Reduction of actinides in higher oxidation states by hydroquinone-enriched humic derivatives

Abstract

Natural humic materials are known to cause a reduction of penta- and hexavalent plutonium; however, contradicting results have been previously reported for neptunium. The goal of this study was to determine if incorporation of additional reducing centers into humic structure would yield material with enhanced reducing performance with respect to higher valent actinides, nominally, Pu(V) and Np(V). Hydroquinone-moieties were used as the redox centers. They were incorporated into humic structures using formaldehyde condensation at different monomer-to-humic ratios to obtain materials of different reducing properties. Reduction of model actinides by the hydroquinone-enriched humic materials was studied under both oxic and anoxic conditions at acidic and neutral pH values. Redox speciation of plutonium and neptunium was monitored using solvent extraction techniques and liquid scintillation counting. It was shown that both nonmodified leonardite humic acid and all the obtained derivatives were able to reduce Pu(V) quantitatively both at neutral and acidic pH and under oxic and anoxic conditions. The reduction rate increased with an increase in the degree of modification of the humic material and reached its maximum for HQ500 derivative. For neptunium, reduction was observed only under anoxic conditions at acidic pH. The hydroquinone-modified derivatives had much higher reducing performance when compared to nonmodified leonardite humic acid. The results obtained show good prospects for a use of hydroquinone-modified humic materials as reactive agents for remediation of actinide contaminated aquifers.