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During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed. [ABSTRACT FROM AUTHOR]

Radioactive waste containing a few grams of plutonium (Pu) was disposed between 1960 and 1968 in trenches at the Little Forest Burial Ground (LFBG), near Sydney, Australia. A water sampling point installed in a former trench has enabled the radionuclide content of trench water and the response of the water level to rainfall to be studied. The trench water contains readily measurable Pu activity (∼12 Bq/L of 239+240Pu in 0.45 μm-filtered water), and uhere is an associated contamination of Pu in surface soils. The highest 239+240Pu soil activity was 829 Bq/kg in a shallow sample (0-1 cm depth) near the trench sampling point. Away from the trenches, the elevated concentrations of Pu in surface soils extend for tens of meters down-slope. The broader contamination may be partly attributable to dispersion events in the first decade after disposal, after which a layer of soil was added above the trenched area. Since this time, further Pu contamination has occurred near the trench-sampler within this added layer. The water level in the trench-sampler responds quickly to rainfall and intermittently reaches the surface, hence the Pu dispersion is attributed to saturation and overflow of the trenches during extreme rainfall events, referred to as the 'bathtub' effect. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) has often served as a model substrate for experimental sorption studies of environmental contaminants. However, various forms of Ti-oxide have been used, and the different sorption properties of these materials have not been thoroughly studied. We investigated uranium sorption on some thoroughly characterized TiO2 surfaces with particular attention to the influence of surface area, surface charge, and impurities. The sorption of U(VI) differed significantly between samples. Aggressive pretreatment of one material to remove impurities significantly altered the isoelectric point, determined by an electroacoustic method, but did not significantly impact U sorption. Differences in sorption properties between the various TiO2 materials were related to the crystallographic form, morphology, surface area, and grain size, rather than to surface impurities or surface charge. In-situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopic studies showed that the spectra of the surface species of the TiO2 samples are not significantly different, suggesting the formation of similar surface complexes. The data provide insights into the effect of different source materials and surface properties on radionuclide sorption. [ABSTRACT FROM AUTHOR]

Phosphorus, a critical environmental pollutant, is effectively removed from stormwater by biofiltration systems, mainly via sedimentation and straining. However, the fate of dissolved inflow phosphorus concentrations in these systems is unknown. Given the growing interest in using biofiltration systems to treat other polluted waters, for example greywater, such an understanding is imperative to optimize designs for successful long-term performance. A mass balance method and a radiotracer, 32P (as H3PO4), were used to investigate the partitioning of phosphorus (concentrations of 2.5-3.5 mg/L, >80% was in dissolved inorganic form) between the various biofilter components at the laboratory scale. Planted columns maintained a phosphorus removal efficiency of >95% over the 15-week study period. Plant storage was found to be the dominant phosphorus sink (64% on average). Approximately 60% of the phosphorus retained in the filter media was recovered in the top 0-6 cm. The 32P tracer results indicate that adsorption is the immediate primary fate of dissolved phosphorus in the system (up to 57% of input P). Plant assimilation occurs at other times, potentially liberating sorption sites for processing of subsequent incoming phosphorus. Plants with high nutrient uptake capacities and the ability to efficiently extract soil phosphorus, for example Carex appressa, are, thus, recommended for use in greywater biofilters. [ABSTRACT FROM AUTHOR]

Increasing concentrations of dissolved silicate progressively retard Fe(II) oxidation kinetics in the circum-neutral pH range 6.0-7.0. As Si:Fe molar ratios increase from 0 to 2, the primary Fe(III) oxidation product transitions from lepidocrocite to a ferrihydrite/silica-ferrihydrite composite. Empirical results, supported by chemical kinetic modeling, indicated that the decreased heterogeneous oxidation rate was not due to differences in absolute Fe(II) sorption between the two solids types or competition for adsorption sites in the presence of silicate. Rather, competitive desorption experiments suggest Fe(II) was associated with more weakly bound, outer-sphere complexes on silica-ferrihydrite compared to lepidocrocite. A reduction in extent of inner-sphere Fe(II) complexation on silica-ferrihydrite confers a decreased ability for Fe(II) to undergo surface-induced hydrolysis via electronic configuration alterations, thereby inhibiting the heterogeneous Fe(II) oxidation mechanism. Water samples from a legacy radioactive waste site (Little Forest, Australia) were shown to exhibit a similar pattern of Fe(II) oxidation retardation derived from elevated silicate concentrations. These findings have important implications for contaminant migration at this site as well as a variety of other groundwater/high silicate containing natural and engineered sites that might undergo iron redox fluctuations. [ABSTRACT FROM AUTHOR]