Early Neanderthal constructions deep in Bruniquel Cave in southwestern France.

Very little is known about Neanderthal cultures, particularly early ones. Other than lithic implements and exceptional bone tools, very few artefacts have been preserved. While those that do remain include red and black pigments and burial sites, these indications of modernity are extremely sparse and few have been precisely dated, thus greatly limiting our knowledge of these predecessors of modern humans. Here we report the dating of annular constructions made of broken stalagmites found deep in Bruniquel Cave in southwest France. The regular geometry of the stalagmite circles, the arrangement of broken stalagmites and several traces of fire demonstrate the anthropogenic origin of these constructions. Uranium-series dating of stalagmite regrowths on the structures and on burnt bone, combined with the dating of stalagmite tips in the structures, give a reliable and replicated age of 176.5 thousand years (±2.1 thousand years), making these edifices among the oldest known well-dated constructions made by humans. Their presence at 336 metres from the entrance of the cave indicates that humans from this period had already mastered the underground environment, which can be considered a major step in human modernity.

Ultrasonic treatment of glassy carbon for nanoparticle preparation.

Glassy carbon particles (millimetric or micrometric sizes) dispersions in water were treated by ultrasound at 20kHz, either in a cylindrical reactor, or in a "Rosette" type reactor, for various time lengths ranging from 3h to 10h. Further separations sedimentation allowed obtaining few nanoparticles of glassy carbon in the supernatant (diameter <200nm). Thought the yield of nanoparticle increased together with the sonication time at high power, it tended to be nil after sonication in the cylindrical reactor. The sonication of glassy carbon micrometric particles in water using "Rosette" instead of cylindrical reactor, allowed preparing at highest yield (1-2wt%), stable suspensions of carbon nanoparticles, easily separated from the sedimented particles. Both sediment and supernatant separated by decantation of the sonicated dispersions were characterized by laser granulometry, scanning electron microscopy, X-ray microanalysis, and Raman and infrared spectroscopies. Their multiscale organization was investigated by transmission electron microscopy as a function of the sonication time. For sonication longer than 10h, these nanoparticles from supernatant (diameter <50nm) are aggregated. Their structures are more disordered than the sediment particles showing typical nanometer-sized aromatic layer arrangement of glassy carbon, with closed mesopores (diameter ∼3nm). Sonication time longer than 5h has induced not only a strong amorphization (subnanometric and disoriented aromatic layer) but also a loss of the mesoporous network nanostructure. These multi-scale organizational changes took place because of both cavitation and shocks between particles, mainly at the particle surface. The sonication in water has induced also chemical effects, leading to an increase in the oxygen content of the irradiated material together with the sonication time.

The Raman-Derived Carbonization Continuum: A Tool to Select the Best Preserved Molecular Structures in Archean Kerogens.

UNLABELLED: The search for indisputable traces of life in Archean cherts is of prime importance. However, their great age and metamorphic history pose constraints on the study of molecular biomarkers. We propose a quantitative criterion to document the thermal maturity of organic matter in rocks in general, and Archean rocks in particular. This is definitively required to select the best candidates for seeking non-altered sample remnants of life. Analysis of chemical (Raman spectroscopy, (13)C NMR, elemental analysis) and structural (HRTEM) features of Archean and non-Archean carbonaceous matter (CM) that was submitted to metamorphic grades lower than, or equal to, that of greenschist facies showed that these features had all undergone carbonization but not graphitization. Raman-derived quantitative parameters from the present study and from literature spectra, namely, R1 ratio and FWHM-D1, were used to draw a carbonization continuum diagram showing two carbonization stages. While non-Archean samples can be seen to dominate the first stage, the second stage mostly consists of the Archean samples. In this diagram, some Archean samples fall at the boundary with non-Archean samples, which thus demonstrates a low degree of carbonization when compared to most Archean CM. As a result, these samples constitute candidates that may contain preserved molecular signatures of Archean CM. Therefore, with regard to the search for the oldest molecular traces of life on Earth, we propose the use of this carbonization continuum diagram to select the Archean CM samples. KEY WORDS: Archean-Early life-Kerogen-Raman spectroscopy-Carbonization. Astrobiology 16, 407-417.

Evaluation of Raman spectroscopy to detect fullerenes in geological materials.

Fullerene C(60) was determined repeatedly from a few types of carbonaceous matter from geological environments. Detailed investigation of structural aspects of pure carbonaceous matrices as well as of their experimental mixtures with fullerene C(60) permits better understanding of the occurrence mode of fullerenes inside the network of natural samples. However, it appears that Raman microspectrometry is not competitive in the case of investigated current geological carbonaceous matrices with added fullerenes, when the concentration of fullerene C(60) is 100 ppm or lower. In such a situation, C(60) is highly dispersed and careful interpretation of the results of Raman microspectrometry does not permit us to obtain valuable quantitative structural data. Obtained sensitivity for detecting C(60) in investigated matrices was only 1%. Analytical reasons for these results are discussed.

Maturation grade of coals as revealed by Raman spectroscopy: progress and problems.

The present study questions the sensitivity and the accuracy of Raman spectroscopy as a tool for determining the maturity of natural organic matter (NOM). It focuses on the definition of optimized experimental parameters in order to maximize the quality of the Raman signal and control the accuracy and reproducibility of measurements. A series of 11 coals has been investigated, sampling a wide maturity range (2-7% vitrinite reflectance VR). The role of experimental parameters is first investigated. An excitation wavelength of 514.5 nm gives better results than 457.9 and 632.8 nm, minimizing the fluorescence background observed in the spectra of low-rank coals. Both Raman and fluorescence spectra were investigated with time-resolved experiments in air and argon. These data show that fluorescence and Raman spectra are sensitive to acquisition time and laser power parameters, and reveal a physicochemical instability of the samples under laser irradiation, mostly due to photo-oxidation processes. These data clearly show that the experiments, especially in air, should be performed with strictly constant acquisition parameters. In addition, the results of a whole series of coal measurements performed in air under constant experimental conditions show that Raman spectroscopy is definitely sensitive to the maturity of coal samples with VR> approximately 1%. The most sensitive spectral maturity tracers are the width of the D-band (FWHM-D), the ratio of the peak intensities of the D- and G-bands (I(D)/I(G)), the normalized ratio of the band integrated intensities A(D)/[A(D)+A(G)] for the maturity range VR=3-7% and the width of the G-band (FWHM-G) for VR=1-5%. However, the accuracy and reproducibility are definitely weaker in such measurements compared to the standard VR. Future work must solve the problem of sample stability under laser irradiation, and greatly increase the number of samples to improve the statistical significance of the results.

On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy.

The applicability of Raman spectroscopy to characterize disordered and heterogeneous carbonaceous materials (CM) is discussed, by considering both natural and synthetic CM. First, different analytical mismatches during the measurement are discussed and technical indications are provided in order to eliminate them. Second, the accuracy and relevance of the different parameters obtained by the decomposition of spectra by conventional fitting procedure, is reviewed. Lastly, a new Raman technique (Raman area mode microspectroscopy) giving an homogeneous repartition of power within a large laser beam is presented, this technique being powerful to study strongly heterogeneous CM and/or photosensitive samples.

Wet chemical method for making graphene-like films from carbon black.

Reduction of strongly oxidized carbon black by hydrazine hydrate yields water-insoluble graphene-like sheets that undergo to self-assembling in thin film on surfaces after drying. The height of a drop-casted graphene-like film was determined by atomic force microscopy (AFM) to be around 20 nm, corresponding to approximately 25 graphene-like layers. The oxidized carbon black and the corresponding reduced form were carefully characterized.