Phosphate Recovery from Aqueous Solutions via Vivianite Crystallization: Interference of FeII Oxidation at Different DO Concentrations and pHs.

Vivianite (Fe3(PO4)2·8H2O) crystallization has attracted increasing attention as a promising approach for removing and recovering P from wastewaters. However, FeII is susceptible to oxygen with its oxidation inevitably influencing the crystallization of vivianite. In this study, the profile of vivianite crystallization in the presence of dissolved oxygen (DO) was investigated at pHs 5-7 in a continuous stirred-tank reactor. It is found that the influence of DO on vivianite crystallization was highly pH-related. At pH 5, the low rate of FeII oxidation at all of the investigated DO of 0-5 mg/L and the low degree of vivianite supersaturation resulted in slow crystallization with the product being highly crystalline vivianite, but the P removal efficiency was only 30-40%. The removal of P from the solution was substantially more effective (to >90%) in the DO-removed reactors at pH 6 and 7, whereas the efficiencies of P removal and especially recovery decreased by 10-20% when FeII oxidation became more severe at DO concentrations >2.5 mg/L (except at pH 6 with 2.5 mg/L DO). The elevated degree of vivianite supersaturation and enhanced rate and extent of FeII oxidation at the higher pHs led to decreases in the size and homogeneity of the products. At the same pH, amorphous ferric oxyhydroxide (AFO)─the product of FeII oxidation and FeIII hydrolysis─interferes with vivianite crystallization with the induction of aggregation of crystal fines by AFO, leading to increases in the size of the obtained solids.

Significantly enhanced P release from vivianite as a fertilizer in rhizospheric soil: Effects of citrate.

The use of vivianite (Fe3(PO4)2∙8H2O) as a slow-release P fertilizer in agriculture could be a promising way for the utilization of the recovered vivianite products from sewage treatment systems but the efficiency of vivianite-P release in the rhizospheric soil was yet unclear. In this work the dissolution of vivianite was investigated under anoxic and aerobic conditions with the focus on the effects of citrate as a common organic matter in the rhizosphere by tracking the kinetics of P release and the variations of aqueous and solid phases. The results show that citrate effectively induced the dissolution of vivianite particles at pH 6 with simultaneous release of Fe and PO4-P. The enhancement of vivianite dissolution was positively correlated to the concentrations of citrate with complete dissolution observed when citrate was above 6 mM. Compared with anoxic conditions, aerobic conditions further enhanced the dissolution of vivianite to some extent, which could be partially attributed to the oxidation and removal of aqueous FeII in the solution that drove the equilibrium towards dissolution. In the presence of 2 mM citrate, the decrease in pH from 6.0 to 4.0 enhanced the vivianite-P release by 56.1%, indicating the pH dependence of the citrate-induced vivianite dissolution. This study has shown that the efficiency of P release from vivianite products as a fertilizer varies largely under different physico-chemical conditions in the rhizospheric microenvironment, which is critical for determining the dosage of vivianite for a specific soil.

Iron Transformation and Its Role in Phosphorus Immobilization in a UCT-MBR with Vivianite Formation Enhancement.

The formation of vivianite (Fe3(PO4)2·8H2O) in iron (Fe)-dosed wastewater treatment facilities has the potential to develop into an economically feasible method of phosphorus (P) recovery. In this work, a long-term steady FeIII-dosed University of Cape Town process-membrane bioreactor (UCT-MBR) system was investigated to evaluate the role of Fe transformations in immobilizing P via vivianite crystallization. The highest fraction of FeII, to total Fe (Fetot), was observed in the anaerobic chamber, revealing that a redox condition suitable for FeIII reduction was established by improving operational and configurational conditions. The supersaturation index for vivianite in the anaerobic chamber varied but averaged ∼4, which is within the metastable zone and appropriate for its crystallization. Vivianite accounted for over 50% of the Fetot in the anaerobic chamber, and its oxidation as it passed through the aerobic chambers was slow, even in the presence of high dissolved oxygen concentrations at circumneutral pH. This study has shown that the high stability and growth of vivianite crystals in oxygenated activated sludge can allow for the subsequent separation of vivianite as a P recovery product.

