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In the Neolithic Gavà mines, variscite and turquoise were exploited for ornaments manufacturing, although some prospective pits and tunnels were dug on other similar greenish minerals such as smectite or kandite. A 3D study of the distribution of mineral phases allows us to determine the parameters involved in variscite colours. Methods are comprised of quantitative colourimetry, thin section petrography, SEM-BSE-EDS, EMPA, XRD, Raman spectroscopy, and 57Fe Mössbauer spectrometry. Mapping of the mines indicates that colour is not directly dependent on depth. Although variscite from Gavà is poor in Cr3+ and V+3 compared with gemmy variscite from other localities, the deep green samples content has the highest values of Cr3+. In the case of cryptocrystalline mixtures with jarosite, phosphosiderite, or goethite, variscite tends to acquire a greenish brown to olivaceous hue. If white minerals such as quartz, kandite, crandallite, or alunite are involved in the mixtures, variscite and turquoise colours become paler. [ABSTRACT FROM AUTHOR]

In Roman wall paintings, blue and green colours are less commonly encountered than red and yellow and were more expensive. Despite this, Pliny and Vitruvius describe the more common compounds used for these pigments, translated today as azurite, lazurite, chrysocolla, indigo and Egyptian blue for blues and verdigris, malachite, celadonite, glauconite and chlorite for greens. A confusion in their nomenclature is often found in the most common blue pigment that is the first manufactured compound, Egyptian blue. For greens, celadonite and glauconite were usual and called generically 'green earths', but they prove to be difficult to characterize analytically. In this paper, we evaluate the Raman spectroscopic identification of the characteristic Roman blue and green pigments as used in wall paintings using two different laser wavelengths (green and near infrared) and clarify their nomenclature. [ABSTRACT FROM AUTHOR]

Variscite is an aluminium phosphate mineral widely used as a gemstone in antiquity. Knowledge of the ancient trade in variscite has important implications on the historical appreciation of the commercial and migratory movements of human population. The mining complex of Gavà, which dates from the Neolithic, is one of the oldest underground mine sites in Europe, from where variscite was extracted from several mines and at different depths, providing minerals with different properties and a range of colours. In this work, machine learning algorithms have been used to classify variscite samples from Gavà with regard to the identification of their mine of origin and extraction depth. The final objective of the study was to see if the Raman spectroscopic signatures selected by these algorithms had a key spectral significance related to mineral structure and/or composition and validate the use of these computational procedures as a useful tool for detecting variances in the mineral Raman spectra that could facilitate the assignment of the specimens to each mine. [ABSTRACT FROM AUTHOR]

Here we report the archaeomagnetic, rock-magnetic and Raman spectroscopy results of sample analysis from two types of limestones that were experimentally heated under controlled conditions. These lithologies have been commonly identified at the middle-palaeolithic sites of Descubierta Cave and Navalmaillo rock-shelter (Pinilla del Valle, Madrid, Spain). By means of a thermocouple system, maximum heating temperatures of 400 - 450 °C were recorded during one hour. The main goal was to characterize the variations in the magnetic mineralogy and (in)organic compounds, and to study the record of the Earth's magnetic field direction at the time of cooling. This allowed us to obtain a pattern that is potentially applicable to archaeological limestones in order to identify combustion structures at the site. All experiments were carried out on representative samples both before and after experimental heating. Before heating, both types of limestones were dominated by dolomite and calcite and as main iron oxides, goethite and magnetite. After heating, the original goethite persisted in samples heated to low temperatures (<200 °C) whereas it transformed to haematite and/or magnetite in those heated to 450 °C. Mineralogical alterations mostly focused on the outermost 1st cm of depth. The neoformation of magnetite as intermediate step in the dehydration process of goethite to haematite has been barely documented and has palaeomagnetic implications. The mineralogical results obtained, their implications for the identification of fire at the site as well as potential applications to similar cases studies are discussed. [ABSTRACT FROM AUTHOR]

