13 C Solid State Nuclear Magnetic Resonance and µ-Raman Spectroscopic Characterization of Sicilian Amber

Abstract

¹³C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) and µ-Raman spectroscopy were applied to characterize Sicilian amber samples. The main goal of this work was to supply a complete study of simetite, highlighting discriminating criteria useful to distinguish Sicilian amber from fossil resins from other regions and laying the foundations for building a spectroscopic database of Sicilian amber. With this aim, a private collection of unrefined simetite samples and fossil resins from the Baltic region and Dominican Republic was analyzed. Overall, the obtained spectra permitted simetite to be distinguished from the other resins. In addition, principal component analysis (PCA) was applied to the spectroscopic data, allowing the clustering of simetite samples with respect to the Baltic and Dominican samples and to group the simetite samples in two sets, depending on their maturity. Finally, the analysis of loadings allowed for a better understanding of the spectral features that mainly influenced the discriminating characteristics of the investigated ambers.

Keywords

Amber simetite fossil resins µ-Raman spectroscopy principal component analysis (PCA)

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References

Langenheim

J.H.

“Plant Resins: Chemistry, Evolution, Ecology, and Ethnobotany”, Portland, OR: Timber Press, 2003.

O. Helm, H. Conwentz. “Sull’ambra di Sicilia”. Malpighia. 1886. 1: 49–56.

Lambert

J.B.

Beck

C.W.

Frye

J.S.

“Analysis of European Amber by Carbon-13 Nuclear Magnetic Resonance Spectroscopy”. Archaeometry 1988; 30(2): 248–263.

Poinar

G.O.

Life in Amber, Stanford, CA: Stanford University Press, 1992.

Winkler

Ch. Kirchner

Asenbaum

Musso

“A Raman Spectroscopic Approach to the Maturation Process of Fossil Resins”. J. Raman Spectrosc 2001; 32(1): 59–63.

Brody

R.H.

Edwards

H.G.M.

Pollard

A.M.

“A Study of Amber and Copal Samples Using FT-Raman Spectroscopy”. Spectrochimica Acta Part A 2001; 57(6): 1325–1338.

Lambert

J.B.

Frye

J.S.

“Carbon Functionalities in Amber”. Science 1982; 217(4554): 55–57.

Lambert

J.B.

Frye

J.S.

Poinar

G.O.

Jr . “Amber from the Dominican Republic: Analysis by Nuclear Magnetic Resonance Spectroscopy”. Archaeometry 1985; 27(1): 43–51.

Lambert

J.B.

Shawl

C.E.

Stearns

J.A.

“Nuclear Magnetic Resonance in Archaeology”. Chem. Soc. Rev 2000; 29: 175–182.

10.

Lambert

J.B.

Santiago-Blay

J.A.

Anderson

K.B.

“Chemical Signatures of fossilized Resins and Recent Plant Exudates”. Angew. Chem 2008; 47(50): 9608–9616.

11.

Lambert

J.B.

Santiago-Blay

J.A.

Wuc

Levy

A.J.

“Examination of Amber and Related Materials by NMR Spectroscopy”. Magn. Reson. Chem 2014; 53(1): 2–8.

12.

Lambert

J.B.

Johnson

S.C.

Poinar

G.O.

Jr . “Nuclear Magnetic Resonance Characterization of Cretaceous Amber”. Archaeometry 1996; 38(2): 325–335.

13.

Abduriyim

Kimura

Sucher

S.D.

Dobrinets

I.A.

Mychaluk

K.A.

Jianjun

Bocchio

“Characterization of ‘Green Amber’ with Infrared and Nuclear Magnetic Resonance Spectroscopy”. Gems and Gemology 2009; 45(3): 158–157.

14.

Lambert

J.B.

Tsai

C.Y.H.

Shah

M.C.

Hurtley

A.E.

Santiago-Blay

J.A.

