Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 115 (2013) 324329

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

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Spectroscopic studies of wood fossils from the Crato Formation, Cretaceous Period
J.H. da Silva a, P.T.C. Freire b,, B.T.O. Abagaro b, J.A.F. Silva b, G.D. Saraiva c, F.J. de Lima d O.A. Barros d, R.A. Bantim d, A.A.F. Saraiva d, B.C. Viana e
a

Campus Cariri, Universidade Federal do Cear, 63000-000 Juazeiro do Norte, CE, Brazil Departamento de Fsica, Universidade Federal do Cear, 60455-970 Fortaleza, CE, Brazil Faculdade de Educao Cincias e Letras do Serto Central, Universidade Estadual do Cear, CEP 63.900-000 Quixad, CE, Brazil d Laboratrio de Paleontologia da Universidade Regional do Cariri, Rua Cel. Antnio Luiz, 1161, 63105-000 Crato, CE, Brazil e Departamento de Fsica, Universidade Federal do Piau, 64049-550 Teresina, PI, Brazil
b c

h i g h l i g h t s
 A detailed Raman and infrared

g r a p h i c a l a b s t r a c t

spectra of wood fossils were reported.

 EDX and X-ray diffraction indicated

the main constituents.

 The environment of Crato Formation,

from Cretaceous Period, was elucidated.

a r t i c l e

i n f o

a b s t r a c t
In this work we study two types of wood fossils (Gymnosperms, Araucariaceae) from the Crato Formation of Araripe Basin in Brazil, from the Cretaceous Period. The samples were characterized by Raman and infrared spectroscopies, X-ray diffraction and scanning electron microscopy. The results obtained by different techniques showed that although the rocks surrounding the fossils have predominantly the same constitution calcite however, the formation processes of these types of wood fossils are quite different. One of the fossils, denominated as light wood, is predominantly composed of gypsum, while the other fossil, the dark wood, is rich in amorphous carbon, possibly the kerogen type. Implications relative to the environment where the plants lived millions years ago are also given. Finally, the results highlight the constitution of one of the most important paleontological sites of the Cretaceous Period in the South America. 2013 Elsevier B.V. All rights reserved.

Article history: Received 21 February 2013 Received in revised form 6 June 2013 Accepted 12 June 2013 Available online 28 June 2013 Keywords: Raman spectroscopy Infrared spectroscopy X-ray diffraction Wood fossils Cretaceous Period

Introduction The physical and chemical processes that produce fossils are very complex. Their understanding involves several kinds of studies, related to chemistry and physics of the materials, beyond
Corresponding author.
E-mail address: tarso@sica.ufc.br (P.T.C. Freire). 1386-1425/$ - see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.saa.2013.06.042

aspects related to the biology, geology and paleontology themselves. These studies contribute to through light on the environment of millions years (Myr) ago, when the process culminated in the formation of the fossil occurred [13]. In the last years, some works have presented the application of spectroscopy in the fossil studies [47], in particular through Raman spectroscopy [3,6,8,9], giving important insights to questions related with several aspects of paleontology.

