Paweł Stach

The review presents methods that are used frequently for multi-analytical study of fossil resins. The preliminary characterization relies on physical methods such as microhardness, density and fluorescence in UV light measurements. The spectroscopic methods: infrared spectroscopy, Raman spectroscopy, fluorescence spectroscopy are also presented in the paper. Besides that, the review also contains examples of the application of chromatographic methods: gas chromatography, thin layer chromatography, high-performance liquid chromatography, two-dimensional gas chromatography coupled to time-of-flight mass spectrometry as well as sample preparation methods for chromatographic studies such as pyrolysis. Additionally, thermal methods such as thermogravimetric analysis and differential scanning calorimetry also are covered by the review. Beside the examples of application, a detailed description with development history and perspective for further improvement are presented for each method. Moreover, fit-for-purpose assessment of each method is illustrated based on many examples from literature. The paper also contains examples of the application of multivariate statistical analysis and chemometric methods for comparing multiple properties of different fossil resin specimens for differentiation and classification purposes.

The paper presents comprehensive mineralogical and geochemical characteristics of Dominican amber-bearing sediments from Siete Cañadas, Hato Mayor Province of the Eastern Mining District (EMD) in the Cordillera Oriental. The characteristics of rocks collected from the borehole in Siete Cañadas area (EMD) were compared with petrography of coaly shales from La Cumbre in the Northern Mining District (NMD). The mineralogy of the rocks was determined using transmitted and reflected light microscopy, scanning electron microscopy, Powder X-ray diffraction and Fourier Transform Raman Spectroscopy. Biomarker analyses by the gas chromatography–mass spectrometry were used to trace the genetic source and transformation stage of organic matter hosted in the core sediments. In this study, the characteristics of rocks from La Cumbre were supplemented with the petrographic data from our studies reported earlier. Based on the findings, it has been concluded that the basins in the investigated parts of the EMD and NMD regions were likely characterized by different, isolated palaeosettings. Transformation and maturation of terrigenous material were affected by locally occurring physicochemical conditions. In both amber deposits, the sedimentation of clastic and organic material proceeded in the presence of marine conditions. In case of the La Cumbre deposit (NMD area), the sedimentation underwent probably in the conditions of the lagoon environment, a shallow maritime lake or periodically flooded plain that facilitated organic matter decomposition and carbonation from meta-lignite to sub-bituminous coal (random reflectance of coal—R_r^o = 0.39%). In the Siete Cañadas (EMD region), the sedimentation took place in a shallow saltwater basin, where terrigenous material was likely mixed with material found in situ (fauna fossils, carbonate-group minerals) to form the mudstones enriched in bituminous substance of low maturity. The organic matter found in the rocks from both deposits is of mixed terrestrial/marine origin and was deposited in the presence of low oxygen concentration and reducing and/or dysoxic conditions.

Mineralogical and geochemical characteristics of amber deposits located in the Dominican Republic, i.e., Hato Mayor Province of the Eastern Mining District (EMD) in the Cordillera Oriental, and Santiago Province of the Northern Mining District (NMD) in the Cordillera Septentrional were performed. The results of analyses of amber-bearing sediments collected from the borehole in Siete Cañadas area (EMD) were referenced to the petrological data obtained for the coaly shales from La Cumbre (NMD). The mineralogy of the rocks was described using transmitted and reflected light microscopy, scanning electron microscopy, Powder X-ray diffraction and Fourier Transform Raman Spectroscopy. Biomarker analyses by the gas chromatography-mass spectrometry were used to trace the genetic source and transformation stage of abundant organic matter hosted in the core sediments. Our findings indicated that basins in EMD and NMD regions were different isolated palaeosettings, in which under the influence of local physicochemical factors the terrigenous material was transformed and got maturated. In both amber deposits, the sedimentation of clastic and organic material proceeded in the presence of marine conditions. In case of the NMD area, the sedimentation underwent probably in the conditions of the lagoon environment, a shallow maritime lake or periodically flooded plain, that facilitated organic matter decomposition and carbonation from meta-lignite to sub-bituminous coal (random reflectance of coal - R_r^o = 0,39%). In the EMD region, the sedimentation took place in a deeper basin, where terrigenous material was likely mixed with material found in situ (fauna fossils, carbonate-group minerals) to form the mudstones enriched in bituminous substance of low maturity. The organic matter found in the rocks from both regions is of mixed terrestrial/marine origin and was deposited in the presence of low oxygen concentration and reducing and/or dysoxic conditions.

