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.

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.