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In the Northeast of Brazil there is an important paleontological site characterized by the occurrence of diverse types of Cretaceous fossils with exceptional conservation, the Araripe Basin. It lies between the meridians 38300 and 40500 W longitude of the Greenwich along with the parallels 7050 , as well as the 7500 S latitude. This Cretaceous sequence was deposited nearly over 50 million years, where today there are laminated limestones, gypsum banks, shales and ne sandstones. The Cretaceous was a period characterized by hot weather with a broad latitudinal temperature gradient and moderately hot poles [10]. The forests growing mainly at high latitudes within the polar circles were well adapted to the combination of two factors that were not experienced by any previously existing vegetation: the polar light regime, characterized by bright summers and dark winters, and the high concentrations of carbon dioxide in the atmosphere [11]. The intense tectonic activity and volcanism that was veried in southern Gondwana during this period resulted in the breakdown of the supercontinent [12]. Related to the plant fossils from the Crato Formation, the following have been identied: roots, stems, sterile and fertile fronds, leaves, owers, fruits and seeds of different groups. The preservation involving several mechanisms such as calcication, limonitization, goethization and sometimes carbonization is considered excellent [13]. Substitution is the most common fossilization process occurring in the fossils of Crato Formation; for instance, the calcium carbonate constituting the shells is replaced by silica, pyrite or limonite, even for a new calcium carbonate. In such cases, the fossils are replicas of primitive shells and plants. In some situations, details of the structure in the tissues can be preserved and according to Ref. [14], the vegetable trunks that have undergone this kind of replacement can be found in the remains of carbonated tissues. The carbonization process occurs when the gradual loss of volatile elements in the organic matter takes place. Therefore, most of the oxygen, hydrogen and nitrogen are released, leaving a carbon lm. This type of fossilization is frequently observed in structures made of lignin, cellulose, chitin and keratin. Despite the changes in the original chemical composition, the microstructure is often preserved, allowing the study of anatomy in plant fossils. Additionally, in some situations, it is also possible the preservation of part of the oxygen, suggesting a degradation of the sample occurring through an oxidation process. The fossil wood, commonly found in the Crato Formation outcrops, belonged to the gymnosperms since this botanical group is abundant in these settled sediments during the Cretaceous [1], as also happened in the global scenario [15]. In the present work, fossils and matrices were chosen based on special criteria, i.e., the stratigraphic location level and the type of coloring. In this study, samples of dark wood and light wood, as well as their rock matrixes (rock surrounding the fossil, i.e., mother stones), were characterized by Raman and infrared spectroscopies, X-ray diffraction and scanning electron microscopy.

Fig. 1. Optical image of the light wood fossil. In order to help the understanding about what parts represent the fossil itself and what part belong to the matrix we have specied these informations in the gure.

and what parts belong to the matrix (The optical image of the dark wood fossil analyzed is presented in Supplementary Materials). These samples were properly fragmented and stored in containers with enough material for spectroscopic measurements. Characterization We have used ve different experimental techniques in order to investigate the fossils. The description of the equipments is as follows: Raman spectroscopy (RS) The Raman spectra were carried through a WiTeC Alpha500 Raman system. The excitation source was the 532 nm line of a laser with power 0.5 mW on the sample. An objective with magnication of 100 and a numerical aperture (NA) of 0.95 was used in order to obtain the Raman spectra. For the Raman image, the sample was placed on an xy stage and scanned under the illumination of the laser. The Raman spectra from every spot of the sample were recorded. The stage movement and data acquisition were controlled using ScanCtrl Spectroscopy Plus software from WiTeC, Germany. Data analysis was done by using WITec Project software. In general terms we had no great problem with luminescence. Infrared spectroscopy (IR) The infrared spectra were measured using KBr pellets, where the samples were mixed with KBr powder in the proportion 1:100 from each sample (at about 510 mg). The pellet thickness varied from 0.5 to 0.6 mm. The IR spectra were measured in the spectral range from 400 to 4000 cm1 with a Vertex 70 from Bruker. X-ray diffraction (XRD) The X-ray diffraction patterns were obtained using a Rigaku powder diffractometer with a BraggBrentano geometry. The Co Ka radiation was used and operated at 40 kV and 25 mA. The XRD measurements were taken in the 2h range of 345th, using step scan procedures (0.02) is counting times of 5 s. To perform the XRD measurements we have used 1 g of powder samples and for data treatment we have used the Xpert High score software with PDFs included. Scanning electron microscopy (SEM) The morphology of fossil samples, were examined through scanning electron microscopy (SEM) and the images were made in the Vega XMU microscope of the TESCAN Instruments.

Experimental Samples The fossil materials were collected in a mine area for exploration of laminated limestone in the municipality of Santana do Cariri, State of Cear, in Brazil. The duly analyzed material consisted in two kinds of wood fossils (Gymnosperms, Araucariaceae), denominated as dark and light wood, as well as, the two matrices (stones where the fossils were collected) with thickness around 2 3 cm. Fig. 1 presents optical image of the light wood fossil, where arrows show explicitly what parts of the material is the fossil itself

