Preliminary thermal characterization of natural resins from different botanical sources and geological environments

The preliminary studies on thermal behavior of differently aged natural resins from Russia (Khatanga), Dominican Republic (El Valle), Colombia and Poland (Jantar) were performed. Thermal stability and behavior under elevated temperature were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC), while the differences in the structure and composition by FT-IR spectroscopy. Analyzed resins show different thermal effects during heating suggesting that possible post-reactions and structural changes occurred. TG results indicated that Dominican, Russian and Colombian resins present relatively high thermal stability under air conditions in the range of 228–300 °C, whereas the mass loss of 5mass% at about 217 °C was observed for Baltic amber. During DSC experiments, the analyzed resins expose thermal events which make impossible determination of glass transition temperature in a raw sample. The results indicate that both TG and DSC cannot be considered as methods for age dating of natural resins and more advanced techniques should be applied. Careful analysis of FT-IR data in the carbonyl region may provide additional information about the composition and history of the natural resin.

     

Raman microspectroscopy of organic inclusions in spodumenes from Nilaw (Nuristan, Afghanistan)

The color varieties of spodumene (green spodumene, kunzite) from Nilaw mine (Nuristan, Afghanistan) have been investigated by microthermometry and Raman spectroscopy analyses. These minerals are rich in primary and secondary fluid inclusions. Measured values of temperature homogenization (T(h)) and pressure (P) for selected fluid-inclusion assemblages (I-IV) FIA in green spodumene and (I-II) FIA in kunzite ranges from 370 to 430°C, 1.16 to 1.44 kbar and 300 to 334°C, 0.81 to 1.12 kbar, respectively. The brine content and concentration varies from 4.3 to 6.6 wt.% eq. NaCl. Numerous and diverse mineral phases (quartz, feldspars, mica, beryl, zirconium, apatite, calcite, gypsum) present in this mineral as solid inclusions were studied by Raman microspectroscopy. Raman spectra of selected fluid, organic and solid inclusions were collected as line or rectangular maps and also depth profiles to study their size and contents. There appeared very interesting calcite (156, 283, 711 and 1085 cm(-1)), beryl (324, 397, 686, 1068 and 3610 cm(-1)), topaz (231, 285, 707, 780 and 910 cm(-1)) and spodumene (355, 707 and 1073 cm(-1)) inclusions accompanied by fluid and/or organic inclusions (liquid and gas hydrocarbons) with bands at 2350 cm(-1) (CO(2), N(2)), 2550 cm(-1) (H(2)S) and 2900 cm(-1) (C(2)H(6)-CH(3)). Some solid inclusions contain carbonaceous matter (D-band at ca. 1320 cm(-1) and/or G-band at ca. 1600 cm(-1)).     

A Raman microspectroscopic study of organic inclusions in “watermelon” tourmaline from the Paprok mine (Nuristan, Afghanistan)

An exceptional mineral specimen, particularly interesting for collectors and researchers, is “watermelon” tourmaline, mined in the Paprok region in Nuristan, Afghanistan. A pale pink core (zone III) is surrounded by a thin, colorless zone (zone II), and a green outer zone (zone I). Differences between zones are clearly seen in the SEM picture, i.e., diversity in the size of constituent forms, and also the presence of inclusions of alien mineral phases which range from a few dozen to a few μm. In the line mapping experiment the Raman spectra were collected from the inner core towards the outer rim. There are observed typical for tourmaline (elbaite) groups of bands: at ca. 3600, 1100, 700, 400 and 250 cm⁻¹. Raman measurements determine the differences in the local chemical composition of particular zones. Interestingly, there is a new band emerging in the outer zone at ca. 840 cm⁻¹, and it could be due to the SiO₄ stretching vibrational modes predisposed by the Fe ion presence in the mineral. The organic inclusions are present in the whole volume of the investigated gem. Organic inclusion content appears to be versatile. Raman spectra confirm the presence of hydrogen sulphide (2610 cm⁻¹), methane (2912 cm⁻¹), ethane (2950 cm⁻¹), and propane (2895 cm⁻¹). In the corresponding bending vibrations region apart from CH₂, CH₃ vibrations and C–O stretching (CO₂) at (1280, 1390 cm⁻¹), characteristic bands are also observed at ca. 1340, 1600 and 1660 cm⁻¹. The last ones possibly mark the evolution of graphitization process occurring from fluid saturated inclusions within condensed ring aromatics (1660 cm⁻¹ band), towards slightly more organized, although still amorphous forms of carbonaceous matter (1340 and 1600 cm⁻¹).