Inducing in Situ Crystallization of Vivianite in a UCT-MBR System for Enhanced Removal and Possible Recovery of Phosphorus from Sewage.

By mimicking iron(Fe)-based phosphorus (P) immobilization in natural environments, an Fe-retrofitted UCT-MBR involving in situ vivianite crystallization for removing and recovering P from sewage was developed, and its performance was examined in this work. We show that dosing of ferrihydrite, once biological P uptake reached its limit, enabled effective ongoing P removal; whereas conventional conditions in the anaerobic chamber of the University of Cape Town (UCT) system (i.e., a sludge retention time of hours and a completely mixed sludge phase) was insufficient for a satisfactory Fe(III) bioreduction, with the overaccumulation of Fe(III) as fine particles finally resulting in severe membrane fouling and collapse in P removal. The enhancement of reductive conditions in the anaerobic chamber by lowering agitation and adding biocarriers to favor Fe(III) reduction was found to be effective in enabling ongoing P removal and recovery. The average level of effluent P was as low as 0.18 mg/L for a period of 258 d under this condition. Using chemical and spectroscopic methods, the P product was identified as primarily vivianite: Fe3(PO4)2·8H2O. The in situ crystallization of vivianite as a sink for P enabled the UCT-MBR to continuously remove and recover sewage P with no need for sludge discharge.

Release of phosphorus through pretreatment of waste activated sludge differs essentially from that of carbon and nitrogen resources: Comparative analysis across four wastewater treatment facilities.

The accumulation of phosphorus in activated sludge in wastewater treatment plants (WWTPs) provides potential for phosphorus recovery from sewage. This study delves into the potential for releasing phosphorus from waste activated sludge through two distinct treatment methods-thermal hydrolysis and pH adjustment. The investigation was conducted with activated sludge sourced from four WWTPs, each employing distinct phosphorus removal strategies. The findings underscore the notably superior efficacy of pH adjustment in solubilizing sludge phosphorus compared to the prevailing practice of thermal hydrolysis, widely adopted to enhance sludge digestion. The reversibility of phosphorus release within pH fluctuations spanning 2 to 12 implies that the release of sludge phosphorus can be attributed to the dissolution of phosphate precipitates. Alkaline sludge treatment induced the concurrent liberation of COD, nitrogen, and phosphorus through alkaline hydrolysis of sludge biomass and the dissolution of iron or aluminium phosphates, offering potential gains in resource recovery and energy efficiency.

Phosphorus release during alkaline treatment of waste activated sludge from wastewater treatment plants with Al salt enhanced phosphorus removal: Speciation and mechanism clarification.

Chemical phosphorus removal (CPR) is being increasingly adopted in wastewater treatment plants (WWTPs) to enhance P elimination to comply with stringent discharge limits. However, strategies to recover P enriched in the produced waste activated sludge (WAS) are not well developed. In this study, we investigated the release of P in WAS from three WWTPs employing Al salt enhanced CPR by alkaline treatment. We also monitored P mobilization by tracking the dynamics of P fractions and species, the dissolution of major metals, and sludge cell integrities as pH was altered. The level of aqueous total phosphorus (TPaq) in the sludge increased significantly to >200 mg/L (from <11 mg/L in the raw sludge) as the pH was increased to 12, with the majority being PO4-Paq especially at high pHs. The dominance of non-apatite inorganic phosphorus (NAIP) in the sludge-P, a good correlation observed between aqueous PO4-P and aqueous Al, and the reversibility of P mobilization all suggest that the dissolution of Al-bound P was largely responsible for the sludge-P release. Sludge cell integrity, on the other hand, was not closely correlated with TPaq concentrations. Although the level of TP released in this study is among the highest, a more efficient strategy still needs to be developed to further enhance sludge-P release when TP content in the sludge mixture (TPmx) is considered (TPmx was >800 mg/L in this work).