Wastewater treatment technologies opened the door for recovery of extracellular polymeric substances (EPS), presenting novel opportunities for use across diverse industrial sectors. Earlier studies showed that a significant amount of phosphorus (P) is recovered within extracted EPS. P recovered within the extracted EPS is an intrinsic part of the recovered material that potentially influences its properties. Understanding the P speciation in extracted EPS lays the foundation for leveraging the incorporated P in EPS to manipulate its properties and industrial applications. This study evaluated P speciation in EPS extracted from aerobic granular sludge (AGS). A fractionation lab protocol was established to consistently distinguish P species in extracted EPS liquid phase and polymer chains. ³¹P nuclear magnetic resonance (NMR) spectroscopy was used as a complementary technique to provide additional information on P speciation and track changes in P species during the EPS extraction process. Findings showed the dominance of organic phosphorus and orthophosphates within EPS, besides other minor fractions. On average, 25% orthophosphates in the polymer liquid phase, 52% organic phosphorus (equal ratio of mono and diesters) covalently bound to the polymer chains, 16% non-apatite inorganic phosphorus (NAIP) precipitates mainly FeP and AlP, and 7% pyrophosphates (6% in the liquid phase and 1% attached to the polymer chains) were identified. Polyphosphates were detected in initial AGS but hydrolyzed to orthophosphates, pyrophosphates, and possibly organic P (forming new esters) during the EPS extraction process. The knowledge created in this study is a step towards the goal of EPS engineering, manipulating P chemistry along the extraction process and enriching certain P species in EPS based on target properties and industrial applications.

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Iron oxide-based adsorbents showed potential to reach ultra-low phosphorus (P) concentrations to prevent eutrophication and recover P. High affinity, high capacity at low P concentrations (<1 mg L⁻¹), good stability, and reusability of the adsorbent are key factors for economic viability. In this study, nanoparticles of goethite (α-FeOOH), a highly stable phase, have been synthesized with increasing Zn²⁺-doping, 0–20 %at. Zn/Fe, to manipulate the surface properties, following the results of a previous work. Mössbauer spectroscopy showed preserved goethite phase and increased point of zero charge (pzc) at low Zn-doping percentages, while at higher percentages (>5%at.) co-existing phases with increased specific surface area formed. Low concentrations (0.1–10 mg L⁻¹) batch adsorption tests showed increased P removal per unit mass with increasing doping. However, the highest pzc, affinity and P removal per unit area were observed for the 5%at. doped sample, suggesting this dopant concentration to provide the most effective surface. A regeneration test, performed at a lower pH than usual, showed preserved, even improved P desorption with increasing doping. Mössbauer spectroscopy showed that the nanoparticle phase and composition, up to 5%at., doping was preserved throughout the process. These results are promising to develop a stable effective Zn-doped goethite-based adsorbent for P recovery at ultra-low concentrations.

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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.

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Phosphorus (P) removal from freshwater bodies to ultra-low concentrations is fundamental to prevent eutrophication, while its recovery is necessary to close the P usage cycle. Iron oxide-based adsorbents seem promising candidates, being abundant, cheap, and easy to synthesize compounds, with good affinity for P. Affinity is the key parameter when targeting ultra-low concentrations. Also, adsorbent regeneration and re-use is fundamental for the economic viability, hence the adsorbent stability is important. Goethite, (α-FeOOH), is one of the most stable iron (Fe³⁺) (hydr)oxide species, with higher affinity, but lower adsorption capacity (per kg) compared to other species. Doping could change goethite surface properties, to boost the adsorption capacity, while preserving the high stability and affinity for P. In this work, pure goethite was compared to goethite doped (5%at.) with different elements of different preferential oxidation states: Zn²⁺, Mn³⁺, and Zr⁴⁺. Doping was successfully achieved for all elements, albeit Zr showed a lower Fe substitution than targeted. Zn doping increased the goethite point of zero charge and adsorption capacity (per mass and per surface area), preserving the high affinity, while Mn- and Zr- doping displayed a decrease in all the parameters. These could be explained with surface protonation as a charge compensation mechanism in Zn²⁺-for-Fe³⁺ substitution. The regeneration test showed improved P recovery for Zr- and Zn-doped goethite. All samples remained stable throughout the whole process. This work provides promising insights on doping as a strategy to manipulate iron oxides surface properties and for developing a highly performing and long-lasting goethite-based adsorbent.

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The study evaluated the combined phosphorus, nitrogen, methane, and extracellular polymeric substances (EPS) recovery from aerobic granular sludge (AGS) wastewater treatment plants. About 30% of sludge organics are recovered as EPS and 25–30% as methane (≈260 ml methane/g VS) by integrating alkaline anaerobic digestion (AD). It was shown that 20% of excess sludge total phosphorus (TP) ends in the EPS. Further, 20–30% ends in an acidic liquid waste stream (≈600 mg PO₄-P/L), and 15% in the AD centrate (≈800 mg PO₄-P/L) as ortho-phosphates in both streams and is recoverable via chemical precipitation. 30% of sludge total nitrogen (TN) is recovered as organic nitrogen in the EPS. Ammonium recovery from the alkaline high-temperature liquid stream is attractive, but it is not feasible for existing large-scale technologies because of low ammonium concentration. However, ammonium concentration in the AD centrate was calculated to be 2600 mg NH₄-N/L _– and ≈20% of TN, making it feasible for recovery. The methodology used in this study consisted of three main steps. The first step was to develop a laboratory protocol mimicking demonstration-scale EPS extraction conditions. The second step was to establish mass balances over the EPS extraction process on laboratory and demonstration scales within a full-scale AGS WWTP. Finally, the feasibility of resource recovery was evaluated based on concentrations, loads, and integration of existing technologies for resource recovery.

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Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH⁻ and the adsorbed P. OH⁻ molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.

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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.

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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.

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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%.

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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.

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Nereda® aerobic granular sludge plants will be urban biorefineries in near future. The development of Kaumera Nereda® Gum extractions from granular sludge was the first step. Kaumera is a biopolymer that can substitute oil derived polymers. Here we share our experiences in the EU funded Water Mining project. A transportable Kaumera extraction installation is build, additional technologies will be integrated: (I) nitrogen recovery, (II) phosphorus recovery and (III) alkaline fermentation of organic sludge residuals.
Together with industrial and public partners we combine fundamental research (alkaline fermentation and phosphorus recovery) with classical engineering (Kaumera Nereda® Gum extraction and nitrogen stripping) and process design. This technological process is supplemented with modern approaches from social, political, economic and environmental sciences to stimulate the commercialisation of these technologies and their concomitant recovery products. @en