and pearls, from private collections and from the Natural History Museum of the University of Parma.

The Stylaster sp. coral (class Hydrozoa) has aragonite based skeleton (703-707 cm-1 characteristic Raman double peak). The pigment 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 (class Anthozoa). Overtones and combination modes are observed up to > 5000 cm-1.

1 2

Resonance Raman spectra of red and pink Corallium rubrum

Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. The four main modes i are indicated Overtones and combination modes are evident.

Pigments are carotenoids (methylated polyenes as cantahaxanthin) OR unmethylated polyenes ?? Freshwater cultured pink pearls, show the characteristic polyenic 1130-1530 cm-1 bands, large and asymmetric. No trace of dyes are found in freshwater white cultured pearls, while the resonance Raman spectrum of saltwater white pearls evidences the polyenic pigment. A dyed black pearl shows the characteristic features of (amorphous) carbon at about 1350 and 1600 cm-1.
Raman spectra of white, pink, black freshwater pearls and white seawater pearls (aragonite). Arrows indicate the main bands of the polyenic pigment.

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 1133 and 1531 cm-1 correspond to C-C and C=C stretching motion in polyenic (unmethylated ?) structures.
v1 v2 v3 v4 Exp Obs Exp Obs Exp
Pearl

Obs
Pearl

Stylaster sp. Stylaster sp. Corallium r. Corallium r.

The aragonite/calcite nature of the skeleton in some corals is still debated. The Raman spectra of different white museum corals unambiguously characterize the skeleton nature and exclude the presence of natural pigments of polyenic nature. . Lazurite and celestine in Pocillopora !?

0 0 0 1 0 0 0 0 0 1 1 1 2 0 0 0 0 1 1 1 1 1 2 0 2 0 2 0

0 1 0 0 0 1 2 0 1 0 1 0 0 0 1 2 3 0 1 2 0 1 0 0 1 2 0 3

1 0 0 0 2 1 0 1 0 1 0 0 0 3 2 1 0 2 1 0 1 0 1 4 0 2 0 1

0 0 1 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 0 1 1 0 0 0 0 1 0

1014 1159 1279 1516 2028 2173 2318 2293 2438 2530 2675 2795 3032 3042 3187 3332 3477 3544 3689 3834 3809 3954 4046 4056 4191 4346 4311 4491

1014 1159 1279 1516 2018 2168 2312 2433 2521 2665 2790 3022 3044 3159 3318 3461 3525 3674 3837 3809 3945 4030 4179 4342 4306 4482

1017 1133 1296 1531 2034 2150 2266 2313 2429 2548 2664 2827 3062 3051 3167 3283 3399 3565 3681 3797 3844 3960 4079 4068 4195 4300 4358 4416

1017 1133 1296 1531 2028 2148 2263 2315 2428 2542 2650 2816 3040 3040 3142 3273 3381 3550 3659 3753 3930 4095 4048 4151

1020 1135 1297 1528 2040 2155 2270 2317 2432 2548 2663 2825 3056 3060 3175 3290 3405 3568 3683 3798 3845 3960 4076 4080 4191 4310 4353 4425

1020 1135 1297 1528 2140 2265 2305 2433 2539 2655 2822 3048 3142 3278 3393 3631 3767

Raman frequencies observed in aragonite corals (Stylaster Bamboo corals are generally sp.), calcitic corals (Corallium r.), freshwater cultured pink artificially colored as evidenced by pearls. The combinations and overtones of the four main i a comparison with natural Isididae. frequencies of the pigment are indicated by the integers in the first four columns. Resonance Raman spectra with the 473.1 nm excitation line are useful to assess the nature of the pigments involved in coral or pearl coloration and are important tests for calculations of the vibrational properties of the polyenic/carotenoid molecules and their interaction with the mineralized structure. The question on the relative importance of methylated or unmethylated polyenes in calcite or aragonite based organisms asks for careful chromatographic measurements. The resonance allows to reveal small quantities of pigments and to immediately distinguish artificially colored corals and pearls.

Universit degli Studi di Parma (Italy)

RAMAN SPECTROSCOPY IN CORALS AND PEARLS


L. Bergamontia, D. Bersania, D. Csermely b, P. P. Lotticia
a bDipartimento di

Dipartimento di Fisica, Universit degli Studi, Viale G.P. Usberti 7/a, 43100 Parma (Italy), +39 0521906212, lottici@fis.unipr.it Biologia Evolutiva e Funzionale, Sezione Museo di Storia Naturale, Universit di Parma, via Farini, 90, 43121 Parma, Italy

Corals and pearls consist mainly of calcium carbonate in calcite, aragonite or vaterite forms. The nature of the pigments responsible for the different colors and even the structure of carbonate matrix in coral and pearls is still debated: to get more information, Raman spectroscopy in resonance conditions has been applied to different colored and white corals and pearls, from private collections and from the Natural History Museum of the University of Parma.

