Kinetics of struvite precipitation in synthetic biologically treated swine wastewaters.

An experimental design was set up to understand the influence of five process parameters on the kinetics of struvite precipitation in synthetic swine wastewaters. The responses studied were the kinetics of phosphorus (P) removal, the struvite precipitation rate and the dissolution rate of amorphous calcium phosphates (ACP). The kinetic study showed that the P-removal was complete in less than 1 h and was influenced positively by the added MgO. The precipitation of struvite with MgO was confirmed to follow a first-order kinetic. This study showed that ACP co-precipitated with struvite during the first 30 min. Afterwards, ACP dissolved to maintain the phosphates balance limiting the struvite growth. An initial Mg:Ca > 1.5 induced a complete dissolution of ACP in 1 h. Another experiment was conducted and it validated the results of the statistical model. This experiment also determined that 7-10 h was the best time to recover large crystals. After 10 h, the crystals were broken by stirring.

Correlation between phosphorus removal technologies and phosphorus speciation in sewage sludge: focus on iron-based P removal technologies.

Phosphorus recovery from sewage sludge as secondary raw materials or as a direct P-rich fertiliser is one of the top frontrunner solutions to tackle Phosphorus (P) scarcity and depletion. However, the efficiency of this P recovery process greatly depends on its phosphorus dissolution potential, which in return relies on the phosphorus speciation in the sewage sludge. This article investigates the potential correlation between P speciation in sewage sludge and the iron-based P removal technologies used in sewage treatment plants (STP) through an innovative sequential extraction method based on the SEDEX method that distinguishes quantitatively between ferrous bound phosphate and ferric bound phosphate. XRD and SEM-EDX were also used to characterise P and Fe species in the studied sludge qualitatively. Principal component analysis showed that the sludge characterised by P bound to ferric iron (as the dominant P fraction) are mostly correlated with sludge produced from the CPR process (chemical phosphorus removal) and primary sludge. Moreover, sludge with a non-negligible amount of P bound to ferrous iron were correlated with sludge from the mixed EBPR-CPR process (Enhanced Biological P Removal assisted with CPR). However, Vivianite was only found in CPR sludge with Fe/P molar ratio higher than 0.6.

Mechanisms governing the dissolution of phosphorus and iron in sewage sludge by the bioacidification process and its correlation with iron phosphate speciation.

In the last two decades, phosphorus (P) recovery from sewage sludge liquors gained much interest for its high-quality product potential. However, the consistently reported constraints are the low phosphorus availability and the technical-economical difficulties to increase it through chemical acidification. This article discusses the mechanisms of phosphorus dissolution by the biological acidification process (Biological acidification or acidic fermentation) as an alternative to chemical acidification. In addition, we investigate the potential correlation between the phosphorus dissolution and iron phosphate speciation of several types of sludge from different sewage treatment plants and P removal technologies. The results show that the percentage of P dissolution by bioacidification is always higher than the P dissolution by chemical acidification at equal pH for all types of sludge except for the settled primary sludge. The highest P dissolution was recorded for the sludge from the Enhanced Biological P Removal process assisted with Chemical P Removal process (EBPR-CPR) with around 65% of P dissolution. Three mechanisms were identified as contributing to the increased P dissolution by bioacidification: P release by the Polyphosphate Accumulating Organisms (PAO), P dissolution by pH decrease, and P dissolution by a biological activity at acidic pH (3.7-4) that includes iron reduction and aluminum dissolution. The principal component analysis and Pearson's correlation indicate that P dissolution by bioacidification is negatively correlated with the P-bound to ferric iron, hence positively correlated with the P-bound to ferrous iron, which characterizes the sludge from the EBPR-CPR process. This study suggests that the choice of the P removal technology significantly influences the P recovery from sewage sludge liquors.

Environmental performances of production and land application of sludge-based phosphate fertilizers-a life cycle assessment case study.

