Batch experiments were conducted to study the uranium U(VI) sorption onto bentonite as a function of pH (3 to 8), and initial U(VI) concentrations (5 × 10 −6 and 5 × 10 −5 M) in the presence and absence of sulfate, carbonate, and phosphate. Uranium sorption onto bentonite depended on the initial U(VI) concentration with a stronger sorption at lower concentrations and was high over a wide range of pH in the absence of complexing ligands. In the presence of 0.005 M sulfate, U(VI) sorption was reduced at low pH values due to the competition between SO 4 2− and the uranyl ion for sorption sites on the bentonite surface, or the formation of uranyl-sulfate complexes. In the presence of 0.003 M carbonate, U(VI) sorption decreased sharply at a pH above 7, because of the formation of negatively charged uranyl-carbonate complexes, which are weakly adsorbed onto the bentonite. Uranium sorption onto bentonite was greatly enhanced in the presence of 0.003 M phosphate. Kinetic batch experiments carried out for 5 × 10 −5 M U(VI) at pH values of 3, 5, and 8 revealed that the sorption rate was generally rapid over the first 10 min of the experiments, then slowed down appreciably after 1 to 24 h. Sulfate had little effect on the kinetics of U(VI) sorption; both in the absence and presence of sulfate, sorption equilibrium was attained after 4 h. In the presence of carbonate, attainment of sorption equilibrium required more time than in its absence. The presence of 0.003 M phosphate reduced the time required to reach sorption equilibrium across a wide range of pH compared to phosphate-free systems.

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4-9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO 2 partial pressure of the atmosphere. Uranium concentrations were kept below 100 lg L -1 to avoid precipitation of amorphous Uraniumhydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the wellcrystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.

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The metal(loid) and in particular the Arsenic (As) burden of thirteen agricultural biogas plants and two sewage sludge digesters were investigated together with the corresponding microbial consortia. The latter were characterized by ARISA (automated ribosomal intergenetic spacer analysis) and next generation sequencing. The consortia were found to cluster according to digester type rather than substrate or metal(loid) composition. For selected plants, individual As species in the liquid and gaseous phases were quantified, showing that the microorganisms actively metabolize and thereby remove the As from their environment via the formation of (methylated) volatile species. The As metabolites showed some dependency on the microbial consortia, while there was no statistical correlation with the substrate mix. Finally, slurry from one agricultural biogas plant and one sewage sludge digester was transferred into laboratory scale reactors (“satellite reactors”) and the response to a defined addition of As (30 and 60 µM sodium arsenite) was studied. The results corroborate the hypothesis of a rapid conversion of dissolved As species into volatile ones. Methanogenesis was reduced during that time, while there was no discernable toxic effect on the microbial population. However, the utilization of the produced biogas as replacement for natural gas, e.g. as fuel, may be problematic, as catalysts and machinery are known to suffer from prolonged exposure even to low As concentrations.