Phosphorus runoff from agricultural land is a major driver of eutrophication, with manure serving as a significant source of phosphorus input. In regions such as the Netherlands, high livestock densities and limited land availability pose challenges for manure management, particularly in pig farming. Recovering phosphorus from manure and redistributing it to phosphorus-deficient areas offers a sustainable solution. This study explores phosphate recovery via vivianite (Fe₃(PO₄)₂·8H₂O) precipitation—a method previously demonstrated in municipal wastewater treatment plant sludge—and evaluates its applicability to pig manure. Vivianite formation was investigated in fresh, 4-month-aged, and digested pig manure, as well as in Thermal Hydrolysis Plant (THP) derived digested sewage sludge. A key finding is that high dissolved inorganic carbon (DIC) concentrations inhibit vivianite formation by promoting siderite (FeCO₃) precipitation. In digested manure, a DIC threshold of approximately 3 g/L HCO₃⁻ was identified, below which vivianite formation is favored. THP sludge, characterized by elevated DIC, exhibited similar inhibitory effects. More generally, vivianite was shown to form without significant competition with siderite if the DIC concentration is <2.5 times the iron concentration. Experimental results were compared with thermodynamic predictions using Visual MINTEQ and experiments in ultrapure water, revealing discrepancies which may be attributed to the ionic composition in environmental matrices. Strategies such as combining ammonia and DIC stripping or targeting fresh manure were shown to enhance vivianite formation. These findings can be used to propose the integration of vivianite-based phosphorus recovery into broader resource recovery frameworks, including biomethane production, ammonium recovery, and carbon capture.

The eutrophic Bouvigne pond (Breda, The Netherlands) regularly suffers from cyanobacterial blooms. To improve the water quality, the external nutrient loading and the nutrient release from the pond sediment have to be reduced. An enclosure experiment was performed in the pond between March 9 and July 29, 2020 to compare the efficiency of dredging, addition of the lanthanum-modified bentonite clay Phoslock® (LMB), the aluminum-modified zeolite Aqual-P™ (AMZ) and FeCl₂ to mitigate nutrient release from the sediment. The treatments improved water quality. Mean total phosphorus (TP) concentrations in water were 0.091, 0.058, 0.032, 0.031, and 0.030 mg P L^-1 in controls, dredged, FeCl₂, LMB and AMZ treated enclosures, respectively. Mean filterable P (FP) concentrations were 0.056, 0.010, 0.009, 0.005, and 0.005 mg P L^-1 in controls, dredged, FeCl₂, LMB and AMZ treatments, respectively. Total nitrogen (TN) and dissolved inorganic nitrogen (DIN) were similar among treatments; lanthanum was elevated in LMB treatments, Fe and Cl in FeCl₂ treatments, and Al and Cl in AMZ treatments. After 112 days, sediment was collected from each enclosure, and subsequent sequential P extraction revealed that the mobile P pool in the sediments had reduced by 71.4%, 60.2%, 38%, and 5.2% in dredged, AMZ, LMB, and FeCl₂ treatments compared to the controls. A sediment core incubation laboratory experiment done simultaneously with the enclosure experiment revealed that FP fluxes were positive in controls and cores from the dredged area, while negative in LMB, AMZ and FeCl₂ treated cores. Dissolved inorganic nitrogen (DIN) release rate in LMB treated cores was 3.6 times higher than in controls. Overall, the applied in-lake treatments improved water quality in the enclosures. Based on this study, from effectiveness, application, stakeholders engagement, costs and environmental safety, LMB treatment would be the preferred option to reduce the internal nutrient loading of the Bouvigne pond, but additional arguments also have to be considered when preparing a restoration.

It was recently discovered that vivianite (Fe₃(PO₄)₂.8H₂O) could be magnetically extracted from digested activated sludge which opened a new route for phosphorus recovery (Wijdeveld et al. 2022). While its formation in digested sludge is regularly reported, it is not yet studied for fresh, undigested activated sludge. In particular, the extent to which vivianite could form during sludge storage is missing. The current research showed that iron reduction was completed after 2–4 days of anaerobic storage, and the vivianite appeared to form quickly from the pool of reduced iron made available. After sludge thickening at the wastewater treatment plant (30 h retention time), around 11% of the iron was vivianite. With subsequent 1–3 days of anaerobic storage, this fraction increased to 50–55%. After this storage, almost all the vivianite that could potentially form did form. This research concluded that efficient vivianite formation can be achieved without a sludge digester, showing phosphorus recovery potential from undigested sludge via vivianite recovery. Besides, the recovery of vivianite from undigested sludge presents advantages like the reduction of the sludge to dispose of and mitigation of the vivianite scaling formation.