Phosphorus (P) is a non-renewable resource extracted from phosphate rock to produce agricultural fertilizers. Since P is essential for life, it is important to preserve this resource and explore alternative sources of P to reduce its criticality. This study aimed to assess whether fertilizing with sludge-based phosphate fertilizers (SBPF) can be a suitable alternative to doing so with fertilizers produced from phosphate rock. Environmental impacts of production and land application of SBPF from four recovery processes were compared to those of two reference scenarios: triple super phosphate (TSP) and sewage sludge. To avoid bias when comparing scenarios, part of the environmental burden of wastewater treatment is allocated to sludge production. The CML-IA method was used to perform life cycle impact assessment. Results highlighted that production and land application of SBPF had higher environmental impacts than those of TSP due to the large amounts of energy and reactants needed to recover P, especially when sludge had a low P concentration. Certain environmental impacts of production and land application of sewage sludge were similar to those of SBPF. Sensitivity analysis conducted for cropping systems highlighted variability in potential application rates of sewage sludge or SBPF. Finally, because they contain lower contents of heavy metals than sewage sludge or TSP, SBPF are of great interest, but they require more mineral fertilizers to supplement their fertilization than sewage sludge. Thus, SBPF have advantages and disadvantages that need to be considered, since they may influence their use within fertilization practices.

Relevance of a perchloric acid extraction scheme to determine mineral and organic phosphorus in swine slurry.

To increase the phosphorus recycling potential from swine slurry, mineral phosphorus products which could be used as fertilizers should be obtained and new processes need to be investigated. A routine method is needed to better evaluate the dissolved and solid mineral phosphorus in swine slurry. Cold perchloric acid extraction method previously developed for wastewater or sludge analysis was adapted. Ionic chromatography was used to measure orthophosphate in extracts. Only one extraction step was needed to distinguish between mineral and organic phosphorus in slurry. Reproducibility of the method was high (less than 5% of variation on the measured fractions). Selectivity was assessed by adding several organic and mineral phosphorus sources in the slurry. Cold perchloric extraction followed by ionic chromatography was very selective in quantifying both the mineral and organic forms of phosphorus in swine slurry.

Physico-chemical, biochemical and nutritional characterisation of 42 organic wastes and residues from France.

The data presented in this article regroup characterisation of organic matter and nutritional composition of 42 organic wastes and residues usually used as substrates for anaerobic digestion. Those wastes have different origins from agro-industrial, agricultural and urban sectors in France including: algae, slaughterhouse waste, fat, food waste, fruits and vegetables residues, green waste, slurry, manure, wastewater treatment plant sludge and agricultural residues. The properties of organic matter are distinguished between global parameters (pH, total solids, volatile solids, COD and BMP), organic matter fractionation (biochemical and Van Soest) and the main nutrients content (N, P, K, Mg, Ca and S).

Sequencing biological acidification of waste-activated sludge aiming to optimize phosphorus dissolution and recovery.

Phosphorus (P) recovery in wastewater treatment plants (WWTP) as pure crystals such as struvite (MgNH4PO4.6H2O), potassium struvite (KMgPO4.6H2O) and calcium phosphates (e.g. Ca3(PO4)2) is an already feasible technique that permits the production of green and marketable fertilizers and the reduction of operational costs. Commercial crystallizers can recovery more than 90% of soluble P. However, most of the P in WWTP sludge is unavailable for the processes (not dissolved). P solubilization and separation are thus the limiting steps in P-crystallization. With an innovative two-step sequencing acidification strategy, the current study has aimed to improve biological P solubilization on waste-activated sludge (WAS) from a full-scale plant. In the first step (P-release), low charges of organic waste were used as co-substrates of WAS pre-fermentation, seeking to produce volatile fatty acids to feed the P-release by Polyphosphate-accumulating organisms, while keeping its optimal metabolic pH (6-7). In this phase, milk serum, WWTP grease, urban organic waste and collective restaurant waste were individually applied as co-substrates. In the second step (P-dissolution), pH 4 was aimed at as it allows the dissolution of the most common precipitated species of P. Biological acidification was performed by white sugar addition, as a carbohydrate-rich organic waste model, which was compared to chemical acidification by HCl (12M) addition. With short retention times (48-96 h) and without inoculum application, all experiences succeeded on P solubilization (37-55% of soluble P), principally when carbohydrate-rich co-substrates were applied. Concentrations from 270 to 450 mg [Formula: see text] were achieved. [Formula: see text].

Dissolution of particulate phosphorus in pig slurry through biological acidification: A critical step for maximum phosphorus recovery as struvite.

