Nitrogen recovery by urea hydrolysis and struvite precipitation from anthropogenic urine.

Human urine is a source of nutrients and has a significant potential for recycle of nitrogen. Recently, much research focused on separate collection and treatment of human urine. Recovery of nutrients from human urine requires hydrolysis of urea into ammonia and subsequent removal of ammonia and sometimes phosphorus. This study attempted to evaluate urea hydrolysis of human urine in both untreated fresh samples and urease added urine samples. Recovery of nutrients by struvite precipitation on pre-hydrolysed samples was also assessed on undiluted and 1:1 diluted samples. Results of urea hydrolysis on untreated urine samples indicated that the process was slow and pH exerted a significant effect on the process. No hydrolysis occurred above pH 10. From pH 2 to 7.5, 25% of urea could be hydrolysed in 30 d. Urease added hydrolysis with the enzyme doses 25-49 mg L(-1) was a rapid process providing complete conversion into ammonia in 1.5 h. Struvite precipitation conducted on enzyme hydrolysed urine sample proved to be an efficient process and ammonia removals up to 95% were obtained. Struvite precipitation also provided 50% organic nitrogen removal.     

Occurrence of micro-organic pollutants on phosphorus recovery from urine

Increased population growth and food prices have resulted in more demand for fertilizers, especially phosphorus (P), to be used in agriculture and production of food crops. Phosphorus is one of the important natural resources and will be exhausted in the near future. Nowadays, struvite production is a good method to recover P from urine. However, the natural urines contain high amounts of micro-organic pollutants which may cause health risks. Therefore, in this contribution, we investigated the amount of micro-organic pollutants in struvite from urine. There are various kinds of pharmaceuticals and hormones which are used in the world. Nevertheless, we focused on 10 pharmaceuticals (amoxycillin, carbamazepine, erythromycin, furosemide, atenolol, ibuprofen, norfloxacin, trimethoprim, tetracycline, and acetylsalicylic acid) and one hormone (17β-estradiol) as representatives. The experiments were carried out with synthetic and natural urines. After the production of struvite, the results from synthetic and natural urine samples showed that only tetracycline, erythromycin, and norfloxacin remained in the struvite, and, especially, tetracycline remained in struvite with quite a high amount.     

Phosphorus recovery from wastewater through struvite formation in fluidized bed reactors: a sustainable approach.

Recovery of phosphate as struvite (MgNH4PO4.6H2O), before it forms and accumulates on wastewater treatment equipment, solves wastewater treatment problems and also provides environmentally sustainable, renewable nutrient source for the agriculture sector. A pilot-scale fluidized bed reactor was used to recover phosphate through crystallization of struvite, from anaerobic digester centrate at the Lulu Island Wastewater Treatment Plant, Richmond, British Columbia, Canada. The desired degree of phosphate removal was achieved by maintaining operating pH (8.0-8.2), and recycle ratio 5-9, to control the supersaturation conditions inside the reactor. The performance of the system was found to be optimal when in-reactor supersaturation ratio was 2-6. Among several other operating parameters, apparent upflow velocity and magnesium to phosphate molar ratio were also found important to maintain system performance, both in terms of efficiency of phosphate removal and recovery as struvite pellets. A narrow window of upflow velocity (400-410 cm/min) was found to be effective in removing 75-85% phosphate. TOC level inside the rector was found to affect the performance to some extent. The precipitation potential of struvite could be successfully predicted using a thermodynamic solubility product value of 10(-13.36) and its temperature dependence in PHREEQC.     

Chemical phosphorus removal model based on equilibrium chemistry.

Regulations in many regions of the world require total phosphorus (TP) levels lower than 0.10 mgP/L (100 microgP/L) in effluents, resulting in the need to achieve very low ortho-phosphate (OP) concentrations. Chemical precipitation is a widely used technology for controlling effluent OP discharge, either on its own or supplementing biological methods. The various chemical and physico-chemical mechanisms that result in extremely low residual OP levels are complex and depend on pH. In practice, engineering calculations frequently use an empirical precipitation model. This model requires pH as input and predicts the lowest achievable OP residual of 35 microgP/L at a narrow optimum pH of 6.9-7.0, when an excess of ferric is added. The model has been combined with a biokinetic and weak acid/base chemistry based pH model, to allow accurate prediction of pH, OP residuals and chemical sludge production. Analysis of effluent data from the Blue Plains plant shows that residuals as low as 10 microgP/L OP can be achieved regularly, over a wider pH range. The precipitation model was recalibrated to match the newly available data. Subsequently it was compared with a new, mechanistic precipitation model based on solubility and dissociation constants for actual chemical compounds. The need for more accurate measurement of extremely low OP concentrations and considering the role of organics, adsorption and coagulation in chemical phosphorus removal is demonstrated.     