Phosphorus (P) is an essential resource for food production and chemical industry. Phosphorus use has to become more sustainable and should include phosphorus recycling from secondary sources. About 20% of P ends up in sewage sludge, making this a substantial secondary P source. There is currently a technological gap to recover P from sludge locally at wastewater treatment plants (WWTP) that remove P by dosing iron. Vivianite (Fe₃(PO₄)₂•8(H₂O)) is the main iron phosphate mineral that forms during anaerobic digestion of sewage sludge, provided that enough iron is present. Vivianite is paramagnetic and can be recovered using a magnetic separator. In this study, we have scaled up vivianite separation from lab-scale to bench- and pilot-scale. Bench-scale tests showed good separation of vivianite from digested sewage sludge and that a pulsation force is crucial for obtaining a concentrate with a high P grade. A pilot-scale magnetic separator (capacity 1.0 m³/h) was used to recover vivianite from digested sewage sludge at a WWTP. Recirculating and reprocessing sludge allows over 80% vivianite recovery within three passes. A concentrated P-product was produced with a vivianite content of up to 800 mg/g and a P content of 98 mg/g. P recovery is limited by the amount of P bound in vivianite and can be increased by increased iron dosing. With sufficient iron dosing, the vivianite content can be increased, and subsequently more P can be recovered. This would allow compliance with existing German legislation, which requires a P recovery larger than 50%.

In a wastewater treatment plant (WWTP), several sludge streams exist and the composition of their liquid phase varies with time and place. For evaluating the potential for formation of precipitates and equilibria for weak acids/bases, the ionic strength and chemical composition need to be known. This information is often not available in literature, and even neglected in chemical model-based research. Based on a literature review, we proposed three ranges of concentration (low, typical and high) for the major constituents of the liquid phase of the different streams in a WWTP. The study also discusses the reasons for the concentration evolution, and the exceptional cases, to allow readers to consider the right range depending on their situation. The ionic strength of the different streams and the contribution of its constituents were calculated based on the ionic composition. The major contributors to the ionic strength for the wastewater-based streams (influent, effluent and mixed sludge) were Na+, Cl-, Mg2+ and Ca2+, representing 50-70% of the ionic strength. For digestate, NH4+ and HCO3- accounted for 65-75% of the ionic strength. Even though the ionic strength is recognized to impact several important wastewater treatment processes, its utilization in literature is not always adequate, which is discussed in this study.

The presence of soluble iron and phosphorus in wastewater sludge can lead to vivianite scaling. This problem is not often reported in literature, most likely due to the difficult identification and quantification of this mineral. It is usually present as a hard and blue deposit that can also be brown or black depending on its composition and location. From samples and information gathered in 14 wastewater treatment plants worldwide, it became clear that vivianite scaling is common and can cause operational issues. Vivianite scaling mainly occurred in 3 zones, for which formation hypotheses were discussed. Firstly, iron reduction seems to be the trigger for scaling in anaerobic zones like sludge pipes, mainly after sludge thickening. Secondly, pH increase was evaluated to be the major cause for the formation of a mixed scaling (a majority of oxidized vivianite with some iron hydroxides) around dewatering centrifuges of undigested sludge. Thirdly, the temperature dependence of vivianite solubility appears to be the driver for vivianite deposition in heat exchanger around mesophilic digesters (37 °C), while higher temperatures potentially aggravate the phenomenon, for instance in thermophilic digesters. Mitigation solutions like the use of buffer tanks or steam injections are discussed. Finally, best practices for safe mixing of sludges with each other are proposed, since poor admixing can contribute to scaling aggravation. The relevance of this study lays in the occurrence of ironphosphate scaling, while the use of iron coagulants will probably increase in the future to meet more stringent phosphorus discharge limits.