1 2

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 1133 and 1531 cm-1 correspond to C-C and C=C stretching motion in polyenic (unmethylated ?). structures.

Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. The four main modes i are indicated Overtones and combination modes are evident.

Bamboo corals are generally artificially colored as evidenced by a comparison with natural Isididae. The Stylaster sp. coral (class Hydrozoa) has aragonite based skeleton (703-707 cm-1 characteristic Raman double peak). The pigment 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 (class Anthozoa). Overtones and combination modes are observed up to > 5000 cm-1.

v1 v2 v3 v4

Exp

Obs

Exp

Obs

Exp
Pearl

Obs
Pearl

Stylaster sp. Stylaster sp. Corallium r. Corallium r.

0 0 0 1 0 0 0 0 0 1 1 1 2 0 0 0 0 1 1 1 1 1 2 0 2 0 2 0

0 1 0 0 0 1 2 0 1 0 1 0 0 0 1 2 3 0 1 2 0 1 0 0 1 2 0 3

1 0 0 0 2 1 0 1 0 1 0 0 0 3 2 1 0 2 1 0 1 0 1 4 0 2 0 1

0 0 1 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 0 1 1 0 0 0 0 1 0

1014 1159 1279 1516 2028 2173 2318 2293 2438 2530 2675 2795 3032 3042 3187 3332 3477 3544 3689 3834 3809 3954 4046 4056 4191 4346 4311 4491

1014 1159 1279 1516 2018 2168 2312 2433 2521 2665 2790 3022 3044 3159 3318 3461 3525 3674 3837 3809 3945 4030 4179 4342 4306 4482

1017 1133 1296 1531 2034 2150 2266 2313 2429 2548 2664 2827 3062 3051 3167 3283 3399 3565 3681 3797 3844 3960 4079 4068 4195 4300 4358 4416

1017 1133 1296 1531 2028 2148 2263 2315 2428 2542 2650 2816 3040 3040 3142 3273 3381 3550 3659 3753 3930 4095 4048 4151

1020 1135 1297 1528 2040 2155 2270 2317 2432 2548 2663 2825 3056 3060 3175 3290 3405 3568 3683 3798 3845 3960 4076 4080 4191 4310 4353 4425

1020 1135 1297 1528 2140 2265 2305 2433 2539 2655 2822 3048 3142 3278 3393 3631 3767
Raman spectra of Stylaster sp. (aragonite) up to > 5000 cm-1 and Corallium r. Overtone and combination modes are evident

Raman frequencies observed in aragonite corals (Stylaster sp.), calcitic corals (Corallium r.), freshwater cultured pink pearls. The combinations and overtones of the four main i frequencies of the pigment are indicated by the integers in the first four columns.

Pigments are carotenoids (methylated polyenes as cantahaxanthin) OR unmethylated polyenes ??

Raman spectra of white, pink, black freshwater pearls and white seawater pearls (aragonite). Arrows indicate the main bands of the polyenic pigment.

Lazurite and celestine in Pocillopora .

!?
The aragonite/calcite nature of the skeleton in some corals is still debated. The Raman spectra of different white museum corals unambiguously characterize the skeleton nature and exclude the presence of natural pigments of polyenic nature.

Freshwater cultured pink pearls, show the characteristic polyenic 1130-1530 cm-1 bands, large and asymmetric. No trace of dyes are found in freshwater white cultured pearls, while the resonance Raman spectrum of saltwater white pearls evidences the polyenic pigment. A dyed black pearl shows the characteristic features of (amorphous) carbon at about 1350 and 1600 cm-1.

Resonance Raman spectra with the 473.1 nm excitation line are useful to assess the nature of the pigments involved in coral or pearl coloration and are important tests for calculations of the vibrational properties of the polyenic/carotenoid molecules and their interaction with the mineralized structure. The question on the relative importance of methylated or unmethylated polyenes in calcite or aragonite based organisms asks for careful chromatographic measurements. The resonance allows to reveal small quantities of pigments and to immediately distinguish artificially colored corals and pearls.

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