Model-based evaluation of struvite recovery from an in-line stripper in a BNR process (BCFS).

Phosphate removal and recovery can be combined in BNR processes. This may be realised by struvite precipitation from the supernatant of the sludge in anaerobic compartments. This can be beneficial for either improving bio-P removal effluent quality or lowering the influent COD/P ratio required for bio-P removal. For this reason, a patented BNR process, BCFS, was developed and applied in The Netherlands. Several questions relating to P-recovery and behaviour of the system remain unclear and need to be ascertained. For this purpose, a modelling technique was employed in this study. With the help of a previous developed model describing carbon oxidation and nutrient removal, three cases were fully simulated. The simulations demonstrated that there was an optimal stripping flow rate and P-recovery would increase in costs and bio-P activity might be negatively affected due to decreased bio-P efficiency if this value was exceeded. The simulations indicated that the minimal COD(biod)/P ratio required for the effluent standard (1 g P/m3) could be lowered from 20 to 10 with 36% of P-recovery. A simulation with dynamic inflow revealed that the dynamic influent loads affected slightly the anaerobic supernatant phosphate concentration but the effluent phosphate concentration would not be affected with regular P-recovery.     

Removal of ammonium from human urine through ion exchange with clinoptilolite and its recovery for further reuse.

Ammonium, from separately collected human urine, had been removed through transfer onto the ammonium selective natural zeolite, clinoptilolite, through ion exchange. In the subsequent treatment steps of washing with tap water, ammonium removed from urine was eluted from the surface of the clinoptilolite to be recovered for further reuse. Different quantities of clinoptilolite were used for a survey of the capacity of the zeolite for the process and to identify removal efficiencies based on initial ammonium loads. The highest surface concentration attained under experimental conditions employed was 15.44 mg ammonium per gram of clinoptilolite for an initial concentration of 110 mg ammonia per litre, and the highest removal was 98%, obtained for a loading of 1 mg ammonium per gram clinoptilolite. In the subsequent elution process, better removals were observed as pH was increased and the highest removal was attained at pH 13. The recovery was calculated as 9.73 mg ammonium per gram of clinoptilolite, corresponding to an efficiency of 63% only through washing with tap water. The results have given positive indications for the possibility of using ion exchange with clinoptilolite for the removal of ammonium from human urine and an incentive for improving methods of elution for its recovery for further reuse.     

Hybrid membrane bioreactor for water recycling and phosphorus recovery.

This paper deals with the performance of hybrid membrane bioreactor (MBR) combining the precoagulation/sedimentation and membrane bioreactor. The hybrid MBR not only produces the treated water with excellent permeate quality but also shows much lower membrane fouling than the conventional MBR. It may come from its extremely low F/M ratio to maintain the low viscosity even in the high MLSS concentration range of about 20,000 mg/L. Some results of microbial community analysis in MBRs was conducted to demonstrate the other reason for its lower membrane fouling. Hybrid MBR has a high potential to be used for the recycling use of the municipal wastewater. Coagulated sludge produced in the hybrid MBR is a promising phosphorus resource. This paper also contains a recent progress of phosphorus recovery technology, which uses a new phosphoric acids absorbent, i.e. the hexagonal mesostructured zirconium sulfate (ZS). The ZS has the extremely high adsorption capacity of phosphoric acids through anion exchange. The adsorbed phosphoric acids are released from the ZS in a high pH range of about 13.     

Ammonium nitrogen removal from slurry-type swine wastewater by pretreatment using struvite crystallization for nitrogen control of anaerobic digestion.

