Using spectroscopic autoradiography of alpha particles for the quantitative mapping of 226Ra ultra-traces in geo-materials.

The measurement of 226Ra and the identification of 226Ra-bearing minerals are important for studying the behavior of radium in the environment. Various instruments for measuring 226Ra are currently used: among the radiometric techniques that measure in bulk (no spatialization), there are gamma spectrometers and alpha spectrometers. Other instruments such as SEM-EDS can map the chemical elements thus providing information on the distribution of 226Ra, but are limited for ultra-trace analyses on natural geomaterials. Finally, autoradiography techniques can locate radioactivity, but are limited to the identification of the contribution of 226Ra when the 238U series is complete. This study focuses on spectroscopic autoradiography, a method for measuring both the energy of the alpha particle emissions and their positions on the autoradiograph. A gas detector based on a parallel ionization multiplier technology was used for this purpose. Alpha particle energy is dependent on the emitting radionuclides. In order to track the 226Ra, the energy spectrum of the 238U series was studied with modeling software. It appears possible to apply a thresholding on the energy spectrum to discriminate the 226Ra from the first alpha emitters of the 238U decay chain (i.e. 238U, 234U and 230Th, all below 5 MeV). The developed method was applied to a U-mill tailing sample prepared as a thin section. The sample was heterogeneous in terms of radioactivity and was not at secular equilibrium with 238U, as expected. The 226Ra was identified and localized, and different regions of interest were also analyzed with SEM-EDS elements cartography. This revealed 226Ra-rich barite (BaSO4) phases measured at 3 ppmRa on average and containing no uranium; and uranium in siderite (FeCO3), showing a strong 226Ra deficit compared with secular equilibrium. Spectroscopic autoradiography opens up possibilities for the analysis of heterogeneous geological samples containing natural alpha emitters such as 238U and 226Ra: the 226Ra can be localized and quantified at ultra-trace content, and the method developed can also identify newly (young) uranium phases by measuring 238U/226Ra activity disequilibrium.

STED nanoscopy - A novel way to image the pore space of geological materials.

STED nanoscopy (Stimulated Emission Depletion). which can resolve details far below the diffraction barrier has been applied hitherto preferentially to life sciences. The method is however also ideal for the investigation of geological matrices containing transparent minerals, an application tested here, to our knowledge, for the first time. The measurements on altered granitic rock and sedimentary clay rock, both containing very fine-grained phases, were conducted successfully. The STED fluorophore was dissolved in C-14-labelled methylmethacrylate (C-14-MMA) monomer which was polymerised within the rock matrix, thereby labelling the pore space in the geomaterials. Double labelling provided by the C-14-labelled MMA enables autoradiography and scanning electron microscopy (SEM), providing necessary complementary information for characterisation and quantification of porosity distributions and mineral and structure identification. Promising perspectives for further investigations of geological matrices by using different fluorophores and the optimisation of measuring procedures or even higher resolution are discussed. The combination of these different methods enlarges the observation scale of porosity from nanometre to centimetre scale.