Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments.

Plutonium, americium, and uranium contribute to the radioactive contamination of the environment and are risk factors for elevated radiation exposure via ingestion through food or water. Due to the significant environmental inventory of these radioelements, a sampling method to accurately monitor their bioavailable concentrations in natural waters is necessary, especially since physicochemical factors can cause significant temporal fluctuations in their waterborne concentrations. To this end, we engineered novel diffusive gradients in thin-film (DGT) configurations using resin gels, which are selective for UO22+, Pu(IV + V), and Am(III) among an excess of extraneous cations. In this work, we also report an improved synthesis of our in-house ion-imprinted polymer resin, which we used to manufacture a resin gel to capture Am(III). The effective diffusion coefficients of Pu, Am, and U in agarose cross-linked polyacrylamide were determined in freshwater and seawater simulants and in natural seawater, to calibrate these configurations for environmental deployments.

Driving forces and barriers in the removal of phosphorus from water using crop residue, wood and sewage sludge derived biochars.

The removal of phosphorus (P) from sewage effluents is necessary to control eutrophication in receiving waters. Biochar has been proposed and is investigated for the capture and reuse of P, however the forces driving and limiting P adsorption are still largely unclear. To identify the forces governing P uptake by biochar, biochars with markedly different physicochemical characteristics derived from a variety of biomass (oilseed rape straw, wheat straw, miscanthus straw, rice husk, soft wood and sewage sludge residue), pyrolysed at various temperatures, were investigated. The biochar samples were characterised in terms of pH, electrical conductivity, total acidity, carbon chemistry, metal composition, surface area, and porosity, and the uptake and release of P was compared to the biochar properties using multivariate analysis. Uptake of P by the biochars as such was low (< 0.71 mg P/g biochar with feed solutions of 50 mg P/l) and, among the variables studied, the biochars' Ca and Mg content was key in P removal and found to be pH dependant. Enhancement of biochar surface area and porosity was carried out by activation with CO2 at 800 °C and the uptake significantly improved (p < 0.05) (i.e. an increased surface area from <20 m2/g up to 781 m2/g gave a limited improvement in P removal to <1.2 mg P/g biochar at feed level of 50 mg P/l). These results confirm that the potential to use these unmodified biochars derived from a variety of biomass for P sorption is low, but that the material provides properties that may be modified or enhanced to increase sorption capacity. This study indicates that biochar/biochar feedstock with greater content of Ca and Mg will be more advantageous for P capture.

Trends in the recovery of phosphorus in bioavailable forms from wastewater.

Addressing food security issues arising from phosphorus (P) scarcity is described as one of the greatest global challenges of the 21st Century. Dependence on inorganic phosphate fertilisers derived from limited geological sources of P creates an urgent need to recover P from wastes and treated waters, in safe forms that are also effective agriculturally - the established process of P removal by chemical precipitation using Fe or Al salts, is effective for P removal but leads to residues with limited bioavailability and contamination concerns. One of the greatest opportunities for P recovery is at wastewater treatment plants (WWTPs) where the crystallisation of struvite and Ca-P from enhanced biological P removal (EBPR) sludge is well developed and already shown to be economically and operationally feasible in some WWTPs. However, recovery through this approach can be limited to <25% efficiency unless chemical extraction is applied. Thermochemical treatment of sludge ash produces detoxified residues that are currently utilised by the fertiliser industry; wet chemical extraction can be economically feasible in recovering P and other by-products. The bioavailability of recovered P depends on soil pH as well as the P-rich material in question. Struvite is a superior recovered P product in terms of plant availability, while use of Ca-P and thermochemically treated sewage sludge ash is limited to acidic soils. These technologies, in addition to others less developed, will be commercially pushed forward by revised fertiliser legislation and foreseeable legislative limits for WWTPs to achieve discharges of <1 mg P/L.