The recovery of phosphorus from secondary sources like sewage sludge is essential in a world suffering from resources depletion. Recent studies have demonstrated that phosphorus can be magnetically recovered as vivianite (Fe(II)₃(PO₄)₂∗8H₂O) from the digested sludge (DS) of Waste Water Treatment Plants (WWTP) dosing iron. To study the production of vivianite in digested sludge, the quantity of Fe dosed at the WWTP of Nieuwveer (The Netherlands) was increased (from 0.83 to 1.53 kg Fe/kg P in the influent), and the possible benefits for the functioning of the WWTP were evaluated. Higher Fe dosing is not only relevant for P-recovery, but also for maximal recovery of organics from influent for e.g. biogas production. The share of phosphorus present as vivianite in the DS increased from 20% to 50% after the increase in Fe dosing, making more phosphorus available for future magnetic recovery. This increase was directly proportional to the increase of Fe in DS, suggesting that vivianite could be favored not only thermodynamically, but also kinetically. Interestingly, analyses suggest that several types of vivianite are formed in the WWTP, and could differ in their purity, oxidation state or crystallinity. These differences could have an impact on the subsequent magnetic separation. Following the Fe dosing increase, P in the effluent and H₂S in the biogas both decreased: 1.28 to 0.42 ppm for P and 26 to 8 ppm for H₂S. No negative impact on the nitrogen removal, biogas production, COD removal or dewaterability was observed. Since quantification of vivianite in DS is complicated, previous studies were reviewed and we proposed a more accurate Mössbauer spectroscopy analysis and fitting for sludge samples. This study is important from a P recovery point of view, but also because iron addition can play a crucial role in future resource recovery wastewater facilities.

To prevent eutrophication of surface water, phosphate needs to be removed from sewage. Iron (Fe) dosing is commonly used to achieve this goal either as the main strategy or in support of biological removal. Vivianite (Fe(II) ₃ (PO ₄ ) ₂ * 8H ₂ O) plays a crucial role in capturing the phosphate, and if enough iron is present in the sludge after anaerobic digestion, 70–90% of total phosphorus (P) can be bound in vivianite. Based on its paramagnetism and inspired by technologies used in the mining industry, a magnetic separation procedure has been developed. Two digested sludges from sewage treatment plants using Chemical Phosphorus Removal were processed with a lab-scale Jones magnetic separator with an emphasis on the characterization of the recovered vivianite and the P-rich caustic solution. The recovered fractions were analyzed with various analytical techniques (e.g., ICP-OES, TG-DSC-MS, XRD and Mössbauer spectroscopy). The magnetic separation showed a concentration factor for phosphorus and iron of 2–3. The separated fractions consist of 52–62% of vivianite, 20% of organic matter, less than 10% of quartz and a small quantity of siderite. More than 80% of the P in the recovered vivianite mixture can be released and thus recovered via an alkaline treatment while the resulting iron oxide has the potential to be reused. Moreover, the trace elements in the P-rich caustic solution meet the future legislation for recovered phosphorus salts and are comparable to the usual content in Phosphate rock. The efficiency of the magnetic separation and the advantages of its implementation in WWTP are also discussed in this paper.

Adsorption is often suggested for to reach very low phosphate levels in municipal wastewater effluent and even to recover phosphate. Adsorbent performance is usually associated with surface area but the exact role of the pore size distribution (PSD) is unclear. Here, we show the effect of the PSD on phosphate adsorption. Granular activated carbons (GACs) with varying PSDs were treated with potassium permanganate followed by reaction with ferric chloride to form iron oxide coated GACs (Fe-GACs). Energy dispersive X-ray and kinetics experiments confirmed that manganese anchored on the GAC is important for subsequent iron attachment. Mössbauer spectroscopy showed presence of ferrihydrite in Fe-GAC. Transmission electron microscopy showed that the iron oxide particles are not present in the micropores of the GACs. Phosphate adsorption isotherms were performed with the Fe-GACs and adsorption at lower phosphate concentrations correlated with the porous area of &#x003E;3 nm of the adsorbents, a high fraction of which is contributed by mesopores. These results show that high surface areas of GACs resulting from micropores do not contribute to adsorption at low phosphate concentrations. This can be explained by the micropores being difficult to coat with iron oxide nanoparticles, but in addition the diffusion of phosphate into these pores could also be hindered. It is therefore recommended to use backbones having high mesoporous areas. This information is useful for developing adsorbents particularly for applications treating low phosphate concentrations, for e.g. in municipal wastewater effluent polishing.