Application of Resonance Ionization Mass Spectrometry for Ultratrace Analysis of Technetium.

This work shows the ability of resonance ionization mass spectrometry (RIMS) to determine 99gTc at the ultratrace level. The characterization of the prepared samples by X-ray photoelectron spectroscopy (XPS) and optimization of the RIMS setup for this purpose, as well as the application of the RIMS method to a soil sample, are presented in this article. 97Tc was used as a tracer isotope to determine the amount of 99gTc in a soil sample with RIMS. With 8.8 × 1010 atoms of 97Tc as the tracer, the concentration of 99gTc was found to be 1.5 × 109 atoms per gram of dried sample material, demonstrating the sensitivity of the method. Furthermore, it could be shown that the 97Tc solution contained 98Tc as well. This is the first time that 97,98,99gTc have been simultaneously measured with RIMS.

High-resolution isotopic monitoring of cave air CO2.

RATIONALE: CO2 is the main driver of many chemical processes in cave environments. Understanding CO2 fluxes in a given cave system through monitoring campaigns has become a standard procedure in a wide variety of fields such as paleoclimatology or show cave management. However, conventional methods lack the resolution of isotopic data to capture many transient processes occurring in caves. METHODS: A novel approach using isotope ratio infrared spectrometry (IRIS) to monitor cave air pCO2 , δ13 C and δ18 O values in situ was tested and compared with conventional monitoring methods (handheld pCO2 meter and discrete cave air samples for conventional isotope ratio mass spectrometry). This also involved the development of a field-deployable experimental setup to operate the equipment in rough cave environments. RESULTS: Comparison between data obtained by means of a Thermo Fisher Scientific Delta Ray IRIS instrument shows overall good agreement with conventional monitoring methods in terms of pCO2 and δ13 C values. In addition, IRIS allows the δ18 O values of cave air CO2 to be measured. CONCLUSIONS: IRIS allows identification and tracking of processes at various timescales ranging from transient visitor impact on the cave atmosphere to seasonal trends in cave ventilation. However, the need for an uninterrupted power supply (110/220 V AC) and the relatively large dimensions of the equipment (698 × 1092 × 704 mm, 80 kg) limit the number of caves where deployment of the instrument is feasible. Copyright © 2017 John Wiley & Sons, Ltd.

Sensitive redox speciation of neptunium by CE-ICP-MS.

Capillary electrophoresis (CE) was used to separate the neptunium oxidation states Np(IV) and Np(V), which are the only oxidation states of Np that are stable under environmental conditions. The CE setup was coupled to an inductively coupled plasma mass spectrometer (Agilent 7500ce) using a Mira Mist CE nebulizer and a Scott-type spray chamber. The combination of the separation capacity of CE with the detection sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) allows identification and quantification of Np(IV) and Np(V) at the trace levels expected in the far field of a nuclear waste repository. Limits of detection of 1 × 10(-9) and 5 × 10(-10) mol L(-1) for Np(IV) and Np(V), respectively, were achieved, with a linear range from 10(-9) to 10(-6) mol L(-1). The method was applied to study the redox speciation of the Np remaining in solution after interaction of 5 × 10(-7) mol L(-1) Np(V) with Opalinus Clay. Under mildly oxidizing conditions, a Np sorption of 31% was found, with all the Np remaining in solution being Np(V). A second sorption experiment performed in the presence of Fe(2+) led to complete sorption of the Np onto the clay. After desorption with HClO(4), a mixture of Np(IV) and Np(V) was found in solution by CE-ICP-MS, indicating that some of the sorbed Np had been reduced to Np(IV) by Fe(2+).