The behaviour of pharmaceuticals and heavy metals during struvite precipitation in urine

Separating urine from wastewater at the source reduces the costs of extensive wastewater treatment. Recovering the nutrients from urine and reusing them for agricultural purposes adds resource saving to the benefits. Phosphate can be recovered in the form of struvite (magnesium ammonium phosphate). In this paper, the behaviour of pharmaceuticals and heavy metals during the precipitation of struvite in urine is studied.When precipitating struvite in urine spiked with hormones and non-ionic, acidic and basic pharmaceuticals, the hormones and pharmaceuticals remain in solution for more than 98%.For heavy metals, initial experiments were performed to study metal solubility in urine. Solubility is shown to be affected by the chemical conditions of stored and therefore hydrolysed urine. Thermodynamic modelling reveals low or very low equilibrium solute concentrations for cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb). Experiments confirmed Cd, Cu and Pb carbonate and hydroxide precipitation upon metal addition in stored urine with a reaction half-life of ca. 7 days.For all metals considered, the maximum specific metal concentrations per gram phosphate or nitrogen showed to be typically several orders of magnitudes lower in urine than in commercially available fertilizers and manure. Heavy metals in struvite precipitated from normal stored urine could not be detected.Phosphate recovery from urine over struvite precipitation is shown to render a product free from most organic micropollutants and containing only a fraction of the already low amounts of heavy metals in urine.     

Treatment processes for source-separated urine

The separate collection and treatment of urine has attracted considerable attention in the engineering community in the last few years and is seen as a viable option for enhancing the flexibility of wastewater treatment systems. This comprehensive review focuses on the status of current urine treatment processes and summarises the properties of collected urine. We distinguish between seven main purposes of urine-treatment processes: hygienisation (storage), volume reduction (evaporation, freeze-thaw, reverse osmosis), stabilisation (acidification, nitrification), P-recovery (struvite formation), N-recovery (ion-exchange, ammonia stripping, isobutylaldehyde-diurea (IBDU) precipitation), nutrient removal (anammox) and handling of micropollutants (electrodialysis, nanofiltration, ozonation). The review shows clearly that a wide range of technical options is available to treat collected urine effectively, but that none of these single options can accomplish all seven purposes. Depending on the overall goal of the treatment process, a specific technical solution or a combination of solutions can be found to meet the requirements. Such combinations are not discussed in this paper unless they are explicitly presented in the literature. Except for 'evaporation' and 'storage', none of the processes described have so far advanced beyond the laboratory stage. Considerable development work remains to be done to optimise urine-processing techniques in order to create marketable products.     

Phosphate removal in agro-industry: Pilot- and full-scale operational considerations of struvite crystallization

Pilot-scale struvite crystallization tests using anaerobic effluent from potato processing industries were performed at three different plants. Two plants (P1 & P2) showed high phosphate removal efficiencies, 89 ± 3% and 75 ± 8%, resulting in final effluent levels of 12 ± 3 mg PO₄³⁻-P L⁻¹ and 11 ± 3 mg PO₄³⁻-P L⁻¹, respectively. In contrast, poor phosphate removal (19 ± 8%) was obtained at the third location (P3). Further investigations at P3 showed the negative effect of high Ca²⁺/PO₄³⁻-P molar ratio (ca. 1.25 ± 0.11) on struvite formation. A full-scale struvite plant treating anaerobic effluent from a dairy industry showed the same Ca²⁺ interference. A shift in the influent Ca²⁺/PO₄³⁻-P molar ratio from 2.69 to 1.36 resulted in average total phosphorus removal of 78 ± 7%, corresponding with effluent levels of 14 ± 4 mg P_total L⁻¹ (9 ± 3 mg PO₄³⁻-P L⁻¹). Under these conditions high quality spherical struvite crystals of 2-6 mm were produced.     

Phosphate recovery using hybrid anion exchange: Applications to source-separated urine and combined wastewater streams

There is increasing interest in recovering phosphorus (P) from various wastewater streams for beneficial use as fertilizer and to minimize environmental impacts of excess P on receiving waters. One such example is P recovery from human urine, which has a high concentration of phosphate (200–800 mg P/L) and accounts for a small volume (∼1%) of total wastewater flow. Accordingly, the goal of this study was to evaluate the potential to recover P from source-separated and combined wastewater streams that included undiluted human urine, urine diluted with tap water, greywater, mixture of urine and greywater, anaerobic digester supernatant, and secondary wastewater effluent. A hybrid anion exchange (HAIX) resin containing hydrous ferric oxide was used to recover P because of its selectivity for phosphate and the option to precipitate P minerals in the waste regeneration solution. The P recovery potential was fresh urine > hydrolyzed urine > greywater > biological wastewater effluent > anaerobic digester supernatant. The maximum loading of P on HAIX resin was fresh urine > hydrolyzed urine > anaerobic digester supernatant ≈ greywater > biological wastewater effluent. Results indicated that the sorption capacity of HAIX resin for phosphate and the total P recovery potential were greater for source-separated urine than the combined wastewater streams of secondary wastewater effluent and anaerobic digester supernatant. Dilution of urine with tap water decreased the phosphate loading on HAIX resin. The results of this work advance the current understanding of nutrient recovery from complex wastewater streams by sorption processes.     