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Results XRD results Fig. 2 shows the X-ray diffractogram of the matrixes where the two fossils were obtained. They are very similar and according to the diffractogram in Fig. 2, the matrix of light wood is constituted basically from calcite, one polymorph of calcium carbonate (CaCO3). This compound exhibits a rhombohedral crystal structure of the type R-3c. On the other hand, the matrix of the dark wood, according to X-ray diffractogram shows the presence of two types of carbonates. The main component is the calcium carbonate (CaCO3), although a secondary phase constituted of magnesium calcium carbonate (Mg0.064Ca0.936)(CO3) is also observed. The occurrence of magnesium calcium carbonate is consistent with the presence of Mg in the dark fossil. Interestingly, both the calcium carbonate (for the both matrices studied) and the magnesium calcium carbonate, presented rhombohedral symmetry with R-3c crystal structures. Because magnesium found in magnesium calcium carbonate appears in small quantity we can understand that it was incorporated as impurity in calcite crystal. The X-ray diffraction patterns of both the dark and the light fossils are presented in Fig. 3. The light wood fossil presents as the major component the compound calcium sulfate hydrate (CaSO42H2O), gypsum, whose crystalline structure appears with monoclinic symmetry and space group I2/a (I2/c). Furthermore, a secondary phase identied as goethite, iron oxide hydroxide, FeO(OH), was veried in the X-ray pattern of the light wood fossil. Related to the dark wood fossil, only two peaks of low intensity were observed, the most intense between them coincides with the most intense peak of the calcite pattern. In fact, for this material the X-ray diffractogram is compatible with a material of low crystallinity, suggesting an amorphous phase. As a consequence this diffraction pattern did not allow us identication of any crystalline phase. As we will discuss below, this result is in full agreement with the Raman spectroscopy measurements, which showed a characteristic spectrum of an amorphous phase. Raman and IR spectroscopies In order to obtain a better understanding of the fossil and their respective matrixes we have investigated them through Raman spectroscopy. While X-ray diffraction furnishes data about a rela-

Fig. 3. X-ray diffractogram of the dark wood fossil (upper trace) and of the light wood matrix (bottom trace). The pattern diffraction les (PDFs) of gypsum (dash vertical trace) and goethite (solid vertical trace) are also given.

Fig. 2. X-ray diffractogram of the matrix of the dark wood fossil (upper trace) and of the matrix of the light wood matrix (bottom trace).

tively great portion of the sample due the need to prepare a powder sample Raman spectroscopy furnishes precise information about the constitution of mineral in small regions of the samples (areas of typically 3 lm2). So, we were also interested to analyze different points of the four samples, in order to additionally discover their homogeneity. Fig. 4 shows the Raman spectra for the light wood and for the dark wood fossils and also for their respective mother stones. A rst observation is that the spectra, taken at different points of a certain sample (marked from P1 to P6), are very similar. As a consequence, the similar prole of the Raman spectra points to the homogeneity of both the fossils and the matrices. Fig. 4a and c show the Raman spectra of both the light wood fossil and the dark wood fossil, respectively, while Fig. 4b presents the Raman spectrum of the light wood matrix and Fig. 4d presents the Raman spectrum of the dark wood matrix. Let us begin the analysis through the matrixes of the fossils. The Raman spectrum of the light wood matrix (Fig. 4b) presents a peak located at 1087 cm1, which coincides with the most intense peak of calcite material [16]. It is known that calcite also presents peaks at 282 and 713 cm1 [16,17] but in our study it was very difcult to observe these two other modes associated with calcite. This conrms the data of X-ray diffraction already discussed. Additionally, the small linewidth of the peak at 1087 cm1 in the Raman spectrum points to a high crystallinity of the calcite present in the light wood matrix, although, obviously, the best method to attest the high crystallinity of calcite is XRD, not Raman. The Raman spectrum of the dark wood matrix (Fig. 4d) presents peaks at 282 and at 1087 cm1, which are characteristic of the calcite crystal. In comparison with the Raman spectrum of the light wood matrix we observe two main differences: (i) the appearance of the band of low wavenumber at 282 cm1 and (ii) the high intensity of the band at 1087 cm1. This means that the quality of the calcite in the dark wood matrix is better than that found in the light wood matrix. Among the Raman spectra presented in Fig. 4, that obtained from the light wood fossil (Fig. 4a) is the most complex one. In these spectra we observe bands at 422, 487 cm1 which were associated with symmetric bending of SO4, m2(SO4); modes located in 612 and 659 cm1, which were assigned as asymmetric bending of SO4 ions, t4(SO4), while the most intense band observed at 992 cm1 (spread up to 1000 cm1, depending on the spectrum)