Precipitation of ammonium together with phosphate and magnesium is a possible alternative for lowering the nitrogen content of wastewater. In this study we examine the removal of ammonium nitrogen and phosphorus from slurry-type swine wastewater containing high concentrations of nutrients by the addition of phosphoric acid along with either calcium oxide or magnesium oxide, which leads to the crystallization of insoluble salts such as hydroxyapatite and struvite. The struvite crystallization method showed a high capacity for the removal of nitrogen when magnesium oxide and phosphoric acid were used as the magnesium and phosphate sources, respectively. When it was applied to swine wastewater containing a high concentration of nitrogen, the injection molar ratio of Mg2+:NH4+:PO4(3-) that gave maximum ammonium nitrogen removal was 3.0:1.0:1.5.     

Development of a process for the recovery of phosphorus resource from digested sludge by crystallization technology.

Removal and recovery of phosphorus from sewage in form of MAP (magnesium ammonium phosphate) have attracted attention from the viewpoint of eutrophication prevention and phosphorus resource recovery as well as scaling prevention inside digestion tanks. In this work, phosphorus recovery demonstration tests were conducted in a 50 m3/d facility having a complete mixing type reactor and a liquid cyclone. Digested sludge, having 690 mg/L T-P and 268 mg/L PO4-P, was used as test material. The T-P and PO4-P of treated sludge were 464 mg/L and 20 mg/L achieving a T-P recovery efficiency of 33% and a PO4-P crystallization ratio of 93%. The reacted phosphorus did not become fine crystals and the recovered MAP particles were found to be valuable as a fertilizer. A case study in applying this phosphorus recovery process for treatment of sludge from an anaerobic-aerobic process of a 21,000 m3/d sewage system, showed that 30% of phosphorus concentration can be reduced in the final effluent, recovering 315 kg/d as MAP.     

Potentials of using nanofiltration to recover phosphorus from sewage sludge.

Due to the depletion of mineral phosphorus resources there is an increasing demand for efficient phosphorus recovery technologies. In this study the potential of nanofiltration to recover phosphorus from pre-treated sewage sludge is investigated. The efficiency of three commercial nanofiltration membranes (Desal 5DK, NP030; MPF34) was tested using model solutions. Desal 5DK showed the best selectivity for phosphorus. A pH of lower than 1.5 was found to be most suitable. Desal 5DK was used on four different sewage sludge ash eluates and on one sewage sludge. In these experiments it was shown that a separation of phosphorus from undesired components such as heavy metals was possible with significant variations in the efficiency for the different ash and sludge types. Additionally the achievable product recovery was investigated with model solutions. A product recovery of 57.1% was attained for pH 1 and 41.4% for pH 1.5.     

湖泊底泥中磷释放的随机动力学模型

本文从随机过程的观点出发，推导出湖泊底泥磷相对释放量概率密度函数的随机微分方程，并给出了相应的定解条件。利用隐式差分法进行求解，分析了磷释放的均方差系数(D)、吸附系数(K1)、解吸系数(K2)及其对磷相对释放量概率函数分布的影响情况。所建立的磷释放随机动力学模型计算结果与实验数据吻合良好。     

Optimization of low-cost phosphorus removal from wastewater using co-treatments with constructed wetlands.

Eighteen wastewater treatment systems were operated for one year to investigate phosphorus (P) removal. Systems paired co-treatment reactors containing iron or calcium drinking water treatment residuals with vertical-flow constructed wetland mesocosms planted with Schoenoplectus tabernaemontani (K.C. Gmel.) Palla. For secondary municipal wastewater, soluble reactive P (SRP) concentrations were reduced from 0.70 to 0.03 mg L(-1) (95%) or 0.01 mg L(-1) (98%) by systems with the calcium or iron co-treatments, respectively (compared to 0.09 mg L(-1) or 87% by controls). Total P (TP) concentrations were reduced from 1.00 to 0.07 mg L(-1) (93%) and 0.05 mg L(-1) (95%) by the same treatments (compared to 0.16 mg L(-1) or 84% by controls). For anaerobically digested dairy wastewater, SRP was reduced from 7.68 to 6.43 mg L(-1) (16%) or 5.95 mg L(-1) (22%) by the systems with calcium or iron, respectively (compared to 7.37 mg L(-1) or 4% by controls). For this wastewater, the TP was reduced from 48.5 to 22.5 mg L(-1) (53%) and 22.7 mg L(-1) (53%) by the same treatments (compared to 24.1 mg L(-1) or 50% by controls) but performance improved substantially with a design modification tested.     

Designing and performing experiments for model calibration using an automated iterative procedure.

Optimal experimental design for parameter estimation involves complex mathematical and practical steps in order to obtain a model with sufficiently accurate parameters. This paper proposes a methodology where user interaction is only required at the beginning of the experimental design procedure. All subsequent steps are carried out automatically, including: (1) finding the optimal experiment, (2) performing the experiments in practice, and (3) recalibrating the model. A software extension to an existing modelling and simulation package which performs this automatic procedure is also presented. Finally an illustration for the calibration of a one-step nitrification model using respirometric data is given. In this case, the application of the proposed procedure resulted, after three iterations, in considerably better confidence intervals on the parameter estimates, within the desired boundaries.     

'Active' filters for upgrading phosphorus removal from pond systems.

This paper investigates limestone and iron slag filters as an upgrade option for phosphorus removal from wastewater treatment ponds. A review of 'active' filter technology and the results from laboratory and field research using packed columns of the different media is presented. It is shown that both limestone and iron slag can remove phosphorus but highlights that different types of limestone give markedly different performance. Filter performance appears to be improved by increasing temperature and by the presence of algae, presumably because of its tendency to elevate pH. Performance is related to hydraulic retention time (HRT), but this relationship is not linear, particularly at low HRTs. Importantly for future research, the results from field-testing with pond effluent show significant differences compared to those obtained when using a synthetic feed in the laboratory. For the iron slag filter, higher performance was observed in the field (72% in field vs. 27% in laboratory, at a 12 hour-HRT), while the opposite was observed for the limestone (64% in laboratory vs. 18% in field, at a 12-hour HRT).     

Evaluation of sludge reduction and phosphorus recovery efficiencies in a new advanced wastewater treatment system using denitrifying polyphosphate accumulating organisms.

A new biological nutrient removal process, anaerobic-oxic-anoxic (A/O/A) system using denitrifying polyphosphate-accumulating organisms (DNPAOs), was proposed. To attain excess sludge reduction and phosphorus recovery, the A/O/A system equipped with ozonation tank and phosphorus adsorption column was operated for 92 days, and water quality of the effluent, sludge reduction efficiency, and phosphorus recovery efficiency were evaluated. As a result, TOC, T-N and T-P removal efficiency were 85%, 70% and 85%, respectively, throughout the operating period. These slightly lower removal efficiencies than conventional anaerobic-anoxic-oxic (A/A/O) processes were due to the unexpected microbial population in this system where DNPAOs were not the dominant group but normal polyphosphate-accumulating organisms (PAOs) that could not utilize nitrate and nitrite as electron acceptor became dominant. However, it was successfully demonstrated that 34-127% of sludge reduction and around 80% of phosphorus recovery were attained. In conclusion, the A/O/A system equipped with ozonation and phosphorus adsorption systems is useful as a new advanced wastewater treatment plant (WWTP) to resolve the problems of increasing excess sludge and depleted phosphorus.     

Apatite as an interesting seed to remove phosphorus from wastewater in constructed wetlands.

Intensive use of phosphates has resulted in high P levels in surface waters and therefore eutrophication problems. Over the last decade many studies have revealed the advantage of using specific materials with efficient phosphorus retention capacities. Recent studies state that Ca materials are of particular interest for long-term retention of P, but can induce negative effects. To improve P retention and avoid negative counter-effects we tested the potential of natural apatites. Apatite sorption was evaluated using batch and open reactor experiments. Batch experiments identify sorption mechanisms and the influence of the ionic characteristics of the solution; open reactor experiments evaluate sorption capacities in relation to the ionic composition of the solution and biomass development. In parallel, observation of the material by electron microscopy was used to give more precision information about the mechanisms involved. This work reveals the strong chemical affinity between apatites and phosphorus. Compared to other calcareous materials apatite is better able to maintain low outlet P levels. After more than 550 days feeding, sorption was still present and low P outlet levels were still being obtained when sufficient contact time and calcium content in the solution were ensured. This work demonstrates the advantages of using apatites for phosphorus removal in constructed wetlands. The behaviour of apatite in phosphorus retention is explained and its suitability for use in such extensive systems defined.     

Slag columns for upgrading phosphorus removal from constructed wetland effluents.

