The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

In contaminated water reservoirs, the sorption and binding of radionuclides to solids (SR) determines their bioavailability and transport and thus human and ecosystem exposure. In this work, the influence of organic matter (OM) on binding of the radionuclides 90 Sr, 137 Cs, sum of 235 U, 238 U, and sum of 239 Pu, 240 Pu to solids are investigated, using experimental data derived from ecological monitoring of radioactive waste deposits in South Ural (Russia). OM in several surface water reservoirs mainly consists of humic substance (HS) which forms humates and fulvates with radionuclides and binds to solids via different mechanisms, such as coordinating bond or covalent bond. These processes are strongly dependent on the phase of HS, which can be colloidal or soluble high-molecular compounds. Based on the spatial distribution of radionuclides, SR and OM in waste deposits, we assumed a specific influence of humic acids (HA) on the binding of radionuclides to SR, and quantified it with invariant values of a modified partitioning coefficient. The mathematical form of this invariant value emphasizes a significant impact of the local mass of HA (mHA/V) and local surface area of SR (s=Ssorb/V) per volume V on the processes involved in binding radionuclides to SR. These processes may retard radionuclide migration into groundwater.

This manuscript elucidates the influence of special functional groups of organic xenobiotic chemicals on partly simultaneous molecular binding mechanisms. Organic xenobiotics are released as contaminants into the environment and are partially bound to soil constituents, such as humic substances (HS) and the mineral phase. The interaction of chemical contaminants with HS of soil was investigated using a labeling technique of soil samples with stable nitroxide radicals as model contaminants. These nitroxide radicals only differed in one functionality, a hydroxy or an amino functional group. Electron spin resonance (ESR) analyses of contaminated soil samples showed that the interaction was a multistage process that comprised an initial increase in the concentration of free organic radicals of soil influenced by contaminants with hydroxy or amino functionality, a decrease in the polarity of the molecular environment of soil, and a change in mobility of contaminant molecules. Towards the end of interaction, the concentration of free organic radicals usually decreased. Binding of contaminants to soil constituents via specific functionality was revealed detecting a change in their ESR spectra. Basing on the ESR analyses, a two-way exchange of protons' electron pairs between contaminants and HS was hypothesized to interpret the beginning of interaction.

Radiological waste disposal and accidents from radionuclide production over several decades have resulted in widespread radioactive contamination of surface water systems in South Ural. Natural attenuation of radioactive contamination of freshwater can be considered as an alternative to manage radioactive materials released into the environment. A management alternative takes advantage of natural remediation processes, especially the binding of radionuclides and their compounds to water body solids via humic substances. The formation of radionuclide complexes with humic acids removes and converts radionuclides to a less hazardous form and is followed by a decrease in radionuclide bioavailability to freshwater biota, especially fish and benthos. Here, we present an investigation and quantification of natural remediation of highly contaminated surface water systems located in South Ural via humic substances. Based on a large set of experimental data, we state that in the surface water systems, humic acids promote the immobilization of radionuclides and thus decrease their bioavailability for fish in the investigated water bodies. We examine the influence of humic substance on the chemical and biological interactions between radionuclides and the environment that has experienced increasing interest concerning the remedial uses of humic materials.