Recycling phosphorus as struvite from pig slurry requires an acidification step to dissolve the inorganic solids containing most of the phosphorus. This study focused on the biological acidification of several pig slurries using sucrose as a model organic co-substrate. Lactic acid fermentation occurred systematically, dissolving 60-90% of TP (total phosphorus) and T-Mg (total magnesium) at pH 6 or lower. Optimal pH range for maximum P dissolution aimed at struvite recovery was 5.5-6. A simple model was developed correlating pH, sucrose and buffer capacity to optimize P dissolution and future recovery using real organic waste.

Effects of organic matter on crystallization of struvite in biologically treated swine wastewater.

A sustainable way to recover phosphorus (P) in swine wastewater involves a preliminary step of P dissolution followed by the separation of particulate organic matter (OM). The next two steps are firstly the precipitation of struvite crystals done by adding a crystallization reagent (magnesia) and secondly the filtration of the crystals. To develop the process successfully at an industrial scale, the control of the mechanisms of precipitation is the key point in order to obtain high value-added products, that is, big struvite crystals easy to harvest and handle. Experiments with process parameters optimized previously in a synthetic swine wastewater were performed on real swine wastewater to assess the role of the OM on struvite crystallization. After 24 h, with a pH increase to 6.8 only, 90% of the initial P was precipitated and 60% was precipitated as struvite. 80% of the solid recovered was in the fraction > 100 µm. The other forms recovered were brushite, amorphous calcium phosphate, NaCl, KCl and OM. The influence of OM on struvite precipitation in acidified swine wastewater was negative on the reaction kinetics but positive on the size of the struvite crystals. The presence of colloidal particles increased the size of the struvite crystals but slowed down the kinetics due to the viscosity induced by the repulsive force of the colloids. The maximum size of single struvite crystals (200 µm) was observed with the presence of particulate OM.

Phosphorus recycling potential assessment by a biological test applied to wastewater sludge.

Phosphorus (P) recycling as mineral fertilizer from wastewater activated sludge (WAS) depends on the amount that can be dissolved and separated from the organic matter before the final crystallization step. The aim of the biological phosphorus dissolution potential (BPDP) test developed here was to assess the maximum amount of P that could be biologically released from WAS prior that the liquid phase enters the recovery process. It was first developed for sludge combining enhanced biological phosphorus removal and iron chloride. Because carbohydrates are known to induce acidification during the first stage of anaerobic digestion, sucrose was used as a co-substrate. Best results were obtained after 24-48 h, without inoculum, with a sugar/sludge ratio of 0.5 gCOD/gVS and under strict anaerobic conditions. Up to 75% of the total phosphorus in sludge from a wastewater treatment plant combining enhanced biological phosphorus removal and iron chloride phosphorus removal could be dissolved. Finally, the test was applied to assess BPDP from different sludge using alum compounds for P removal. No dissolution was observed when alum polychloride was used and less than 20% when alum sulphate was used. In all the cases, comparison to chemical acidification showed that the biological process was a major contributor to P dissolution. The possibility to crystallize struvite was discussed from the composition of the liquids obtained. The BPDP will be used not only to assess the potential for phosphorus recycling from sludge, but also to study the influence of the co-substrates available for anaerobic digestion of sludge.

Optimization of struvite precipitation in synthetic biologically treated swine wastewater--determination of the optimal process parameters.

A sustainable way to recover phosphorus (P) in swine wastewater involves a preliminary step of P dissolution followed by the separation of particulate organic matter. The next two steps are firstly the precipitation of struvite crystals done by adding a crystallization reagent (magnesia) and secondly the filtration of the crystals. A design of experiments with five process parameters was set up to optimize the size of the struvite crystals in a synthetic swine wastewater. More than 90% of P was recovered as large crystals of struvite in optimal conditions which were: low Mg:Ca ratio (2.25:1), the leading parameter, high N:P ratio (3:1), moderate stirring rate (between 45 and 90 rpm) and low temperature (below 20 °C).These results were obtained despite the presence of a large amount of calcium and using a cheap reactant (MgO). The composition of the precipitates was identified by Raman analysis and solid dissolution. Results showed that amorphous calcium phosphate (ACP) co-precipitated with struvite and that carbonates were incorporated with solid fractions.