Ioannis Ignatiadis

Novel CeO2-based Screen-Printed Potentiometric Electrodes for pH monitoring

Nuclear waste repositories are being installed in deep excavated rock formations in some places in Europe to isolate and store radioactive waste. In France, the Callovo-Oxfordian formation (COx) is a possible candidate for nuclear waste storage. This work investigates the applicability of CeO(2)-based oxides (CeO(2), Ce(0.8)Sm(0.2)O(2) and Ce(0.8)Zr(0.2)O(2)) for monitoring the pH of the COx pore water (T=25°C). The study is limited to the pH range between 5.5 and 13.2, which includes the pH values that have been encountered or are anticipated in the COx formation during its evolution as radioactive waste repository due mainly to alkalinisation, an increase in salinity, and a decrease in redox potential. Screen-printing was done to assemble electrodes and rapidly generate data sets. The electrochemical behavior of CeO(2)-based screen-printed electrodes (CeO(2)-based SPEs) was determined by cyclic voltammetry and electrochemical impedance spectroscopy. The use of the electrodes for pH sensing was then evaluated by potentiometric measurements. The feasibility of measuring pH with CeO(2)-based SPEs was first tested in NH(4)Cl/NH(3) buffer solutions, leading to electrode calibration over the widest range of pH, from around neutral to basic pH. Experiments were then conducted in NaHCO(3)/Na(2)CO(3) buffer samples similar to conditions prevailing in the COx formation. Ce(0.8)Zr(0.2)O(2) SPEs exhibit a near-Nernstian behavior (sensitivity -(51±2)mV/pH) in the pH range of 5.5-13.2 at 25°C. Electrode response was slightly affected by the direction of the pH change. Electrode reliability was clearly demonstrated for pH monitoring. Probes based on the same components, but more durably designed, could be considered for pH measurements in radioactive waste repositories.

Diazonium Salt-Based Surface-Enhanced Raman Spectroscopy Nanosensor: Detection and Quantitation of Aromatic Hydrocarbons in Water Samples

Here, we present a surface-enhanced Raman spectroscopy (SERS) nanosensor for environmental pollutants detection. This study was conducted on three polycyclic aromatic hydrocarbons (PAHs): benzo[a]pyrene (BaP), fluoranthene (FL), and naphthalene (NAP). SERS substrates were chemically functionalized using 4-dodecyl benzenediazonium-tetrafluoroborate and SERS analyses were conducted to detect the pollutants alone and in mixtures. Compounds were first measured in water-methanol (9:1 volume ratio) samples. Investigation on solutions containing concentrations ranging from 10−6 g L−1 to 10−3 g L−1 provided data to plot calibration curves and to determine the performance of the sensor. The calculated limit of detection (LOD) was 0.026 mg L−1 (10−7 mol L−1) for BaP, 0.064 mg L−1 (3.2 × 10−7 mol L−1) for FL, and 3.94 mg L−1 (3.1 × 10−5 mol L−1) for NAP, respectively. The correlation between the calculated LOD values and the octanol-water partition coefficient (Kow) of the investigated PAHs suggests that the developed nanosensor is particularly suitable for detecting highly non-polar PAH compounds. Measurements conducted on a mixture of the three analytes (i) demonstrated the ability of the developed technology to detect and identify the three analytes in the mixture; (ii) provided the exact quantitation of pollutants in a mixture. Moreover, we optimized the surface regeneration step for the nanosensor.

A Multi-Parametric Device with Innovative Solid Electrodes for Long-Term Monitoring of pH, Redox-Potential and Conductivity in a Nuclear Waste Repository

We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl− selective electrodes, one Ag2S/Ag-based reference or S2− selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors.