Phosphate and potassium recovery from source separated urine through struvite precipitation

Phosphate can be recovered as struvite or apatite in fluidised bed reactors. Urine has a much higher phosphate concentration than sludge reject water, allowing simpler (and less expensive) process for precipitation of phosphates. A stirred tank reactor with a special compartment for liquid solid separation was used to precipitate struvite from urine. Magnesium ammonium phosphate as well as potassium magnesium phosphate are two forms of struvite that were successfully precipitated. Liquid/solid separation was very effective, but the compaction of struvite was rather poor in the case of potassium struvite. Crystals did not form clusters and maintained the typical orthorhombic structure. Ammonium struvite had slightly lower effluent phosphate concentrations, but an average of 95% of influent phosphate was removed regardless of ammonium or potassium struvite precipitation. Fluid mechanics is believed to be important and should inform further work.     

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.     

Enhancing anaerobic digestibility and phosphorus recovery of dairy manure through microwave-based thermochemical pretreatment

Anaerobic digestion and struvite precipitation are two effective ways of treating dairy manure for recovering biogas and phosphorus. Anaerobic digestion of dairy manure is commonly limited by slow fiber degradation, while struvite precipitation is limited by the availability of orthophosphate. The aim of this work is to study the possibility of using microwave-based thermochemical pretreatment to simultaneously enhance manure anaerobic digestibility (through fiber degradation) and struvite precipitation (through phosphorus solubilization). Microwave heating combined with different chemicals (NaOH, CaO, H₂SO₄, or HCl) enhanced solubilization of manure and degradation of glucan/xylan in dairy manure. However, sulfuric acid-based pretreatment resulted in a low anaerobic digestibility, probably due to the sulfur inhibition and Maillard side reaction. The pretreatments released 20-40% soluble phosphorus and 9-14% ammonium. However, CaO-based pretreatment resulted in lower orthophosphate releases and struvite precipitation efficiency as calcium interferes with phosphate to form calcium phosphate. Collectively, microwave heating combined with NaOH or HCl led to a high anaerobic digestibility and phosphorus recovery. Using these two chemicals, the performance of microwave- and conventional-heating in thermochemical pretreatment was further compared. The microwave heating resulted in a better performance in terms of COD solubilization, glucan/xylan reduction, phosphorus solubilization and anaerobic digestibility. Lastly, temperature and heating time used in microwave treatment were optimized. The optimal values of temperature and heating time were 147 °C and 25.3 min for methane production, and 135 °C and 26 min for orthophosphate release, respectively.     

The contribution of exopolysaccharides induced struvites accumulation to ammonium adsorption in aerobic granular sludge

Aerobic granular sludge from a lab-scale reactor with simultaneous nitrification/denitrification and enhanced biological phosphorus removal processes exhibited significant amount of ammonium adsorption (1.5 mg NH₄⁺-N/g TSS at an ammonium concentration of 30 mg N/L). Potassium release accompanied ammonium adsorption, indicating an ion exchange process. The existence of potassium magnesium phosphate (K-struvite) as one of potassium sources in the granular sludge was studied by X-ray diffraction analysis (XRD). Artificially prepared K-struvite was indeed shown to adsorb ammonium. Alginate-like exopolysaccharides were isolated and their inducement for struvite formation was investigated as well. Potassium magnesium phosphate proved to be a major factor for ammonium adsorption on the granular sludge. Struvites (potassium/ammonium magnesium phosphate) accumulate in aerobic granular sludge due to inducing of precipitation by alginate-like exopolysaccharides.     

Struvite crystallisation and recovery using a stainless steel structure as a seed material

A metallic system acting as a seed substrate has been designed and developed in order to assess its efficiency in recovering phosphorus as struvite. The device, consisting of two concentric stainless steel meshes, was immerged in the upper section of a pilot crystallisation reactor fed with synthetic liquors (MgCl₂·6H₂O, NH₄H₂PO₄,) for 2 h. Apart from soluble PO₄-P removals which remained in the range 79-80% with or without application of the metallic system, it was found that under the specific operating conditions tested the meshes were capable of accumulating struvite at a rate of 7.6 gm⁻² h⁻¹, hence reducing significantly the amount of fine particles remaining in solution from 302.2 to 12 mg L⁻¹ when compared to trials without mesh.     

Usage of phosphoric acid plant's circulate pond waters in struvite precipitation—Effect of conditions

Struvite is a suitable fertilizer, and electrochemical precipitation of nutrients from industrial waters provides one answer to the circular economy. Molar ratio between ammonium and phosphate is crucial: Water suitable for the precipitation includes more or at least the same amount ammonium than phosphate. That kind of water typically does not exist in industry. Therefore, ammonium-rich industrial water was mixed with phosphorus-rich water to obtain a suitable molar ratio for struvite precipitation. Parameters were studied to determine their effect on removal-% and struvite yield. 100% struvite yield was obtained under several conditions even without pH control with pH 7–9. The highest phosphate removal (99.7%) was occurred with the molar ratio 1.7:2:1 for Mg:NH₄:PO₄ (pH 9.0). Waters dilution prevents magnesium anode corrosion. Formed struvite has potential as recycled fertilizer due to low bioavailability of metals and high leachability of nutrients studied by four-stage sequential leaching.     

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.     

Fate of the pathogen indicators phage ΦX174 and Ascaris suum eggs during the production of struvite fertilizer from source-separated urine

Human urine has the potential to be a sustainable, locally and continuously available source of nutrients for agriculture. Phosphate can be efficiently recovered from human urine in the form of the mineral struvite (MgNH₄PO₄·6H₂O). However, struvite formation may be coupled with the precipitation of other constituents present in urine including pathogens, pharmaceuticals, and heavy metals. To determine if struvite fertilizer presents a microbiological health risk to producers and end users, we characterized the fate of a human virus surrogate (phage ΦX174) and the eggs of the helminth Ascaris suum during a low-cost struvite recovery process. While the concentration of phages was similar in both the struvite and the urine, Ascaris eggs accumulated within the solid during the precipitation and filtration process. Subsequent air-drying of the struvite filter cake partially inactivated both microorganisms; however, viable Ascaris eggs and infective phages were still detected after several days of drying. The infectivity of both viruses and eggs was affected by the specific struvite drying conditions: higher inactivation generally occurred with increased air temperature and decreased relative humidity. On a log-log scale, phage inactivation increased linearly with decreasing moisture content of the struvite, while Ascaris inactivation occurred only after achieving a minimum moisture threshold. Sunlight exposure did not directly affect the infectivity of phages or Ascaris eggs in struvite cakes, though the resultant rise in temperature accelerated the drying of the struvite cake, which contributed to inactivation.     

Controlled struvite crystallisation for removing phosphorus from anaerobic digester sidestreams

Enhanced biological phosphorus removal wastewater treatment plants that use anaerobic digesters for sludge treatment, have high phosphorus concentrations in the sidestreams from their sludge dewatering equipment. To remove phosphorus from such sidestreams controlled struvite crystallisation can be used. Struvite (or MAP) is a naturally occurring crystal of magnesium, ammonium and phosphate. We present operational results obtained with a continuously operated pilot-scale MAP reactor. The pilot-scale reactor (143 l) was an air agitated column reactor with a reaction and a settling zone, based on the Phosnix process of Unitika Ltd., Japan. The influent to the MAP reactor was centrate from the centrifuge that dewaters anaerobically digested sludge at the Oxley Creek wastewater treatment plant in Brisbane. We used a 60% magnesium hydroxide slurry to add the required magnesium to the process and to obtain the alkaline pH value required. The pilot-scale MAP process achieved an ortho-P removal ratio of 94% from an average influent ortho-P concentration of 61 mg/l. The reactor was operated at a pH of around 8.5. Insufficient dosing of magnesium reduced the P removal performance. There was no influence of the hydraulic residence time on the process in the range of 1-8 h. The dry MAP product had cadmium, lead and mercury concentrations well below the legal limits for fertilisers in Queensland, Australia and can be reused as a valuable slow-release fertiliser.     

Removal of phosphate from aqueous solution by thermally treated natural palygorskite

The potential of activated palygorskite was assessed for sorption of phosphate from aqueous solution. The natural palygorskite used was treated by thermal activation over 100-1000 °C for 2 h. The thermal activation increased the phosphate sorption capacity and the highest phosphate sorption capacity occurred at 700 °C. H700 (palygorskite heated at 700 °C) showed higher sorption rate than natural palygorskite (NPAL), and the removal was favorable in acidic media. The sorption data were described using Freundlich isotherm equation over the concentration range (5-1000 mg/L) (25 °C). Calcium bound phosphorus was the main fraction of the adsorbed phosphorus, about 98.0% in NPAL and 58.2% in H700, but the extractive Ca-P species varied greatly, Ca₂-P was 87.7% in NPAL and 3.0% in H700, Ca₈-P was 10.1% in NPAL and 54.5% in H700, and metal bound phosphorus was less than 2% in NPAL but more than 41.4% in H700, respectively. The dependence of the phosphate sorption capacity in the heating samples on thermal activation appears to be related to major changes in the crystal structure of palygorskite, and more calcium, iron and aluminum were released from the crystal matrix at 700 °C, which promoted phosphorus sorption.     

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.     

Sulfide-induced nitrate reduction in the sludge of an anaerobic digester of a zero-discharge recirculating mariculture system

The anaerobic digester is a vital component in a zero-discharge mariculture system as therein most of the organic matter is mineralized and nitrogen-containing compounds are converted to gaseous N₂. Although denitrification is a major respiratory process in this nitrate-rich treatment stage, also sulfate respiration takes place and may cause undesirable high sulfide concentrations in the effluent water. To examine the effect of sulfide on nitrate reduction, in situ depth profiles of inorganic nitrogen and sulfur compounds were determined. Additionally, nitrate reduction was examined as a function of ambient sulfide concentrations in sludge collected from different locations in the anaerobic reactor. Depth profiles showed high concentrations of nitrate and low concentrations of sulfide and ammonia in the aqueous layer of the reactor. A sharp decrease of nitrate and an increase in sulfide and ammonia concentrations was measured at the water-sludge interface. Nitrate reduction was highest in this interface zone with rates of up to 8.05 ± 0.57 μmol NO₃⁻ h⁻¹ g_(sludge)⁻¹. Addition of sulfide increased the nitrate reduction rate at all sludge depths, pointing to the important role of autotrophic denitrification in the anaerobic reactor. Dissimilatory nitrate reduction to ammonia (DNRA) was found to be low in all sludge layers but was enhanced when sludge was incubated at high sulfide concentrations. Although nitrate reduction rates increased as a result of sulfide addition to sludge samples, no differences in nitrate reduction rates were observed between the samples incubated with different initial sulfide concentrations. This as opposed to sulfide oxidation rates, which followed Michaelis-Menten enzymatic kinetics. Partial oxidation of sulfide to elemental sulfur instead of a complete oxidation to sulfate, could explain the observed patterns of nitrate reduction and sulfide oxidation in sludge incubated with different initial sulfide concentrations.     

Interactions of land use and dynamic river conditions on sorption equilibria between benthic sediments and river soluble reactive phosphorus concentrations

Within-river cycling of P is a crucial link between catchment pollution sources and the resulting ecological impacts and integrates the biogeochemistry and hydrodynamics of river systems. This study investigates benthic sediment P sorption in relation to river soluble reactive phosphorus (SRP) concentrations during high- to low-flow changes in a major mixed land use river system in NE Scotland. We hypothesised that sediments comprised P sinks during moderate to higher flows but became P saturated with loss of buffering function during prolonged baseflow. Sediment characteristics were evaluated and equilibrium P concentrations (EPC₀) calculated using a standardised batch adsorption method (EPC₀ values 0.04-1.75 μmol P l⁻¹). Pollution-impacted tributaries (32-69% catchment agricultural land cover) had increased SRP concentrations (0.19-2.62 μmol P l⁻¹) and maintained EPC₀ < SRP values during changing flow conditions. Moorland-dominated tributaries and main stem sites had small SRP concentrations (0.03-0.19 μmol P l⁻¹) but showed EPC₀ > SRP values during summer baseflow so that sediments were indicated as P sources. This deviation from a geochemical sediment-water P equilibrium was attributed to biological accumulation of P from the water column into the sediments. In particular, large stores of sediment P accumulated in main stem reaches below agricultural tributaries and this may be consequential for sensitive downstream ecosystems. Hence, biogeochemical processes at the river bed may strongly influence river SRP cycling between geochemical and biotic pools. The nature of this internal reservoir of river P and its ecosystem interactions needs better understanding to enable best results to be attained from catchment mitigation actions designed to maintain/improve ecological status under the Water Framework Directive.     

Phosphorus recovery by struvite crystallization in WWTPs: Influence of the sludge treatment line operation

Phosphorus recovery by struvite (MgNH₄PO₄·6H₂O) crystallization is one of the most widely recommended technologies for treating sludge digester liquors especially in wastewater treatments plants (WWTP) with enhanced biological phosphorus removal (EBPR). In this paper, phosphorus recovery by struvite crystallization is assessed using the rejected liquors resulting from four different operational strategies of the sludge treatment line. Phosphorus precipitation and recovery efficiencies of between 80-90% and 70-85%, respectively, were achieved in the four experiments. The precipitates formed were mainly struvite, followed by amorphous calcium phosphate and, in some experiments, by calcite. The highest global phosphorus recovery taking into account both the sludge line and the crystallizer was achieved when mixed thickening and high elutriation were carried out (8.4 gP/kg treated sludge). However, low struvite content was obtained in the crystallizer with this operation scheme due to the high calcium content in the elutriation stream. Therefore, if the final purpose is to obtain struvite, the reduction of the elutriation flowrate is widely recommended in the case of high water hardness.     

Enhanced biological phosphorus removal by granular sludge: From macro- to micro-scale

In this study, phosphorus accumulating microbial granules were successfully cultivated in a sequencing batch reactor (SBR) using synthetic wastewater. The average diameter of the granules was 0.74 mm and the diameter distribution fitted well with normal distribution with a correlation coefficient of 0.989. Good performance of biological phosphorus removal (BPR) was obtained in the granular system. The average phosphorus removal efficiency was over 94.3% and the level of phosphorus in the effluent was below 0.50 mg/L during 300 days of operation. Particle analysis showed that positive charged particles were formed with the release of phosphorus in the anaerobic stage. These particles served as the cores of granules and stimulate the granulation. The maturated granules had a well-formed micro-pore structure with an average pore width between 291.5 nm and 446.5 nm. The spatial distribution of phosphorus decreased gradually from the surface to the center of the granules. Smaller granules had a higher specific area, pore width and phosphorus removal activity than bigger granules.     

Anthropogenic phosphorus flow analysis of Hefei City, China

The substance flow analysis (SFA) method was employed to examine phosphorus flow and its connection to water pollution in the city of Hefei, China, in 2008. As human activity is the driving force of phosphorus flux from the environment to the economy, the study provides a conceptual framework for analyzing an anthropogenic phosphorus cycle that includes four stages: extraction, fabrication and manufacturing, use, and waste management. Estimates of phosphorus flow were based on existing data as well as field research, expert advice, local accounting systems, and literature. The total phosphorus input into Hefei in 2008 reached 7810 tons, mainly as phosphate ore, chemical fertilizer, pesticides, crops and animal products. Approximately 33% of the total phosphorus input left the area, and nearly 20% of that amount was discharged as waste to surface water. Effluent containing excessive fertilizer from farming operations plays an important role in phosphorus overloads onto surface water; the other major emission source is sewage discharge. We also provide suggestions for reducing phosphorus emissions, for example reducing fertilizer use, recycling farming residues, and changing human consumption patterns.     

Distribution of uranium in soil components of agricultural fields after long-term application of phosphate fertilizers

Long-term application of phosphate fertilizers causes accumulation of U in the surface soil of agricultural fields. We investigated the soil constituents that contribute to the accumulation of U by using chemical extraction methods. Surface soil samples were obtained from upland fields, pastures, and paddy fields cultivated without any phosphate fertilizer (control site), with NPK fertilizer (NPK site), and with both NPK fertilizer and compost (NPK + compost site) for more than 20 years. In addition to the total U (U_t) concentration in soil, the concentrations of pyrophosphate- and acid oxalate-extractable U were determined as a measure of U associated with soil organic matter and poorly crystalline Fe/Al minerals in soil, respectively. The total, pyrophosphate-extractable, and acid oxalate-extractable U concentrations were higher in the soil obtained from the NPK and NPK + compost sites than in that obtained from the control site. The difference in the U concentrations between the NPK or NPK + compost site and the control site corresponded with the increased U concentration observed after the application of the phosphate fertilizer or both the fertilizer and compost. In the upland field and pasture soil, the increase in pyrophosphate-extractable U was 83-94% of that in U_t. On the other hand, the increase in acid oxalate-extractable U was 44-58% of that in U_t in the upland field and pasture soil, but it was almost equivalent to the increase in U_t in the paddy soil with NPK. In conclusion, most of the phosphate fertilizer-derived U was either incorporated into the soil organic matter or poorly crystalline Fe/Al minerals in the surface soil of agricultural fields. Thus, soil organic matter is an important pool of U in upland field and pasture soil, whereas poorly crystalline Fe/Al minerals are important pools of U in paddy soil experiencing alternating changes in redox conditions.     

Influence of clay minerals, used as supports in anaerobic digesters, in the precipitation of struvite

This work studies the influence of clay minerals used as supports in anaerobic digesters on the precipitation of ammonium magnesium phosphate. The magnesium exchange cation present in the sample originally or from experimental saturation plays an important role in the precipitation of struvite crystal growth depending on the greater or lesser facility of its liberation to the medium. Vermiculite, and probably stevensite, influence the formation of struvite, transferring the magnesium cation only from their exchange positions, while sepiolite does so by contributing from its structure. In vermiculite, struvite crystal formation is on the edges or fractures of the laminas. The presence of other cations in the supports, such as exchange Ca²⁺—either structural or as a component of accessory minerals, as in the case of stevensite—causes precipitation of calcium ammonium phosphate. In minerals with a high iron content, such as nontronite, iron phosphates are produced. The type of digester influences the size of the struvite crystals, these being larger in the semi-continuous digesters.     

Degradation of fifteen emerging contaminants at μg L initial concentrations by mild solar photo-Fenton in MWTP effluents

The degradation of 15 emerging contaminants (ECs) at low concentrations in simulated and real effluent of municipal wastewater treatment plant with photo-Fenton at unchanged pH and Fe = 5 mg L⁻¹ in a pilot-scale solar CPC reactor was studied. The degradation of those 15 compounds (Acetaminophen, Antipyrine, Atrazine, Caffeine, Carbamazepine, Diclofenac, Flumequine, Hydroxybiphenyl, Ibuprofen, Isoproturon, Ketorolac, Ofloxacin, Progesterone, Sulfamethoxazole and Triclosan), each with an initial concentration of 100 μg L⁻¹, was found to depend on the presence of CO₃²⁻ and HCO₃⁻ (hydroxyl radicals scavengers) and on the type of water (simulated water, simulated effluent wastewater and real effluent wastewater), but is relatively independent of pH, the type of acid used for release of hydroxyl radicals scavengers and the initial H₂O₂ concentration used. Toxicity tests with Vibrio fisheri showed that degradation of the compounds in real effluent wastewater led to toxicity increase.     

Removal of veterinary antibiotics from sequencing batch reactor (SBR) pretreated swine wastewater by Fenton's reagent

The large-scale application of veterinary antibiotics in livestock industry makes swine wastewater an important source of antibiotics pollution. This work investigated the degradation of six selected antibiotics, including five sulfonamides and one macrolide, by Fenton's reagent in swine wastewater pretreated with sequencing batch reactor (SBR). The dosing mode and practical dosage of Fenton's reagent were optimized to achieve an effective removal of antibiotics while save the treatment cost. The effects of initial pH, chemical oxygen demand (COD) and suspended solids (SS) of the SBR effluent on antibiotics degradation were examined. The results indicate that the optimal conditions for Fenton's reagent with respect to practical application were as follows: batch dosing mode, 1.5:1 molar ratio of [H₂O₂]/[Fe²⁺], initial pH 5.0. Under the optimal conditions, Fenton's reagent could effectively degrade all the selected antibiotics and was resistant to the variations in the background COD (0-419 mg/L) and SS (0-250 mg/L) of the SBR effluent. Besides, Fenton's reagent helped to not only remove total organic carbon (TOC), heavy metals (As, Cu and Pb) and total phosphorus (TP), but also inactivate bacteria and reduce wastewater toxicity. This work demonstrates that the integrated process combining SBR with Fenton's reagent could provide comprehensive treatment to swine wastewater.