The amber-bearing coaly shale from the La Cumbre deposit (Cordillera Septentrional, Dominican Republic) contains a large quantity of altered, coalified plant detritus. The coals in these shales are in the transition stage from meta-lignite to subbituminous coals. They are composed mainly of inertinite macerals such as fusinite, semifusinite, macrinite and secretinite. Fossil resin found in the deposit occurs in two forms: detrital grains up to several centimetres in size (type I) and very fine authigenic grains, of a few micrometers in size, inside the humic laminae (type II, resinite). The detrital fossil resins are transparent, with few mineral and organic inclusions. In their composition they contain sulfides, which may come from sulfate reduction, inclusions of plants and/or insects or be caused by volcanic activity developed in surrounding coal series. The resinites are strongly saturated with various inclusions and spatially associated with framboidal pyrite aggregates. Both fossil resin types were probably deposited in a shallow coastal lake environment in the zone bordering the floodplain of the river, with periodic floods. The marine environment conditions, which were progressively changing from oxidizing to reducing, are likely associated with the formation of the fossil resin.

Comparative studies of fossil resins of various ages, botanical sources, geological environments, and provenience were provided via a handheld portable Near-Infrared (NIR)-Raman spectrometer and benchtop instrument both working with laser line 1064 nm. The recorded Raman spectra of individual fossil resins were found to be sufficiently similar irrespective to the device type applied, i.e., handheld or benchtop. Thus, the portable equipment was found to be a sufficient tool for the preliminary identification of resins based on botanical and geographical origin criteria. The observed height ratio of 1640/1440 cm⁻¹ Raman bands did not correlate well with the ages of fossil resins. Hence, it may be assumed that geological conditions such as volcanic activity and/or hydrothermal heating are plausible factors accelerating the maturation of resins and cross-linking processes.

Testing of the correlation between physical properties of natural resins such as microhardness, density and UV-excited fluorescence emission with their age, geological conditions, botanical and geographical origin and chemical structure was performed. These physical parameters, especially microhardness, are the result of resins fossilization processes like cross-linking and polymerizations of compounds present in the fossils. In addition, hardening of the resins may be also an effect of miscellaneous chemical processes induced by various environmental, biological and geological conditions. The principal component analysis found that the correlation of microhardness, density and fluorescence intensity with the resin age is quite low. The results suggest that variability of physical properties is caused by geographic location and locally occurring geological conditions. The physical properties of natural resins are most strongly correlated with chemical structure and geographic location. The resins with higher microhardness values come from marine environment depositions. The same trend was observed for resins affected by volcanic activity. Moreover, high fluorescence intensity was also observed for resins affected by above mentioned geological conditions. However, the density values of tested resins revealed the lowest correlation with their age, botanical source and geological history.

A unique specimen of fossil resin originating from the Dipterocarpaceae tree family found in Miocene brown coal deposits in Jambi Province (Sumatra, Indonesia) was investigated via microscopic observations, microhardness testing and infrared and Raman spectroscopic methods. Its form is rare in nature, being an aggregate of three varieties of resin differing in colour, transparency and internal structure. This suggests the formation of the resins at different stages. Further alteration processes, including fossilization and maturation of the resin in a swamp environment resulted in stepwise aromatization of the cyclohexane ring in steroids and cross-linking through formation of ester bonds as well as carbon–carbon bonds between steroid molecules. The various environmental and geological conditions affecting the formation processes of the resins were recorded in their physico-chemical properties. Additionally, heating conditions accelerated by volcanism were proposed as a factor determining the maturation grade of the resin.