Renata D. van der Weijden

Copper Recovery Combined with Electricity Production in a Microbial Fuel Cell

A metallurgical microbial fuel cell (MFC) is an attractive alternative for recovery of copper from copper containing waste streams, as the metal is recovered in its metallic form at the cathode, while the energy for metal reduction can be obtained from oxidation of organic materials at the anode with possible additional production of electricity. We studied the recovery of copper in an MFC using a bipolar membrane as a pH separator. Under anaerobic conditions, the maximum power density was 0.43 W/m(2) at a current density of 1.7 A/m(2). In the presence of oxygen, MFC performance improved considerably to a maximum power density of 0.80 W/m(2) at a current density of 3.2 A/m(2). Pure copper crystals were formed on the cathode, and no CuO or Cu(2)O was detected. Removal efficiencies of >99.88% were obtained. The cathodic recovery of copper compared to the produced electricity was 84% (anaerobic) and 43% (aerobic). The metallurgy MFC with the Cu(2+) reducing cathode further enlarges the application range of MFCs.

Calcium phosphate granulation in anaerobic treatment of black water: a new approach to phosphorus recovery.

Recovery of phosphorus from wastewater as calcium phosphate could diminish the need for mining of scarce phosphate rock resources. This study introduces a novel approach to phosphorus recovery by precipitation of calcium phosphate granules in anaerobic treatment of black water. The granules formed in the Upflow Anaerobic Sludge Blanket (UASB) reactor at lab- and demonstration-scale were analyzed for chemical composition and mineralogy by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), Electron microprobe (EMP), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and micro X-ray Diffraction (XRD). The granules had a diameter of 1-2 mm, organic content of 33 wt%, and phosphorus content of 11-13 wt%. Three calcium phosphate phases were identified in the granules: hydroxyapatite, calcium phosphate hydrate and carbonated hydroxyapatite. Without any addition of chemicals, 7 gP/person/year can be recovered with the calcium phosphate granules, representing 2% of the incoming phosphorus in the UASB reactor. As the heavy metal content was lower compared to other phosphorus recovery products, phosphate rock and phosphorus fertilizer, the calcium phosphate granules could be considered as a new phosphorus product.

Biogenic scorodite crystallization by Acidianus sulfidivorans for arsenic removal

Scorodite is an arsenic mineral with the chemical formula FeAsO(4)*2H(2)O. It is the most common natural arsenate associated with arsenic-bearing ore deposits. In the present study we show that the thermoacidophilic iron-oxidizing archaeon Acidianus sulfidivorans is able to precipitate scorodite in the absence of any primary minerals or seed crystals, when grown on 0.7 g L(-1) ferrous iron (Fe(2+)) at 80 degrees C and pH 1 in the presence of 1.9 g L(-1) arsenate (H(3)AsO(4)). The simultaneous biologically induced crystallization of ferric iron (Fe(3+)) and arsenic to scorodite prevented accumulation of ferric iron. As a result, crystal growth was favored over primary nucleation which resulted in the formation of highly crystalline biogenic scorodite very similar to the mineral scorodite. Because mineral scorodite has a low water solubility and high chemical stability, scorodite crystallization may form the basis for a novel method for immobilization of arsenic from contaminated waters with high arsenic concentrations.

High rate copper and energy recovery in microbial fuel cells.

Bioelectrochemical systems (BESs) are a novel, promising technology for the recovery of metals. The prerequisite for upscaling from laboratory to industrial size is that high current and high power densities can be produced. In this study we report the recovery of copper from a copper sulfate stream (2 g L-1 Cu2+) using a laboratory scale BES at high rate. To achieve this, we used a novel cell configuration to reduce the internal voltage losses of the system. At the anode, electroactive microorganisms produce electrons at the surface of an electrode, which generates a stable cell voltage of 485 mV when combined with a cathode where copper is reduced. In this system, a maximum current density of 23 A m-2 in combination with a power density of 5.5 W m-2 was produced. XRD analysis confirmed 99% purity in copper of copper deposited onto cathode surface. Analysis of voltage losses showed that at the highest current, most voltage losses occurred at the cathode, and membrane, while anode losses had the lowest contribution to the total voltage loss. These results encourage further development of BESs for bioelectrochemical metal recovery.

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery.

