In this study, Raman micro spectroscopy is applied to investigate two manganese oxides: lithiophorite [(Al,Li)Mn4+O2(OH)2] and asbolane [(Ni,Co)xMn4+(O,OH)4.nH2O], along with their intermediates (“Asbolane-Lithiophorite Intermediates”: ALI). These oxides typically incorporate variable concentrations of Co, Ni, Cu and Li. They represent a group of economically interesting phases that are difficult to identify and characterize with classical X-ray diffraction techniques. We show that Raman micro spectroscopy is useful to the investigation of those phases, but they require to be tested in very low laser power conditions to avoid sample degradation (e.g. 0.2mW 532nm). We propose reference Raman spectroscopic signatures for lithiophorite, asbolane and ALI phases. These spectra are mainly composed of two spectral domains, the first one is located between 370-630 cm-1 and the second one between 900-1300 cm-1. We then assess the impact of their highly variable chemistry on their Raman peak positions, intensities and FWHM using a semi-systematic curve-fitting method profiled for these phases.
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Abstract Mercantour National Park (France) is recognized as a highly heterogeneous region with extremely varied geology, geomorphology and climatology, resulting in an exceptional biodiversity. From a hydrogeological point of view, it is also an area organized of small and discontinuous aquifers, their obligate groundwater fauna remaining absolutely unknown. This work explores the species richness of groundwaters in Mercantour National Park, using a sampling design at the catchment (six major valleys) and aquifer scales (aquifers in consolidated rocks and unconsolidated sediments). A major finding of this study is the discovery of 44 species restricted to groundwater, from which 43 are new to the Park and 10 are new to Science. Although a relatively small number of sites were sampled (53), the area may be considered as a new hotspot of groundwater biodiversity at the European level. The particular structure of the groundwater network, the high environmental heterogeneity of the region, and its Mediterranean position may explain such a high biodiversity. Species rarefaction curve showed that many species have yet to be discovered in groundwater of the Mercantour National Park. With more than 78% of species collected in the hyporheic zone, this study also highlights the importance of porous aquifers in sustaining groundwater biodiversity of mountainous regions. Key words: groundwater invertebrates, stygobionts, biodiversity hotspot, Mercantour National Park, hyporheic zone, spring. Résumé Biodiversité dans les eaux souterraines de montagne. Le Parc National du Mercantour: un ‘hotspot’ européen. Le Parc National du Mercantour est une région physiquement très hétérogène, avec des faciès géologiques, géomorphologiques et climatologiques extrêmement variés, à l’origine d’une biodiversité exceptionnelle. D'un point de vue hydrogéologique, son réseau souterrain est organisé en aquifères discontinus et de petite taille, dont la faune aquatique (stygobie) est aujourd’hui inconnue. Ce travail explore la richesse spécifique des eaux souterraines du Parc National du Mercantour, après la mise en œuvre d'un plan d'échantillonnage prenant en compte l'hétérogénéité environnementale à l’échelle du bassin versant (six vallées majeures) et de l'aquifère (aquifère fissuré ou poreux). Le premier fait marquant est la récolte de 44 espèces stygobies, 43 étant nouvelles pour le parc et 10 nouvelles pour la Science. Sur la base d’un nombre relativement faible de sites (53), cette zone peut être considérée comme un nouveau ‘hotspot’ de biodiversité des eaux souterraines à l'échelle européenne. La structure particulière du réseau hydrogéologique, l'hétérogénéité environnementale élevée, et la position méditerranéenne de cette région, pourraient expliquer une telle biodiversité. La courbe de raréfaction des espèces montre que nos connaissances sur le Mercantour sont néanmoins loin d'être complètes et que de nombreuses espèces restent encore à découvrir. Avec plus de 78 % des espèces récoltées dans la zone hyporhéique, ce travail souligne également le rôle des aquifères poreux, dans le maintien de la biodiversité des eaux souterraines de montagne. Mots-clés: invertébrés souterrains, stygobies, ‘hotspot’ de biodiversité, Parc National du Mercantour, zone hyporhéique, source.
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1. The Pleistocene glaciations during the Quaternary appear to have resulted in an impoverished groundwater fauna in northern Europe. Re-colonisation may have occurred either through long-distance dispersal from unglaciated southern areas or from local refugia. 2. The Belgian groundwater fauna was sampled at multiple sites, and its habitats characterised, to assess whether the composition of present-day stygobiotic assemblages can be attributed to either of these mechanisms. 3. A total of 202 sampling sites were selected in four hydrogeographic units of the Meuse River catchment. Sites were equally divided among the saturated and unsaturated zones of fractured aquifers (karst) and within the hyporheic and phreatic zones of porous aquifers. Seventeen environmental parameters were determined in parallel. 4. More than 140 species were recorded, including representatives of the Amphipoda, Cladocera, Copepoda, Hydrachnidia, Isopoda, Oligochaeta, Ostracoda, Mollusca, Syncarida and Nematoda. Thirty stygobiont specieswere identified, of which10 species were new to the Belgian fauna, raising the total number of stygobiotic species in Belgium to 41. 5. The frequency of occurrences of stygobiotic species was always low, with 37% of the sampled sites lacking stygobionts. A few species were exclusive to one hydrological zone, although no statistically significant differences were detected in species richness at any of the four hierarchial levels considered (Meuse catchment = region, hydrogeographic units, aquifer type and hydrological zone). 6. Overall, results suggest that the stygobiotic fauna of Belgium is species-poor and mostly comprises widely distributed species with broad ecological tolerances. This supports the view that eurytopic species re-colonised the area by long-distance dispersal from refugia in southern Europe. The virtual absence of endemic species further suggests that the scenario of an ancient fauna that survived in local refugia is of minor importance.
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