Raman spectroscopy is a valuable analytical technique for the identification of biomolecules and minerals in natural samples, which involves little or minimal sample manipulation. In this paper, we evaluate the advantages and disadvantages of this technique applied to the study of extremophiles. Furthermore, we provide a review of the results published, up to the present point in time, of the bio- and geo-strategies adopted by different types of extremophile colonies of microorganisms. We also show the characteristic Raman signatures for the identification of pigments and minerals, which appear in those complex samples. [ABSTRACT FROM AUTHOR]

The discovery of small, spherical nodules termed 'blueberries' in Gusev Crater on Mars, by the NASA rover Opportunity has given rise to much debate on account of their interesting and novel morphology. A terrestrial analogue in the form of spherical nodules of similar size and morphology has been analysed using Raman spectroscopy; the mineralogical composition has been determined and evidence found for the biological colonisation of these nodules from the spectral signatures of cyanobacterial protective biochemical residues such as scytonemin, carotenoids, phycocyanins and xanthophylls. This is an important result for the recognition of future sites for the planned astrobiological exploration of planetary surfaces using remote robotic instrumentation in the search for extinct and extant life biosignatures and for the expansion of putative terrestrial Mars analogue geological niches and morphologies. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: A novel type of colonisation of a basaltic rock, collected on the Arctic island of Svalbard, Norway, during the AMASE expedition in 2004, was characterised using Raman spectroscopy and Scanning Electron Microscopy (SEM). The sample contains two different types of extremophile communities, one occurring behind a radial white crystallisation and the other occurring inside a dark vacuole. Several types of minerals and microbial colonies have been identified by both Raman spectroscopy and SEM analyses. It is the first time that photosynthetic communities have been documented to colonise the inside of dark basaltic rocks. Our discovery has important implications for planetary exploration because it extends the analytical capability and our understanding of microbial rock colonisations to subaerial volcanic outcrops and has wide implications towards the search for life in extraterrestrial planets. In this work we also demonstrate that the use of different laser wavelengths for Raman spectroscopic studies and complementary microscopic analysis are critical for a comprehensive organic and inorganic compound identification. [Copyright &y& Elsevier]

Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces. [ABSTRACT FROM AUTHOR]

Abstract: The Rio Tinto site is recognised as a terrestrial Mars analogue because of the presence of jarosite and related sulfates which have recently been identified by the NASA Mars Exploration Rover “Opportunity” in the El Capitan region of Meridiani Planum on Mars. It has long been known that acidophilic microbial action is responsible for the deep blood-red colour of the water in Rio Tinto, where the pH varies from about 1.5 to 3.0 and the water is rich in iron and sulfur. Following recent Raman spectroscopic characterisation of the mineral phases of the Rio Tinto system, we report here a study of the biological components found in several specimens of deposited minerals and near the waterside that were collected during a GeoRaman VI Conference organized field trip in 2006. Key biosignatures were found for carotenoids, scytonemin and mycosporine-like amino acids, which are indicative of the biological colonisation of exposed mineral substrates; information from this study will be useful for targeting Martian sites using a miniaturized Raman instrument where the biosignatures of relict or extant life could remain in the geological record. [Copyright &y& Elsevier]

Abstract: With proposals that micro-miniaturised Raman spectrometers could soon be part of a suite of analytical instrumentation on the surface of Mars, it is critically important to examine the spectral information that could be forthcoming from attempts to determine key molecular biosignatures under the hostile conditions of extra-terrestrial planetary exploration. Current approaches include the analysis of genuine martian geological material in the form of the SNC class meteorites, the formulation of simulated martian regoliths and the examination of putative martian terrestrial analogues; the latter provide the basis of this paper in the form of Antarctic extremophile habitats. In particular, specimens of epilithic, chasmolithic and endolithic lichen and cyanobacterial colonies sampled along a progressively worsening transect towards a “limits of life” situation, beyond which survival of organisms becomes impossible, provide what is arguably the best terrestrial proving-ground for prototype Raman spectrometers for martian exploration. Here, we report the results of experiments on these extant Antarctic extremophile colonies using a range of Raman excitation wavelengths and experimental conditions and also include a compilation of molecular spectral biosignatures, which may be considered as a suitable database for recognition of bioorganic modification of geological strata. [Copyright &y& Elsevier]