The current best option to upgrade constructed wetlands (CWs) for phosphorus (P) retention, in terms of efficiency, cost and simplicity, consists in using media having a strong P affinity. The media can be used either in the planted beds or in a filtration system downstream of the beds. The use of slag filters was shown to be efficient for removing P from wastewater as it represented a slow release source of calcium and hydroxide, favouring the formation of hydroxyapatite. Our study aimed at maximising the P retention capacity of slag filters located at the outlet of CWs since electric arc furnace slag has been shown to inhibit the growth of macrophytes when used in the filtration matrix. Bench-scale columns (Vtot = 6.2 L) filled with various combinations of filter media (slag, granite, limestone) of different sizes (2-5, 5-10, 10-20 mm) were fed on-site during four months with a CW effluent (in mg/L: 30 COD, 30 TSS, 10 Pt). Results showed that the best media combination enabling the maximum o-PO4 retention (more than 80% removal without clogging) consisted in a series of a ternary mix column (slag 5-10 mm, granite 2-5 mm, limestone 5-10 mm) followed by a slag column (slag 5-10 mm). Pilot scale columns (Vtot = 300 L), filled with the best media combination, were installed at the outlet of a 28 m2 CW. These columns showed more than 75% removal efficiency during one year and were designed to be easily replaced each year.     

Adsorption and recovery of alkylphenol polyethoxylates from synthetic wastewater using hexagonal mesoporous silicate.

A large amount of alkylphenol polyethoxylate (APnEOs), one of endocrine disrupters, is disposed of directly to biological wastewater treatment plants. But microbial oxidation processes cannot completely degrade these molecules to nontoxic forms. Adsorption and recovery efficiency of APnEOs was investigated using four different types of Hexagonal Mesoporous Silicate (HMSs) and powdered activated carbon (PAC). HMSs were synthesized by surfactant-templating methods, and two of them were subsequently grafted with surface functional groups. The two types of organic functional groups grafted on the surface were n-octyldimethyl- and 3-mercaptopropyl- groups. Titanium substituted HMS was also made in the same way as HMS. Adsorption of APnEOs on synthesized HMSs was higher than that on PAC. Larger pore sizes of HMS and Ti-HMS enhanced accessibility of APnEOs to active surface sites in mesopores, which realized higher adsorption capacities and L-shape (Langmuir) adsorption isotherms. Adsorption capacities of APnEOs are influenced by water solubility of APnEOs. APnEOs adsorbed on HMSs can be completely recovered by a mixture of alcohol and water at 5:5 ratio, which is more effective than the recovery from PAC.     

Resource recovery and nitrogen removal from piggery waste using the combined anaerobic processes.

The combined ADEPT (Anaerobic Digestion Elutriated Phased Treatment)- SHARON (Single reactor system High Ammonium Removal Over Nitrite)--ANAMMOX (Anaerobic Ammonium Oxidation) processes were operated for the purpose of resource recovery and nitrogen removal from slurry-type piggery waste. The ADEPT operated at acidogenic loading rates of 3.95 gSCOD/L-day, the SCOD elutriation rate and acid production rate were 5.3 gSCOD/L-day and 3.3 gVFAs(as COD)/L-day, respectively. VS reduction and SCOD reduction by hydrolysis were 13% and 0.19 gSCOD(prod.)/gVS(feeding), respectively. Also, the acid production rate was 0.80 gVFAs/gSCOD(production). In the methanogenic reactor, the gas production rate and methane content were 2.8 L/day (0.3 m3CH4/kgCOD(removal)STP) and 77%, respectively. With these operating condition, the removal of nitrogen and phosphorus were 94.1% as NH4-N (86.5% as TKN) and 87.3% as T-P, respectively.     

Sensory evaluation of the odors produced during bromophenol formation using a multi-level statistical model.

In response to reports of medicinal taste and odor problems in suburban Paris, a lab scale study was conducted to investigate the contribution of different water quality parameters--pH, phenol, bromide, chlorine, temperature and dissolved oxygen levels--on bromophenol medicinal odor formation using the Flavor Profile Analysis (FPA) method. A study of six parameters at 2 levels (64 experiments) analyzed by the FPA method suggests that chlorine at high concentration is more important as a controlling agent than phenol under similar conditions and the ratio of HOBr:Phenol and the time for reaction will control subsequent brominated products of reaction. Results from a three-level statistical model indicate that high pH was associated with lower odor intensities, whereas high levels of chlorine, phenol and temperature were associated with high odor intensities. Potential worst case scenarios of water quality conditions were determined for evaluation by chemical identification and kinetics.