Biological phosphate uptake and release: effect of pH and magnesium ions.

Enhanced biological phosphorus removal (EBPR) is based on poly-phosphate accumulating organisms' (PAOs) unique features of "luxury" phosphate uptake during aerobic conditions and phosphate release in anaerobic conditions. It is believed that poly-phosphate accumulation is accompanied by the uptake and accumulation of potassium ions (K+) and magnesium ions (Mg2+). The release of phosphate under anaerobic conditions is also accompanied by the release of both cations. The objective of this research was to evaluate the effect of pH and Mg2+ on the biological phosphate uptake and release behavior of activated sludge mixed liquor during aeration and sedimentation. Research results indicate that Mg2+, supplied either by magnesium chloride (MgCl2) or magnesium hydroxide [Mg(OH)2], stimulated phosphate uptake during the aeration period, while pH increase, caused by the application of Mg(OH)2, enhanced phosphate release during the sedimentation period. It is also noted in our experiments with MgCl2 that Mg2+ slightly inhibited anaerobic phosphate release.     

Case study II: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-using alternatives to sodium-based chemicals.

The objective of this study was to investigate the application of the divalent cation bridging theory (DCBT) as a tool in the chemical selection process at an activated sludge plant to improve settling, dewatering, and effluent quality. According to the DCBT, to achieve improvements, the goal of chemical selection should be to reduce the ratio of monovalent-to-divalent (M/D) cations. A study was conducted to determine the effect of using magnesium hydroxide [Mg(OH)2] as an alternative to sodium hydroxide (NaOH) at a full-scale industrial wastewater treatment plant. Floc properties and treatment plant performance were measured for approximately one year during two periods of NaOH addition and Mg(OH)2 addition. A cost analysis of plant operation during NaOH and Mg(OH)2 use was also performed. During NaOH addition, the M/D ratio was 48, while, during Mg(OH)2 addition, this ratio was reduced to an average of approximately 0.1. During the Mg(OH)2 addition period, the sludge volume index, effluent total suspended solids, and effluent chemical oxygen demand were reduced by approximately 63, 31, and 50%, respectively, compared to the NaOH addition period. The alum and polymer dose used for clarification was reduced by approximately 50 and 60%, respectively, during Mg(OH)2 addition. The dewatering properties of the activated sludge improved dewatering as measured by decreased capillary suction time and specific resistance to filtration (SRF), along with an increase in cake solids from the SRF test. This corresponded to a reduction in the volume of solids thickened by centrifuges at the treatment plant, which reduced the disposal costs of solids. Considering the costs for chemicals and solids disposal, the annual cost of using Mg(OH)2 was approximately 30,000 dollars to 115,000 dollars less than using NaOH, depending on the pricing of NaOH. The results of this study confirm that the DCBT is a useful tool for assessing chemical-addition strategies and their potential effect on activated sludge performance.     

Thermal decomposition of struvite and its phase transition

Intentional crystallization of struvite, before it forms and accumulates on wastewater treatment equipment, solves an important and costly wastewater treatment problem and on the other hand, provides an environmentally sound and renewable nutrient source to the agricultural industry. Struvite was synthesized in the laboratory; it was also produced as pellets in a pilot-scale, fluidized bed reactor, using real centrate resulting from an anaerobic digester. The thermal decomposition of both synthetic struvite and struvite pellets was studied. The decomposition of struvite was found to be dependent on the rate of heating. Through gradual loss of ammonia and water molecules, ultimately struvite was found to be transformed into amorphous magnesium hydrogen phosphate. When struvite was heated in excess water, it was partially transformed into bobierrite, through the gradual loss of ammonia. It was transformed into monohydrate, dittmarite by losing its five water molecules of crystallization, when boiled in excess water.     

酸性条件下剩余污泥中Ca2＋和Mg2＋溶出对磷回收的影响

为了在酸性条件下实现剩余污泥中磷的高效回收,对pH=3时剩余污泥水解酸化过程中氨氮、正磷酸盐和钙镁离子的溶出现象以及磷回收进行了研究分析。结果表明：当pH=3时,所溶出的氨氮、镁离子和钙离子与磷酸盐的摩尔比均大于1,能满足采用鸟粪石沉淀法或者羟磷灰石沉淀法回收磷的要求;但所溶出的钙镁离子的摩尔比大于1,会对鸟粪石沉淀法回收磷的顺利进行有较大影响;有无外加镁剂对磷回收率影响不大。采用改型后的镁型强酸性阳离子交换树脂进行离子交换可以得到较高纯度的鸟粪石沉淀产品,通过XRD检测其纯度为95％以上。     

Nitrogen conservation in simulated food waste aerobic composting process with different Mg and P salt mixtures

To assess the effects of three types of Mg and P salt mixtures (potassium phosphate [K3PO4]/magnesium sulfate [MgSO4], potassium dihydrogen phosphate [K2HPO4]/MgSO4, KH2PO4/MgSO4) on the conservation of N and the biodegradation of organic materials in an aerobic food waste composting process, batch experiments were undertaken in four reactors (each with an effective volume of 30 L). The synthetic food waste was composted of potatoes, rice, carrots, leaves, meat, soybeans, and seed soil, and the ratio of C and N was 17:1. Runs R1-R3 were conducted with the addition of K3PO4/ MgSO4, K2HPO4/MgSO4, and KH2PO4/MgSO4 mixtures, respectively; run R0 was a blank performed without the addition of Mg and P salts. After composting for 25 days, the degrees of degradation of the organic materials in runs R0-R3 were 53.87, 62.58, 59.14, and 49.13%, respectively. X-ray diffraction indicated that struvite crystals were formed in runs R1-R3 but not in run R0; the gaseous ammonia nitrogen (NH3-N) losses in runs R0-R3 were 21.2, 32.8, 12.6, and 3.5% of the initial total N, respectively. Of the tested Mg/P salt mixtures, the K2HPO4/ MgSO4 system provided the best combination of conservation of N and biodegradation of organic materials in this food waste composting process.     

