Bioleaching of valuable and hazardous metals from dry discharged incineration slag. An approach for metal recycling and pollutant elimination.

Recycling of process wastes will be in future an essential step to meet the demands for valuable metals of a growing market. Depending on their particle sizes incineration slags are already used to recover metals but particle size fractions below 4 mm are still difficult to recycle. Therefore, different particle size fractions (mesh size 2 and 4 mm, high energy grinded) of dry discharged slags were used for bioleaching with and without the pure cultures Acidithiobacillus ferrooxidans or Leptospirillum ferrooxidans or a mixture of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans in batch cultures. Regarding Al, Cr, Cu, Ni, Mn and the rare earth elements Ce, La and Er, bioleaching was significantly more successful with iron oxidizing bacteria compared to abiotic controls. Metal mobilization for Al, Cu, Mn, Cr and Er with bacteria was between 70 and 100% and for Ce, Ni and La around 50% almost after 7 days, making an industrial application for the high concentrated metals like Al and Cu feasible. In addition to the recovery of valuable metals, a reduction in cost of landfilling was identified. After treatment of the slag with the microorganisms, concentrations of harmful substances in the residues could be reduced and thus a classification in lower safety levels regarding the LAGA or EU regulations was calculated.

Pilot-scale removal and recovery of dissolved phosphate from secondary wastewater effluents with reusable ZnFeZr adsorbent @ Fe3O4/SiO2 particles with magnetic harvesting.

Advanced nanocomposite magnetic particles functionalized with ZnFeZr-adsorbent are developed, characterized and tested for the removal and recovery of phosphate directly from spiked secondary wastewater effluent (∼10 mg/L PO4-P). The phosphate loaded particles can be extracted from the liquid phase via magnetic separation, regenerated in a NaOH solution where phosphate desorption takes place, and reused in numerous cycles. Laboratory experiments demonstrate their reusability and stability in 60 consecutive adsorption/desorption runs where under optimal conditions > 90% total P-recovery efficiency is reached. In addition, pilot tests are performed to verify the proof-of-concept by upscaling the technology and maintain high efficiency of phosphate removal and recovery after treating 1.5 m3 wastewater in 20 cycles. Effluent concentrations <0.05 mg/L PO4-P can be achieved in the treated wastewater. The reclaimed desorption solution is concentrated with phosphate ions through its repetitive application, attaining up to 38-times enrichment (∼380 mg/L PO4-P) compared to the initial concentration in wastewater. The P-rich eluate is used as a source for subsequent precipitation of a solid fertilizer product such as struvite.

Coatings with a Mole-hill Structure of Nanoparticle-Raspberry Containers for Surfaces with Abrasion-Refreshable Reservoir Functionality.

Active silica nanoparticle-based raspberry-like container depots for agents such as antimicrobial substances are presented. The nano raspberry-containers are integrated into coatings in a way that they form a mole-hill structure; i.e., they are partly standing out of the coating. As an application example, it is demonstrated that the containers can be filled with antimicrobially active agents such as nano ZnO or Ag or organic molecules such as thymol. It is demonstrated that the containers can be partly chopped-off via abrasion by rubbing over the surface. This mechanism proves to be an attractive approach to render surfaces refreshable. A first proof of principle for antimicrobial activity of the intact containers in the coatings and the abrasion treated, chopped-off (and thereby reactivated) containers is demonstrated.

Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF).

Modified superparamagnetic nanocomposite microparticles for highly selective Hg(II) or Cu(II) separation and recovery from aqueous solutions.

The synthesis of a reusable, magnetically switchable nanocomposite microparticle, which can be modified to selectively extract and recover Hg(II) or Cu(II) from water, is reported. Superparamagnetic iron oxide (magnetite) nanoparticles act as the magnetic component in this system, and these nanoparticles were synthesized in a continuous way, allowing their large-scale production. A new process was used to create a silica matrix, confining the magnetite nanoparticles using a cheap silica source [sodium silicate (water glass)]. This results in a well-defined, filigree micrometer-sized nanocomposite via a fast, simple, inexpensive, and upscalable process. Hence, because of the ideal size of the resulting microparticles and their comparably large magnetization, particle extraction from fluids by low-cost magnets is achieved.

Effect of pH on the synthesis and properties of luminescent SiO2/calcium phosphate:Eu3+ core-shell nanoparticles.

A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.

Luminescent silicate core-shell nanoparticles: synthesis, functionalization, optical, and structural properties.

SiO(2)/Zn(2)SiO(4):Mn(2+) core-shell nanoparticles with mean diameters in the range of 55-220 nm were prepared by a modified Pechini sol-gel method followed by lyophilization and annealing at temperatures of 800-1100°C. The as-synthesized nanoparticles were characterized by transmission electron microscopy, X-ray diffraction analysis, and photoluminescence spectroscopy. The results demonstrate that the crystal structure of the shell and the optical properties can be tuned by the annealing temperature and a variation of the concentration of doping ions. Under UV excitation, the samples emit green luminescence with its maximum at 525 nm, typical for the Mn(2+) ions in α-Zn(2)SiO(4). The resulting nanoparticles were successfully modified with amine and carboxyl functions with respect to a later attachment of biological moieties.