The reducibility of iron oxides, depending on their properties, influences the kinetics of dissimilatory iron reduction (DIR) during vivianite recovery in sewage. This study elucidated the correlation between properties of iron oxides and kinetics of DIR during the long-term transformation into vivianite, mediated by Geobacter sulfurreducens PCA and sewage. The positive correlation between surface reactivity of iron oxides and reduction rate constant (k) influenced the terminal vivianite recovery efficiency. Akaganeite with the highest adhesion work and surface energy required the lowest reduction energy (Ea), obtained the highest k of 1.36 × 10-2 day-1 and vivianite recovery efficiency of 43 %. The vivianite yield with akaganeite as iron source was 76-164 % higher than goethite, hematite, feroxyhyte, and ferrihydrite in sewage. The distribution of P with akaganeite during DIR in sewage further suggested a more efficient pathway of direct vivianite formation via bio-reduced Fe(II) rather than indirect reduction of ferric phosphate precipitates. Thus, akaganeite was screened out as superior iron source among various iron oxides for vivianite recovery, which provided insights into the fate of iron sources and the cycle of P in sewage.

Iron minerals in nature are pivotal hosts for heavy metals, significantly influencing their geochemical cycling and eventual fate. It is generally accepted that, vivianite, a prevalent iron phosphate mineral in aquatic and terrestrial environments, exhibits a limited capacity for adsorbing cationic heavy metals. However, our study unveils a remarkable phenomenon that the synergistic interaction between sulfide (S2-) and vivianite triggers an unexpected sulfidation-reoxidation process, enhancing the immobilization of heavy metals such as cadmium (Cd), copper (Cu), and zinc (Zn). For instance, the combination of vivianite and S2- boosted the removal of Cd2+ from the aqueous phase under anaerobic conditions, and ensured the retention of Cd stabilized in the solid phase when shifted to aerobic conditions. It is intriguing to note that no discrete FeS formation was detected in the sulfidation phase, and the primary crystal structure of vivianite largely retained its integrity throughout the whole process. Detailed molecular-level investigations indicate that sulfidation predominantly targets the Fe(II) sites at the corners of the PO4 tetrahedron in vivianite. With the transition to aerobic conditions, the exothermic oxidation of CdS and the S sites in vivianite initiates, rendering it thermodynamically favorable for Cd to form multidentate coordination structures, predominantly through the Cd-O-P and Cd-O-Fe bonds. This mechanism elucidates how Cd is incorporated into the vivianite structure, highlighting a novel pathway for heavy metal immobilization via the sulfidation-reoxidation dynamics in iron phosphate minerals.

Recycling phosphorus from waste activated sludge (WAS) is an effective method to address the nonrenewable nature of phosphorus and mitigate environmental pollution. To overcome the challenge of low phosphorus recovery from WAS due to insufficient disintegration, a method using a citric acid-based natural deep eutectic solvent (CA-NADES) assisted with low-temperature pretreatment was proposed to efficiently release and recover phosphorus. The results of 31P nuclear magnetic resonance (NMR) confirmed that low-temperature pretreatment promoted the conversion of organic phosphorus (OP) to inorganic phosphorus (IP) and enhanced the effect of CA-NADES. Changes in the three-dimensional excitation-emission matrix (3D-EEM) and flow cytometry (FCM) indicated that the method of CA-NADES with low-temperature thermal simultaneously release IP and OP by disintegrating sludge flocs, dissolving extracellular polymeric substances (EPS) structure, and cracking cells. When 5 % (v/v) of CA-NADES was added and thermally treated at 60 °C for 30 min, 43 % of total phosphorus (TP) was released from the sludge. The concentrations of proteins and polysaccharides reached 826 and 331 mg/L, respectively, which were 6.30 and 14.43 times higher than those of raw sludge. The dewatering and settling of the sludge were also improved. Metals were either enriched in the solid phase or released into the liquid phase in small quantities (most efficiencies of less than 10 %) for subsequent clean recovery. The released phosphorus was successfully recovered as vivianite with a rate of 90 %. This study develops an efficient, green, and sustainable method for phosphorus recovery from sludge using NADES and provides new insights into the high-value conversion of sludge.