Complete nutrient recovery from source-separated urine by nitrification and distillation

In this study we present a method to recover all nutrients from source-separated urine in a dry solid by combining biological nitrification with distillation. In a first process step, a membrane-aerated biofilm reactor was operated stably for more than 12 months, producing a nutrient solution with a pH between 6.2 and 7.0 (depending on the pH set-point), and an ammonium to nitrate ratio between 0.87 and 1.15 gN gN⁻¹. The maximum nitrification rate was 1.8 ± 0.3 gN m⁻² d⁻¹. Process stability was achieved by controlling the pH via the influent. In the second process step, real nitrified urine and synthetic solutions were concentrated in lab-scale distillation reactors. All nutrients were recovered in a dry powder except for some ammonia (less than 3% of total nitrogen). We estimate that the primary energy demand for a simple nitrification/distillation process is four to five times higher than removing nitrogen and phosphorus in a conventional wastewater treatment plant and producing the equivalent amount of phosphorus and nitrogen fertilizers. However, the primary energy demand can be reduced to values very close to conventional treatment, if 80% of the water is removed with reverse osmosis and distillation is operated with vapor compression. The ammonium nitrate content of the solid residue is below the limit at which stringent EU safety regulations for fertilizers come into effect; nevertheless, we propose some additional process steps that will increase the thermal stability of the solid product.     

Ammonium nitrogen removal from coking wastewater by chemical precipitation recycle technology

Ammonium nitrogen removal from wastewater has been of considerable concern for several decades. In the present research, we examined chemical precipitation recycle technology (CPRT) for ammonium nitrogen removal from coking wastewater. The pyrolysate resulting from magnesium ammonium phosphate (MAP) pyrogenation in sodium hydroxide (NaOH) solution was recycled for ammonium nitrogen removal from coking wastewater. The objective of this study was to investigate the conditions for MAP pyrogenation and to characterize of MAP pyrolysate for its feasibility in recycling. Furthermore, MAP pyrolysate was characterized by scanning electron microscope (FESEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR) as well as X-ray diffraction (XRD). The MAP pyrolysate could be produced at the optimal condition of a hydroxyl (OH⁻) to ammonium molar ratio of 2:1, a heating temperature of 110 °C, and a heating time of 3 h. Surface characterization analysis indicated that the main component of the pyrolysate was amorphous magnesium sodium phosphate (MgNaPO₄). The pyrolysate could be recycled as a magnesium and phosphate source at an optimum pH of 9.5. When the recycle times were increased, the ammonium nitrogen removal ratio gradually decreased if the pyrolysate was used without supplementation. When the recycle times were increased, the ammonium nitrogen removal efficiency was not decreased if the added pyrolysate was supplemented with MgCl₂·6H₂O plus Na₂HPO₄·12H₂O during treatment. A high ammonium nitrogen removal ratio was obtained by using pre-formed MAP as seeding material.     

超声强化污泥释磷及MAP法磷回收优化研究

为提高剩余污泥的磷释放与回收效果,采用超声强化EDTA-厌氧处理后的剩余污泥释磷,并以鸟粪石(MAP)结晶法回收上清液中的磷,探究超声对磷释放的影响,同时确定了最佳超声工作参数,采用响应曲面法构建MAP法磷回收的二次多项式模型并验证了模型的适用性。结果表明,超声可以强化污泥中磷的释放,最佳超声工作参数如下:声能密度为1.0 W/m L、超声时间为40 min,在最佳工作参数下可向液相释放60%的TP,TP、PO34--P浓度分别达到未超声处理的1.6倍和1.4倍;经超声后污泥上清液中TP增加量与MLSS、MLVSS减少量呈正相关关系,每溶解1 mg的MLSS向上清液中释放0.010 1 mg的TP;磷回收的最优工艺条件:nMg/nP=2、pH值=9、搅拌时间为21 min,此时磷回收率为89.29%,回收的晶体产物主要成分是磷酸铵镁,其纯度为77.56%,且相比未超声,该条件下的回收量提高了30%。