In this study, the efficiency of electrocoagulation (EC) with iron electrodes was applied to remove two phosphonates, 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) and nitrilotris(methylene) triphosphonic acid (NTMP) from concentrates. This work provides a detailed description of the experimental procedure and results on phosphonate removal and recovery from different electrolytes, including synthetic and real reverse osmosis (RO) membrane concentrates. This research showed high selectivity of EC, removing 100% and 80% of the NTMP and the HEDP respectively, confirming no competition with sulfates, nitrates, or silica. When experimenting with other electrolytes, calcium showed to be critical in enhancing the flocculation process, while calcium carbonate precipitation contributed to capturing the phosphonates from the concentrate. The produced iron oxide (sludge) was confirmed as goethite and akaganéite, and finally transformed into hematite, indicating the oxidation from Fe2+ to Fe3+ during the EC process. After the iron precipitate collection, an alkaline wash of the sludge was enough to recover 100% of the initial phosphorus from the NTMP phosphonate. However, further research is needed to optimize the recovery procedure and to improve the results with the HEDP. 70 and 140 A·m-2 current densities were optimal to bring HEDP and NTMP concentrations down to 32 μM (1 mg·L-1) in only 30 and 10 min respectively. In these conditions, the operational costs, 1.10 and 0.03 €·m-3 of treated concentrate, were estimated for HEDP and NTMP respectively. Even when EC has been widely studied for phosphate removal, this technique has been barely applied to treat concentrates containing phosphonate-based antiscalants. EC opens new possibilities for phosphonates and phosphorus to be removed and recovered respectively from membrane and other concentrates.

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.