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Fig. 4. Raman spectra of (a) the light wood fossil; (b) the light wood matrix; (c) the dark wood fossil; and (d) the dark wood matrix.

was associated with the symmetric stretching vibration of SO4, m1(SO4), because of their presence in various sulfate crystals [18,19]. As we can observe in the spectrum of Fig. 4a, the symmetric stretching is the most intense peak among those associated with SO4 ions in sulfate crystals. In fact, it is known that in melanterite, copiapite and ferricopiapite, the stretching vibration of SO4 is observed at 978, 995 and 997 cm1, respectively [20]; in K2SO4, the same vibration is observed at 984 cm1, while in Na2SO4, m1(SO4) is observed at 994 cm1 [21]. The stretching vibration of SO4 in gypsum is observed at 1009 cm1 [21] or at 1006 cm1 [22,23]. Although there is some quantitative difference between our spectrum and that of gypsum, qualitatively they are very similar. Finally, a mode observed at about 1126 cm1 was associated with the asymmetric stretching of the ion SO4, m3(SO4). In general terms the spectrum has resemblance with the spectrum of CaSO42H2O [16] what should conrm the data of X-ray diffraction measurements, although the peaks are shifted to lower frequencies. From discussion above we cannot discard the possibility of other sulfates are present in the sample. The Raman spectra of the dark wood fossil in several points of the sample are presented in Fig. 4c. These spectra are characteristic of materials consisting of amorphous carbon which present two characteristic peaks. The rst band is observed at 1355 cm1 and

is known as band of disorder (D band). The second peak, centered at 1600 cm1, is assigned as G (graphitic) band, being related to double bond C@C (rAp bond) in materials with this type of connection. These results reinforce the data obtained by the X-ray diffraction measurements, which show the occurrence of an amorphous phase. So, the Raman spectroscopy gives us a unied picture about the main material constituting the dark wood fossil. In order to complement the vibrational analysis of the samples we have recorded the infrared of the two fossils and their respective matrixes (Fig. 5). The matrixes of these woods show infrared spectra with the same prole, except for small difference in their intensities. The main peaks, appearing at 712, 876 and 1426 cm1 are characteristic of calcite when observed under infrared spectroscopy; they are associated, respectively to the m4(CO3) symmetric deformation, m2(CO3) anti-symmetric deformation and m3(CO3) anti-symmetric stretching [24,25]. We remember that the intense band observed in the Raman spectrum of calcite at 1087 cm1, which is associated with the symmetric stretching of CO3, m1(CO3), is not active in the infrared. On the other hand, when we observe the infrared spectra of the dark and the light fossils we note that they are very different. The infrared spectrum of the light wood fossil shows bands at 605 and 672 cm1, which are associated with the anti-symmetric bending of SO4, m4(SO4), at

