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.

Radon emanation from fresh, altered and disturbed granitic rock characterized by 14C-PMMA impregnation and autoradiography.

Radon emanation from intact samples of fresh ("BG"), altered ("Fract") and disturbed ("EDZ") Finnish granitic rock from Kuru (Finland) and its dependence on humidity and rock structural factors was studied. The pore network of the rock was characterized by microscopy and impregnation with 14C-PMMA (polymethylmethacrylate) resin and autoradiography. The radon emanation factor was increasing linearly with the relative humidity. 14C-PMMA autoradiography of the altered zones and the EDZ indicated significant, mineral-specific increase of porosity and porosity gradients towards the fracture surfaces (Fract) and microcracks within the EDZ. For small samples in the cm-scale emanation was not diffusion, but source term controlled.

Multidisciplinary analysis of Finnish esker sediment in radon source identification.

In order to define the naturally-occurring radioactive materials that are the source of radon in natural environments, a comprehensive analytical (geochemical, physical and chemical) methodology was employed to study sand samples from the Hollola esker in the city of Hollola (Lahti area, Finland). Techniques such as gamma-spectrometry, emanation measurements, sequential chemical extraction, scanning electron microscopy (SEM), electron probe microanalyses (EPMA) and inductively-coupled plasma mass spectrometry (ICP-MS) were used to determine the potential source of radon. Monazite and xenotime, uranium- and thorium-bearing minerals and potential radon sources, occurred in significant amounts in the samples and were also the main reason for the distribution of uranium and thereby radium in separate grain-size fractions. Following deposition, the esker sand has been exposed to no significant weathering, and radium has not therefore been much separated from uranium. However, considering its non-compatibility with crystal lattices, it was recognized rather in easily leachable species (44% of the total (226)Ra) than uranium (21% of the total (238)U) in our analyses. The smallest grain-size fraction of the esker sand had a higher emanation power (0.24) than the other fractions (around 0.17). Due to the small relative proportion of this fraction, however, it contributed only slightly to the total emanation (4%). The emanation power of the leachable species was about three times higher (ca. 0.20) than that of the species tightly bound to the crystal lattice (ca. 0.07).

Interpretation of out-diffusion experiments on crystalline rocks using random walk modeling.

Matrix diffusion in saturated rocks with very low permeability is one of the major mechanisms of solute transport. Laboratory out-diffusion experiments on rock samples may provide an estimate of the bulk diffusion coefficient. However, numerous results have shown that this average parameter does not really depict the complex mechanism of diffusion as a function of the internal heterogeneity of crystalline rocks. Two-dimensional images of the porosity distribution in a granite sample were obtained by impregnation with a radioactive resin and autoradiography. Some examples based on these images and synthetic images were used to perform numerical simulations of out-diffusion using two different random walk methods. The simulated shapes of the out-diffusion curves depend on the spatial distribution of the porosity and on the pore connectivity with the border of the sample. Such relations might explain the multiple nested slopes or the convex shapes often observed on real experimental curves.