Francis Claret

Generation of humic and fulvic acid from Callovo-Oxfordian clay under high alkaline conditions

Low-carbon-containing clay from four different depths (447 to 516 m) of the Meuse Haute Marne (MHM) site is kept in contact with alkaline solution simulating conditions expected from cement dissolution in the near-field of a nuclear waste repository. Original organic material in the clay consists mainly of aliphatic hydrophobic compounds basically without oxygen-containing functional groups. After contact with solid young fluid (mimicking cement dissolution, initial pH 13.22) for approximately one and a half years, high concentrations of hydrophilic organic matter are found (243-355 mg DOC/L). Characterization by solubility behavior, UV/Vis absorption, IR and fluorescence properties show that the dissolved hydrophilic organic matter has the characteristic features of humic and fulvic acids. Estimation of humic and fulvic acid content via UV/Vis spectroscopy results in 97.5 (+/-9.7)% of DOC being humic and fulvic acid. The results indicate that this could be an important source of complexing mobile organic matter influencing the mobility of radionuclides in a nuclear waste repository under consideration for this site. Investigations were conducted under oxic conditions representing the situation in the excavation disturbed zone (EDZ) of an underground facility. Sample amounts were very small and thus some characterization results are partly of preliminary character.

Effects of charging on the chromophores of dissolved organic matter from the Rio Negro basin

This study demonstrates that the deprotonation of dissolved organic matter (DOM) originating from a small creek characteristic for DOM-rich waters located in the Rio Negro basin can be quantified based on measurements of pH effects on its absorbance spectra. The method was ascertained by the data of Near-Edge X-Ray Absorbance Spectroscopy (NEXAFS), potentiometric titration to quantify the structural and compositional differences between the colloidal and hydrophobic fractions that contribute 91% of black-water creek DOM. Changes in the absorbance spectra of the DOM fractions caused by deprotonation quantified via numeric deconvolution which indicated the presence of six well-resolved Gaussian bands in the differential spectra. The emergence of these bands was determined to be associated with the engagement of carboxylic and phenolic functionalities and changes of inter-chromophore interactions in DOM molecules. Interpretation of the data based on the NICA-Donnan approach showed that behavior of DOM chromophores was consistent with results of potentiometric titrations. Similar trends were observed for changes of the spectral slope of the DOM absorbance spectra in the range of wavelengths 325-375xa0nm (DSlope325-375). The behavior of DSlope325-375 values was modeled based on the NICA-Donnan approach and correlated with potentiometrically-estimated charges attributed to the carboxylic and phenolic groups. The correlations between DSlope325-375 and charges of low- and high-affinity protonation-active groups in DOM were monotonic but not linear and had important differences between the colloidal and hydrophobic fractions.