Phosphorus in sewage is mostly enriched in activated sludge in wastewater treatment plants, making excess sludge an appropriate material for phosphorus recovery. The potential of vivianite (Fe3(PO4)2·8H2O) crystallization-based phosphorus recovery during the anaerobic digestion of thermally hydrolyzed sludge was discussed with influences of organic compounds on the formation of vivianite crystals being investigated in detail. Bovine serum albumin, humic acids and alginate, as model compounds of proteins, humic acids and polysaccharides, all inhibited vivianite crystallization, with the influence of humic acids being the most significant. A sludge retention time of >12 d for effective degradation of organic compounds and a certain degree of FeII excess are suggested to decrease the organics resulting inhibition. The results demonstrate the compatibility of vivianite-crystallization pathway of phosphorus recovery with anaerobic sludge digesters, and reveal the complexity of vivianite formation in the sludge with further research warranted to minimize the inhibitory influences.

Past and present habitability of Mars have been intensely studied in the context of the search for signals of life. Despite the harsh conditions observed today on the planet, some ancient Mars environments could have harbored specific characteristics able to mitigate several challenges for the development of microbial life. In such environments, Fe2+ minerals like siderite (already identified on Mars), and vivianite (proposed, but not confirmed) could sustain a chemolithoautotrophic community. In this study, we investigate the ability of the acidophilic iron-oxidizing chemolithoautotrophic bacterium Acidithiobacillus ferrooxidans to use these minerals as its sole energy source. A. ferrooxidans was grown in media containing siderite or vivianite under different conditions and compared to abiotic controls. Our experiments demonstrated that this microorganism was able to grow, obtaining its energy from the oxidation of Fe2+ that came from the solubilization of these minerals under low pH. Additionally, in sealed flasks without CO2, A. ferrooxidans was able to fix carbon directly from the carbonate ion released from siderite for biomass production, indicating that it could be able to colonize subsurface environments with little or no contact with an atmosphere. These previously unexplored abilities broaden our knowledge on the variety of minerals able to sustain life. In the context of astrobiology, this expands the list of geomicrobiological processes that should be taken into account when considering the habitability of environments beyond Earth, and opens for investigation the possible biological traces left on these substrates as biosignatures.

Class A biosolids from water resource recovery facilities (WRRFs) are increasingly used as sustainable alternatives to synthetic fertilizers. However, the high phosphorus to nitrogen ratio in biosolids leads to a potential accumulation of phosphorus after repeated land applications. Extracting vivianite, an FeP mineral, prior to the final dewatering step in the biosolids treatment can reduce the P content in the resulting class A biosolids and achieve a P:N ratio closer to the 1:2 of synthetic fertilizers. Using ICP-MS, IC, UV-Vis colorimetric methods, Mössbauer spectroscopy, and SEM-EDX, a full-scale characterization of vivianite at the Blue Plains Advanced Wastewater Treatment Plant (AWTTP) was surveyed throughout the biosolids treatment train. Results showed that the vivianite-bound phosphorus in primary sludge thickening, before pre-dewatering, after thermal hydrolysis, and after anaerobic digestion corresponded to 8 %, 52 %, 40 %, and 49 % of the total phosphorus in the treatment influent. Similarly, the vivianite-bound iron concentration also corresponded to 8 %, 52 %, 40 %, and 49 % of the total iron present (from FeCl3 dosing), because the molar ratio between total iron and total incoming phosphorus was 1.5:1, which is the same stoichiometry of vivianite. Based on current P:N levels in the Class A biosolids at Blue Plains, a vivianite recovery target of 40 % to ideally 70 % is required in locations with high vivianite content to reach a P:N ratio in the resulting class A biosolid that matches synthetic fertilizers of 1:1.3 to 1:2, respectively. A financial analysis on recycling iron from the recovered vivianite had estimated that 14-25 % of Blue Plain\'s annual FeCl3 demand can potentially be met. Additionally, model simulations with Visual Minteq were used to evaluate the pre-treatment options that maximize vivianite recovery at different solids treatment train locations.

