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Separation of the minor actinides americium(III) and curium(III) by hydrophobic and hydrophilic BTPhen ligands: exploiting differences in their rates of extraction and effective separations at equilibrium
The complexation and extraction of the adjacent minor actinides Am(III) and Cm(III) by both hydrophobic and hydrophilic pre-organized 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands has been studied in detail. It has been shown that Am(III) is extracted more rapidly than Cm(III) by the hydrophobic CyMe4-BTPhen ligand into different organic diluents under non-equilibrium extraction conditions, leading to separation factors for Am over Cm (SFAm/Cm) as high as 7.9. Furthermore, the separation of Am(III) from Cm(III) can be tuned through careful choice of the extraction conditions (organic diluent, contact time, mixing speed, ligand concentration). This ‘kinetic’ effect is attributed to the higher presumed kinetic lability of the Am(III) aqua complex towards ligand substitution. A dependence of the Am(III)/Cm(III) selectivity on the structure of the alkyl groups attached to the triazine rings is also observed, and BTPhens bearing linear alkyl groups are less able to separate Am(III) from Cm(III) than CyMe4-BTPhen. Under equilibrium extraction conditions, hydrophilic tetrasulfonated BTPhen ligands complex selectively Am(III) over Cm(III) and prevent the extraction of Am(III) from nitric acid by the hydrophobic O-donor ligand N,N,N’,N’-tetraoctyldiglycolamide (TODGA), giving separation factors for Cm(III) over Am(III) (SFCm/Am) of up to 4.6. These results further underline the utility of the BTPhen ligands for the extremely challenging separation of the chemically similar minor actinides Am(III) and Cm(III) in future processes to close the nuclear fuel cycle
Raman spectroscopy as a tool for provenancing black limestones ( bigi morati
Among precious stones used in antiquity, bigi morati stand out for their importance. They consist in black limestones mainly employed in sculptures and architectural heritages and quarried from several sites through the Mediterranean area. Their provenance is difficult to assess due to their similar appearance to the naked-eye observation and the possible confusion with black marbles (i.e., bigi antichi). Classical methods used for studying ancient marbles, such as minero-petrographic and stable isotopes analyses (δ13C and δ 16O), resulted to be powerful in provenancing these black lithotypes. However, these methods are microdestructive and cannot be always applied in the case of precious artefacts for which sampling is not allowed. Bearing carbonaceous matter conferring them the typical black-dark grey colour, Raman spectroscopy might support studies on these limestones, bringing important information about the structural state of organic/carbonaceous matter and their geological evolution. In this study, the potential of Raman spectroscopy in determining geological and geographic provenance of bigi morati was tested on quarry samples from six among the most famous ancient exploitation sources. The obtained results demonstrated that the use of Raman parameters typical of low-ordered carbon matter is an effective tool in discriminating provenance. Moreover, the laboratory-based approach lays the groundwork for future development and validation of the method for in situ measurements on artefacts by using portable equipment