Interaction of calcium, phosphorus and natural organic matter in electrochemical recovery of phosphate

To address the issues of eutrophication and the potential risk of phosphorus (P) shortage, it is essential to remove and recover P from P-containing streams to close this nutrient cycle. Electrochemical induced calcium phosphate (CaP) precipitation was shown to be an efficient method for P recovery. However, the influence of natural organic matter (NOM) is not known for this treatment. In this paper, the behavior of NOM and its effect on CaP precipitation was studied. In contrast to studies where NOM hindered CaP precipitation, results show that the interaction of NOM with CaP improves the removal of P, independent of the types of NOM. The P removal at the average increased from 43.8 ± 4.9% to 58.5 ± 1.2% in the presence of 1.0 mg L-1 NOM. Based on the yellow color of the CaP product, NOM is co-precipitated. The bulk solution pH with and without buffers has totally different effects on the precipitation process. Without buffer, CaP precipitates on the cathode surface in a wide pH range (pH 4.0-10.0). However, the precipitation process is completely inhibited when the bulk solution is buffered at pH 4.0 and 6.0. This is probably due to neutralization of OH- by the buffers. Regardless of the presence or absence of NOM and solution pH, the recovered products are mainly amorphous CaP unless the electrolysis time was increased to seven days with 4.0 A m-2, in which crystalline CaP formed. These findings advance our understanding on the interaction of Ca, P and NOM species for the application of electrochemical method for P recovery from real wastewater.

The effect of bio-induced increased pH on the enrichment of calcium phosphate in granules during anaerobic treatment of black water

Simultaneous recovery of calcium phosphate granules (CaP granules) and methane in anaerobic treatment of source separated black water (BW) has been previously demonstrated. The exact mechanism behind the accumulation of calcium phosphate (Cax(PO4)y) in CaP granules during black water treatment was investigated in this study by examination of the interface between the outer anaerobic biofilm and the core of CaP granules. A key factor in this process is the pH profile in CaP granules, which increases from the edge (7.4) to the center (7.9). The pH increase enhances supersaturation for Cax(PO4)y phases, creating internal conditions preferable for Cax(PO4)y precipitation. The pH profile can be explained by measured bioconversion of acetate and H2, HCO3– and H+ into CH4 in the outer biofilm and eventual stripping of CO2 and CH4 (biogas) from the granule. Phosphorus content and Cax(PO4)y crystal mass quantity in the granules positively correlated with the granule size, in the reactor without Ca2+ addition, indicating that the phosphorus rich core matures with the granule growth. Adding Ca2+ increased the overall phosphorus content in granules >0.4 mm diameter, but not in fine particles (<0.4 mm). Additionally, H+ released from aqueous phosphate species during Cax(PO4)y crystallization were buffered by internal hydrogenotrophic methanogenesis and stripping of biogas from the granule. These insights into the formation and growth of CaP granules are important for process optimization, enabling simultaneous Cax(PO4)y and CH4 recovery in a single reactor. Moreover, the biological induction of Cax(PO4)y crystallization resulting from biological increase of pH is relevant for stimulation and control of (bio)crystallization and (bio)mineralization in real environmental conditions.

Is There a Precipitation Sequence in Municipal Wastewater Induced by Electrolysis

Electrochemical wastewater treatment can induce calcium phosphate precipitation on the cathode surface. This provides a simple yet efficient way for extracting phosphorus from municipal wastewater without dosing chemicals. However, the precipitation of amorphous calcium phosphate (ACP) is accompanied by the precipitation of calcite (CaCO3) and brucite (Mg(OH)2). To increase the content of ACP in the products, it is essential to understand the precipitation sequence of ACP, calcite, and brucite in electrochemical wastewater treatment. Given the fact that calcium phosphate (i.e., hydroxyapatite) has the lowest thermodynamic solubility product and highest saturation index in the wastewater, it has the potential to precipitate first. However, this is not observed in electrochemical phosphate recovery from raw wastewater, which is probably because of the very high Ca/P molar ratio (7.5) and high bicarbonate concentration in the wastewater resulting in formation of calcite. In the case of decreased Ca/P molar ratio (1.77) by spiking external phosphate, most of the removed Ca in the wastewater was used for ACP formation instead of calcite. The formation of of brucite, however, was only affected when the current density was decreased or the size of cathode was changed. Overall, the removal of Ca and Mg is much more affected by current density than the surface area of cathode, whereas for P removal, the reverse is true. Because of these dependencies, though there is no definite precipitation sequence among ACP, calcite, and brucite, it is still possible to influence the precipitation degree of these species by relatively low current density and high surface area or by targeting phosphorus-rich wastewaters.