“Distinguishing Amber and Copal Classes by Proton Magnetic Resonance Spectroscopy”. Archaeometry 2012; 54(2): 332–348.

15.

Jehlicka

Jorge Villar

S.E.

Edwards

H.G.M.

“Fourier Transform Raman Spectra of Czech and Moravian Fossil Resins from Freshwater Sediments”. J. Raman Spectrosc 2004; 35(8-9): 761–767.

16.

Edwards

H.G.M.

Farwell

D.W.

“Fourier Transform-Raman Spectroscopy of Amber”. Spectrochimica Acta Part A 1996; 52(9): 1119–1125.

17.

Vandenabeele

Grimaldi

D.M.

Edwards

G.M.H.

Moens

“Raman Spectroscopy of Different Types of Mexican Copal Resins”. Spectrochimica Acta Part A 2003; 59(10): 2221–2229.

18.

Moreno

Y.M.

Christensen

D.H.

Faurskov

Nielsen

“NIR-FT-Raman Spectroscopic Study of Amber.”. Asian J. Spectrosc 2000; 4: 49–56.

19.

Edwards

H.G.M.

Farwell

D.W.

Villar

S.E.J.

“Raman Microspectroscopic Studies of Amber Resins with Insect Inclusions”. Spectrochimica Acta Part A 2007; 68(4): 1089–1095.

20.

Łydżba-Kopczyńska

B.I.

Gediga

Chojcan

Sachanbiński

“Provenance Investigations of Amber Jewelry Excavated in Lower Silesia (Poland) and Dated Back to Early Iron Age”. J. Raman Spectrosc 2012; 43(11): 1839–1844.

21.

Edwards

H.G.M.

Falk

M.J.

“Fourier Transform Raman Spectroscopic Study of Ancient Resins: A Feasibility Study of Application to Archaeological Artefacts”. J. Raman Spectrosc 1997; 28(4): 211–218.

22.

Edwards

H.G.M.

Farwell

D.W.

Quye

“‘Dragon’s Blood’ I: Characterization of an Ancient Resin Using Fourier Transform Raman Spectroscopy”. J. Raman Spectrosc 1997; 28(4): 243–249.

23.

Metz

Smith

S.O.

“Ramped-Amplitude Cross Polarization in Magic Angle Spinning NMR”. J. Magn. Reson 1994; 110(2): 219–227.

24.

Brereton

R.G.

Chemometrics: Data Analysis for the Laboratory and Chemical Plant, Chichester, UK: Wiley, 2003, pp. 449–456.

25.

Luke

Reisner

A.C.

Pandya

A.K.

“An Integrated Software System for Processing, Analyzing, and Classifying Raman Spectra”. Chemom. Intell. Lab. Syst 2011; 105(1): 83–90.

26.

Anderson

K.B.

Winans

R.E.

Botto

R.E.

“The Nature and Fate of Natural Resins in the Geosphere II. Identification, Classification, and Nomenclature of Resinite”. Org. Geochem 1992; 18(6): 829–841.

27.

Pereira

San Gil

R.A.S.

Carvalho

I.S.

Fernandes

A.C.S.

Azevedo

D.A.

“Solid State 13C NMR Analysis of Brazilian Cretaceous Ambers”. J. Braz. Chem. Soc 2011; 22(1): 92–97.

28.

Mannina

Sobolev

A.P.

Viel

“Liquid State 1H High Field NMR in Food Analysis”. Progr. Magn. Reson. Spectrosc 2012; 66: 1–39.

29.

Calabrò

Gralka

Luchinat

Saccenti

Tenori

“A Metabolomic Perspective on Coeliac Disease”. Autoimmune Dis. 2014 2014, pp. 756138.

30.

Lambert

J.B.

Heckenbach

E.A.

Santiago-Blay

G.A.

“Characterization of Plant Exudates by Principal-Component and Cluster Analysis with Nuclear Magnetic Resonance Variables”. J. Nat. Prod 2010; 73(10): 1643–1648.