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assigned as stretching of CAC and bending of CAH [27]. So, we see that the infrared spectrum of the dark wood fossil is compatible with amorphous carbon as suggested by other techniques. In summary, we can say that infrared spectra corroborate well the Raman spectroscopic and the X-ray diffraction measurements. The difference in the composition of light and dark fossil was also investigated through SEM technique. Fig. 6 presents an SEM image of the dark wood fossil (image of the light wood fossil is shown in Supplementary Material). From the light wood SEM image is easily seen that microcrystals are present, while for the latter, from the dark wood fossil SEM image, no indication of a crystalline structure is observed, conrming the results of Raman spectroscopy that showed amorphous carbon in the dark wood fossil. Discussion The high calcium content from calcite in the matrixes of the two fossils indicates that the rock is deposited in a slightly reducing environment. The darker color in the dark wood matrix can be attributed to the amount of iron, magnesium which characterizes an environment with reducing conditions. This reducing environment may have been a consequence of a higher concentration of organic matters, deposited in the bottom of the lake (Paleolake) with a higher consumption of dissolved oxygen in the water by decomposing agents. These results are interesting because the two fossils are originated from the same geological formation Crato Formation and the matrix is constituted mainly by the same material, calcite. However, the constitutions of the two fossils are very different. This suggests that in the same region two processes were responsible by the fossilization of the woods presented in this work. Additionally, it is worth to mention that the presence of oxygen in the dark wood fossil is consistent with a study on charcoal fossils from Kebara Cave and Tel Dor (two archeological sites in Israel) where it was observed that in fossils with amorphous carbon there is also the presence of oxygen [28]. As a consequence, the presence of this chemical element indicates that degradation of the fossil produced in natural res occurred via oxidation, even there is the minor possibility of oxidation of the material was produced by other causes. Although the age of the fossils from the archeological sites (3000 50,000 years) and the fossils analyzed in the present paper are very different, it is possible that the previous conclusion on charcoal fossils could be applied to the fossil of Cretaceous Period, at least to explain a hypothesis about the appearance of the amorphous carbon on the sample. On the other hand, the light fossil is rich in CaSO42H2O. Gypsum can be found in fossils as result of replacement of calcite as was previously reported in shells [29]. Obviously, the process that produces a gypsum fossil having as original substance the calcite as veried in shells is different from a process occurring in a plant that is originally poor in calcite. However, there are examples of fossil plants in gypsum beds, as those found in Zhoujiadian Formation in Guixi City, Jiangxi Province in China, where two species of Pseudofrenelopsis were analyzed [30]. The fact that the light wood fossil presented in this work is associated with gypsum bed suggests an environment of high salinity and high rates of evaporation. This is compatible with the environment of Crato Formation in the Cretaceous Period, where it is supposed the existence of an interior sea with salt water. Conclusion We have studied in this work two samples of wood fossils (Gymnosperms, Araucariaceae), as well as their respective arrays, i.e., the rocks surrounding the fossils. The fossil matrices studied

Fig. 5. Infrared spectra of the light wood fossil, dark wood fossil, light wood matrix and dark wood matrix, from top to bottom.

1175 cm1, associated with the anti-symmetric stretching of SO4, m3(SO4), and bands at 3406 and 3546 cm1, assigned as symmetric stretching of H2O, m1(H2O), and anti-symmetric stretching of H2O, m3(H2O), respectively [26]. As a consequence, we can realize that the infrared spectrum of light wood fossil is consistent with CaSO42H2O, conrming both the Raman spectroscopy and X-ray diffraction results. Finally, we have the infrared spectrum of the dark wood fossil where it is possible to observe a very complex spectrum prole. To understand this spectrum we remember that generally the amorphous carbon is not a pure material, i.e., it is common hydrogen to be incorporated to the structure of carbon. Amorphous carbon can be consisted of different quantities of sp3, sp2 and even sp1 carbon atoms and hydrogen atoms incorporated to the network [27]. As a consequence the infrared spectrum of amorphous carbon consists of stretching of CAH, in the range 28003300 cm1 and bands below 2000 cm1, which can be

Fig. 6. SEM image of the dark wood fossil.

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belong to the Crato Formation in Araripe Basin, from the Cretaceous Period, which were chosen based on criteria regarding the location, stratigraphic level and their type of coloring. These samples were characterized by Raman and infrared spectroscopies, X-ray diffraction and the scanning electron microscopy. The results obtained by different techniques showed that the rock matrices are formed mainly by calcite. However, the two kinds of fossils have different compositions: while the sample of light wood fossil is constituted predominantly by CaSO42H2O, the dark wood fossil is constituted mainly by amorphous carbon. The techniques used in this study are complementary and have given sufcient evidence to support the proposed results regarding the types of fossilization. One hypothesis about the origin of the dark wood fossil is a natural re, occurred in a dry period. The origin for the light wood fossil is an environment of high salinity and high rates of evaporation. Consequently, the present study conrms the previous reports of an interior sea in the Araripe Basin and, additionally, suggests the occurrence of dry periods during the Cretaceous Period, at least in the region of the Crato Formation. This opens the perspective to obtain a better understanding of a Formation rich in fossils from the Cretaceous Period. Acknowledgments The authors thank CNPq, FUNCAP and CAPES for partial support. B.C. Viana thanks CNPq for partial support, Process numbers: 401821/2010-2 and 553005/2011-1. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.saa.2013.06.042. References
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