Electro-fermentation (EF) has been extensively studied for recovering hydrogen and phosphorus from waste activated sludge (WAS), while was limited for the further application due to the low hydrogen yield and phosphorus recovery efficiency. This study proposed an efficient strategy for hydrogen and vivianite recovery from the simulated sludge fermentation liquid by sacrificial iron anode in EF. The optimum hydrogen productivity and the utilization efficiency of short chain fatty acids (SCFAs) reached 45.2 mmol/g COD and 77.6% at 5 d in pH 8. Phosphate removal efficiency achieved at 90.8% at 2 d and the high crystallinity and weight percentage of vivianite (84.8%) was obtained. The functional microbes, i.e., anaerobic fermentative bacteria, electrochemical active bacteria, homo-acetogens and iron-reducing bacteria were highly enriched and the inherent interaction between the microbial consortia and environmental variables was thoroughly explored. This work may provide a theoretical basis for energy/resource recovery from WAS in the further implementation.

Phosphorus recovery is a vital element for the circular economy. Wastewater, especially sewage sludge, shows great potential for recovering phosphate in the form of vivianite. This work focuses on studying the iron, phosphorus, and sulfur interactions at full-scale wastewater treatment plants (Viikinmäki, Finland and Seine Aval, France) with the goal of identifying unit processes with a potential for vivianite formation. Concentrations of iron(III) and iron(II), phosphorus, and sulfur were used to evaluate the reduction of iron and the formation potential of vivianite. Mössbauer spectroscopy and X-ray diffraction (XRD) analysis were used to confirm the presence of vivianite in various locations on sludge lines. The results show that the vivianite formation potential increases as the molar Fe:P ratio increases, the anaerobic sludge retention time increases, and the sulfate concentration decreases. The digester is a prominent location for vivianite recovery, but not the only one. This work gives valuable insights into the dynamic interrelations of iron, phosphorus, and sulfur in full-scale conditions. These results will support the understanding of vivianite formation and pave the way for an alternative solution for vivianite recovery for example in plants that do not have an anaerobic digester.

Damaging the outer layer of the body (the skin) has been a common issue for decades. Fabrication of nanofibrous membranes via the electrospinning technique for the sake of making the wound healing process more facile has caught a lot of interest. For this purpose, a polymeric scaffold of polylactic acid (PLA) was doped with nanoparticles with different concentrations of turmeric/hydroxyapatite/vivianite/graphene oxide. The obtained membrane was tested by XRD, SEM, FTIR, and XPS. The surface topography of the scaffold has experienced changes upon adding different concentrations of the nanoparticles. The contact angle was measured by water droplets. It accentuated change in CA starting from 43.9o for pure condition of PLA to 67.7o for PLA/turmeric/vivianite. The thermogravimetric analysis (TGA) test stated that the PLA scaffold features are thermally stable in relatively high-temperature conditions initiating from room temperature to about 300 °C, meeting the maximum loss in mass of about 5 %. The cell viability was carried out in prepared vitro for the sample which contains PLA/turmeric/vivianite/GO, it was elucidated that the IC50 was around 3060 μg/ml.

Vivianite (Fe3(PO4)2·8H2O), a sink for phosphorus, is a key mineralization product formed during the microbial reduction of phosphate-containing Fe(III) minerals in natural systems, and also in wastewater treatment where Fe(III)-minerals are used to remove phosphate. As biovivianite is a potentially useful Fe and P fertiliser, there is much interest in harnessing microbial biovivianite synthesis for circular economy applications. In this study, we investigated the factors that influence the formation of microbially-synthesized vivianite (biovivianite) under laboratory batch systems including the presence and absence of phosphate and electron shuttle, the buffer system, pH, and the type of Fe(III)-reducing bacteria (comparing Geobacter sulfurreducens and Shewanella putrefaciens). The rate of Fe(II) production, and its interactions with the residual Fe(III) and other oxyanions (e.g., phosphate and carbonate) were the main factors that controlled the rate and extent of biovivianite formation. Higher concentrations of phosphate (e.g., P/Fe = 1) in the presence of an electron shuttle, at an initial pH between 6 and 7, were needed for optimal biovivianite formation. Green rust, a key intermediate in biovivianite production, could be detected as an endpoint alongside vivianite and metavivianite (Fe2+Fe3+2(PO4)2.(OH)2.6H2O), in treatments with G. sulfurreducens and S. putrefaciens. However, XRD indicated that vivianite abundance was higher in experiments containing G. sulfurreducens, where it dominated. This study, therefore, shows that vivianite formation can be controlled to optimize yield during microbial processing of phosphate-loaded Fe(III) materials generated from water treatment processes.