Lucyna Natkaniec-Nowak

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 authors present the history of chrysoprase discovery and the progress of knowledge about this material over the millennia, based on the extended review of world literature. Tracing the oldest archaeological artifacts from before 9,000 years, the lens of history turns on a stone that has not been properly identified mineralogically for centuries. In the 1830s, chrysoprase was finally included into the chalcedony group and its green color was associated, very correctly, with nickel compounds dispersed in its structure. After all, the most current mineralogy of chrysoprase is presented on the basis of the results of modern analytical studies. These data clearly indicate that chrysoprase is a mixture of several SiO₂ polymorphs with varying degrees of structural order (opal, chalcedony, moganite, quartz). This radically changes the previous taxonomy of chrysoprase and its position in current mineralogical and petrographic systematics.

This paper presents basic mineralogical and petrological data of the rocks hosting larimar deposit from the Sierra de Bahoruco, in the SW part of the Dominican Republic. Larimar is a unique ornamental stone with a wealth of decorative qualities. The Las Filipinas Larimar Mine in Barahona Province is the only place of this type in the world. Its production and distribution require radical action; hence, the paper also provides current information on the extraction of this raw material and prospects for the future. The paper indicates the possibility of using a new adit support system based on a mixed support (arch support and shotcrete). Numerical analysis shows the need to create a shotcrete coating around the entire circumference, about 15 cm thick. The variable geotechnical situation around the excavation, caused by the planned operation, prompts the use of slightly different solutions in the field of support. The article presents an outline of the technology using Polish experience. It is a support-bolt casing system with the latest achievements in this field.

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.

Agate samples collected from the vicinity of Asni and Agouim (Western Atlas, Morocco) were investigated using microscopic observations supported by Raman micro-spectroscopy. The agates are marked by the presence of various microtextures typical of epithermal vein deposits, including jigsaw-puzzle, feathery, and lattice-bladed. The first two indicate that the formation of agates was likely marked by recrystallization of metastable silica phases (i.e., opaline silica or massive chalcedony). The presence of lattice-bladed (after barite and calcite) quartz may be, in turn, ascribed to the boiling-related conditions that could have triggered the formation of abundant copper and iron sulfides found within silica matrix. Additionally, the local occurrence of growth lines (so-called Bambauer quartz) and intergrowth of length-slow and length-fast chalcedony are linked to the variations of physico-chemical conditions during rock formation (alkaline-acidic). According to Raman spectroscopy, silica matrix of the agates is made of α-quartz with a local admixture of moganite (from 0.0 up to 78 wt.%), but also contains numerous solid inclusions of hematite, celadonite, as well as poorly-organized carbonaceous material and rutile. These phases were likely emplaced during low-temperature hydrothermal activity of SiO₂-bearing fluids that originated from post-magmatic hydrothermal activity developed within host rocks and/or meteoric waters.

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.

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.

Amber-bearing sands from Zdolbuniv mine are Paleogene fine-grained (0.6-0.12 mm) clastic rocks. The material is poorly rounded and moderately sorted out. It mainly consists of quartz, glauconite, and subordinately, feldspars (K-feldspars and plagioclases), mica, carbonates, zircon, epidote,fossil resins (Baltic amber) and ore minerals such as hematite, rutile, anatase, ilmenite. The presence of glauconite in the sands proves that sedimentation basin had to be marine reservoir. The variable composition of individual glauconite grains suggests the environmental conditions had to change during the sedimentation of clastic rocks. The occurrence of minerals, assembly such as zircon, epidote, ilmenite, rutile, anatase in the sands as well as the brown CL color of quartz grains, may suggest that majority of clastic material originated from metamorphic rocks, most probably coming from the Ukrainian Shield. Together with metamorphic material the fragment of fossil resins, i.e. Baltic amber, from the Paleogene off-shore forests could be transported to the sedimentation basin. Nowadays the bottom part of the analyzed profile is the most promising for the recovery of glauconite, whereas the exploration of Baltic amber may be initiated from the top of the profile.

Agate nodules from Kerrouchen (Khénifra Province, Meknés-Tafilalet Region) in Morocco occur in Triassic basalts and reach up to 30 cm in diameter. Monocentric, banded agates—mainly in pastel pink, grey, white and yellow—with infiltration canals (osculum) are observed. Raman microspectroscopy revealed that the agates mainly consist of low quartz and subordinately moganite with distinctive 460 and 501 cm⁻¹ marker bands, respectively. Linear mapping indicated that moganite mainly concentrates in grey zones of the monocentric agate nodules. The other types, polycentric and pseudostalactitic agates, are usually brown and red and contain minerals such as hematite and goethite. They form both regular and irregular mosaics rich in ornamentation. Occasionally, aggregates of copper sulphides or titanium oxides (rutile) can also be observed. These minerals are sometimes accompanied by carbonaceous material marked by 1320 and 1585 cm⁻¹ Raman bands. It seems that formation of agates from Kerrouchen was induced by Si-rich and Fe-moderate fluids. Copper sulphides, rutile, and carbonates (possibly calcite) were most likely incorporated during post-magmatic processes. The origin of solid bitumen can be the result of hydrothermal or hypergenic processes.

Hornfels from the closed “Wolność” mine (Kowary, the Lower Silesia) are recognized as thermally metamorphosed rocks belonging to hornblende-hornfels facies or locally a facies of pyroxene hornfels. Their texture reveal the traces of some deformations such as folding or fractures. Their protholit is described as a pelitic deposit enriched with clay minerals. The sediment was altered into meta-pelities-aleurites after the diagenesis, and later the rock was intensely thermally metamorphosed at the contact with the intrusion of the Karkonosze granitoid. Three varieties are distinguished based on their colour: green, grey and black. Green and black colours result from the predominance of hornblende and biotite over other rock components, respectively. Whereas grey hornfels are composed of similar amounts of both mafic minerals: biotite and hornblende. Quartz, mica minerals (biotite and muscovite), amphibole, (hornblende), acid plagioclase and andalusite, epidote group (clinozoisite), orthoclase and pyroxene make up hornfels components. Locally, andalusite is accompanied by sillimianite, which indicates a higher degree of contact metamorphism alterations. Three generations of minerals are distinguished in the rocks: allogenic (I), metamorphic (II) and hydrothermal (III). The allogenic phases are represented by heavy minerals such as zircon, apatite and monazite, which are characteristic of the protholit. The main components of the rocks (e.g. quartz, hornblende, feldspars, andalusite, sillimanite, mica minerals) belong to metamorphic minerals. Chalcopyrite, pyrite and fluorite are surely hydrothermally originated phases. Granitoides found at the contact zone with hornfels indicate traces of metasomatic alteration as a result of endomorphism in this region.