Predicting the bioavailability of sediment-bound uranium to the freshwater midge (Chironomus dilutus) using physicochemical properties.

Assessment of uranium (U)-contaminated sediment is often hindered by the inability to accurately account for the physicochemical properties of sediment that modify U bioavailability. The present goal was to determine whether sediment-associated U bioavailability could be predicted over a wide range of conditions and sediment properties using simple regressions and a geochemical speciation model, the Windermere Humic Aqueous Model (WHAM7). Data from a U-contaminated field sediment bioaccumulation test, along with previously published bioaccumulation studies with U-spiked field and formulated sediments, were used to examine the models. Observed U concentrations in Chironomus dilutus larvae exposed to U-spiked and U-contaminated sediments correlated well (r2 > 0.74, p < 0.001) with the WHAM-calculated concentration of U bound to humic acid, indicating that humic acid may be a suitable surrogate for U binding sites (biotic ligands) in C. dilutus larvae. Subsequently, the concentration of U in C. dilutus was predicted with WHAM7 by numerically optimizing the equivalent mass of humic acid per gram of organism. The predicted concentrations of U in C. dilutus larvae exposed to U-spiked and U-contaminated field sediment compared well with the observed values, where one of the regression models provided a slightly better fit (mean absolute error = 18.1 mg U/kg dry wt) than WHAM7 (mean absolute error = 34.2 mg U/kg dry wt). The regression model provides a predictive capacity with a minimal number of variables, whereas WHAM7 provides additional complementary insight into the chemical variables influencing the speciation, sorption, and bioavailability of U in sediment. The present results indicate that physicochemical properties of sediment can be used to account for variability in U bioavailability as measured through bioaccumulation in chironomids exposed to U-contaminated sediments. Environ Toxicol Chem 2018;37:1146-1157. © 2017 SETAC.

The role of sediment properties and solution pH in the adsorption of uranium(VI) to freshwater sediments.

Uranium (U) can enter aquatic environments from natural and anthropogenic processes, accumulating in sediments to concentrations that could, if bioavailable, adversely affect benthic organisms. To better predict the sorption and mobility of U in aquatic ecosystems, we investigated the sediment-solution partition coefficients (Kd) of U for nine uncontaminated freshwater sediments with a wide range of physicochemical characteristics over an environmentally relevant pH range. Test solutions were reconstituted to mimic water quality conditions and U(VI) concentrations (0.023-2.3 mg U/L) found downstream of Canadian U mines. Adsorption of U(VI) to each sediment was greatest at pH 6 and 7, and significantly reduced at pH 8. There were significant differences in pH-dependent sorption among sediments with different physicochemical properties, with sorption increasing up until thresholds of 12% total organic carbon, 37% fine fraction (≤50 µm), and 29 g/kg of iron content. The Kd values for U(VI) were predicted using the Windermere Humic Aqueous Model (WHAM) using total U(VI) concentrations, and water and sediment physicochemical parameters. Predicted Kd-U values were generally within a factor of three of the observed values. These results improve the understanding and assessment of U sorption to field sediment, and quantify the relationship with sediment properties that may influence the bioavailability and ecological risk of U-contaminated sediments.

Assessment of co-contaminant effects on uranium and thorium speciation in freshwater using geochemical modelling.

Speciation modelling of uranium (as uranyl) and thorium, in four freshwaters impacted by mining activities, was used to evaluate (i) the influence of the co-contaminants present on the predicted speciation, and (ii) the influence of using nine different model/database combinations on the predictions. Generally, co-contaminants were found to have no significant effects on speciation, with the exception of Fe(III) in one system, where formation of hydrous ferric oxide and adsorption of uranyl to its surface impacted the predicted speciation. Model and database choice on the other hand clearly influenced speciation prediction. Complexes with dissolved organic matter, which could be simulated by three of the nine model/database combinations, were predicted to be important in a slightly acidic, soft water. Model prediction of uranyl and thorium speciation needs to take account of database comprehensiveness and cohesiveness, including the capability of the model and database to simulate interactions with dissolved organic matter. Measurement of speciation in natural waters is needed to provide data that may be used to assess and improve model capabilities and to better constrain the type of predictive modelling work presented here.

Metal-based nanoparticles in soil: fate, behavior, and effects on soil invertebrates.

Metal-based nanoparticles (NPs) (e.g., silver, zinc oxide, titanium dioxide, iron oxide) are being widely used in the nanotechnology industry. Because of the release of particles from NP-containing products, it is likely that NPs will enter the soil compartment, especially through land application of sewage sludge derived from wastewater treatment. This review presents an overview of the literature dealing with the fate and effects of metal-based NPs in soil. In the environment, the characteristics of NPs (e.g., size, shape, surface charge) and soil (e.g., pH, ionic strength, organic matter, and clay content) will affect physical and chemical processes, resulting in NP dissolution, agglomeration, and aggregation. The behavior of NPs in soil will control their mobility and their bioavailability to soil organisms. Consequently, exposure characterization in ecotoxicological studies should obtain as much information as possible about dissolution, agglomeration, and aggregation processes. Comparing existing studies is a challenging task, because no standards exist for toxicity tests with NPs. In many cases, the reporting of associated characterization data is sparse, or missing, making it impossible to interpret and explain observed differences in results among studies.

Estimation of Model VII humic binding constants for Pd2+, Sn2+, U4+, NpO2(2+), Pu4+ and PuO2(2+).

Using previously established procedures that utilise linear free energy relationships, we estimated binding constants for the Windermere Humic Aqueous Model VII (WHAM/Model VII) for several radionuclide cations (Pd(2+), Sn(2+), U(4+), NpO(2)(2+), Pu(4+) and PuO(2)(2+)). This extends the number of cations that can be calculated with the model above the 40 included in the original Model VII work. When combined with equilibrium constants for inorganic species this allows the calculation of equilibrium distributions of chemical species under a wide range of conditions.