Removal of nitrogen and phosphate from wastewater by addition of bittern

Removal of nitrogen and phosphate through crystallization of struvite (MgNH(4)PO(4).6H(2)O) has gained increasing interest. Since wastewaters tend to be low in magnesium relative to ammonia and phosphates, addition of this mineral is usually required to effect the struvite crystallization process. The present study evaluated the feasibility of using bittern, a byproduct of salt manufacture, as a low-cost source of magnesium ions. High reaction rates were observed; the extent of nitrogen and phosphorus removals did not change beyond 10 min. Phosphorus removals from pure solutions with bittern added were equivalent to those obtained with MgCl(2) or seawater. Nitrogen removals with bittern were somewhat lower than with the alternate Mg(2+) sources, however. Application of bittern to biologically treated wastewater from a swine farm achieved high phosphate removal, but ammonia removals were limited by imbalance in the nitrogen:phosphorus ratio.     

Phosphate Recovery from Greenhouse Wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca₅(PO₄)₃OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K‐struvite, MgKPO₄·6H₂O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

Prevention of struvite scaling in digesters combined with phosphorus removal and recovery--the FIX-Phos process

The fixation of phosphorus (FIX-Phos) combines struvite prevention and phosphorus recovery by the addition of calciumsilicatehydrate (CSH) particles into the anaerobic digester. The CSH fixates phosphorus as calcium phosphate and reduces the phosphorus concentration in the sludge water that allows for control of struvite formation. The phosphorus-containing recovery product can be separated and recovered from the digested sludge. In pilot plant experiments, 21% to 31% of phosphorus contained in digested sludge could be recovered when CSH was added at concentrations of 2 g/L to 3.5 g/L to a mixture of primary sludge and waste activated sludge (WAS) from enhanced biological phosphorus removal. The recovery product contained few heavy metals and a phosphorus content of 18 wt % P2O5, which allows for recycling as fertilizer. The fixation of phosphorus within the digester may increase wastewater sludge dewaterability. The phosphorus recycle stream to the headworks of the wastewater treatment plant is reduced.     

工艺条件对鸟粪石晶体的粒径和沉降速度的影响

采用激光粒度仪实验测定了小型套管式空气曝气填料层磷回收装置中不同条件下生成的鸟粪石晶体的体积平均粒径,考察了其变化规律,并结合Stokes公式计算了晶体的沉降速率,同时考虑鸟粪石晶体形状的影响,进行了相应的修正。实验结果表明,鸟粪石的粒径在10—200μm之间,主要集中于20～100μm;在磷回收装置中添加填料并通人空气有利于增大鸟粪石晶体的粒径和沉降速度,无填料无空气时和有填料有空气时的平均粒径分别在30～55μm和40～65μm之间。随着pH值的增大,鸟粪石晶体的粒径和沉降速度逐渐增大,但当pH大于9．0后,鸟粪石晶体的粒径和沉降速度又逐渐减小;氮磷比值从1：1增大到2：1,鸟粪石晶体的粒径和沉降速度小幅度增加,氮磷比进一步增大,鸟粪石晶体的粒径和沉降速度基本不变;镁磷摩尔比在1：1—1．2：1的范围内时,鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大而增大;镁磷摩尔比大于1．2：1后,鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大逐渐减小;初始磷浓度越高,鸟粪石晶体的平均粒径和沉降速度越大。     

Prospect of recovering phosphorus in magnesium slag-packed wetland filter

Phosphorus recovery from wastewater not only reduces the unbearable impacts of excessive nutrient discharge on environmental systems but also favor the reuse of phosphorus resource. Based on the mechanism as well as technical analysis for major phosphorus recovery techniques including struvite precipitation and wetland substrate adsorption, a novel magnesium slag-packed wetland filter and corresponding operational procedures are proposed, which aim to reduce the dependence of using magnesium-containing chemical reagent as magnesium sources for struvite precipitation, and improve the accumulation and recovery performance for struvite precipitation within porous wetland substrate. Results from preliminary experiments indicated that magnesium slag particles with approximately 2 mm in diameter can recover 43.20–72.39% phosphorus from 1–25 mol/L PO₄ ^3? solution, and the presence of 5–50 mol/L NH₄ ⁺ contributed to 11.71–29.11% enhancement of phosphorus recovery mainly due to struvite precipitation. The detected generation of struvite via XRD spectrum analysis partly demonstrated the potential of phosphorus recovery in magnesium slag-packed wetland filter. The proposed phosphorus recovery technology is free of secondary pollution and solid waste generation; phosphorus-saturated (mainly due to struvite precipitation and adsorption) magnesium slag particles can be potentially used as phosphorus fertilizer and thus partly solved the traditional shortages of disposing phosphorus-saturated substrate due to low phosphorus contents.     

Microalgae growth using high-strength wastewater followed by anaerobic co-digestion

Integration of algal biofuel production to wastewater anaerobic digestion infrastructure has the potential to increase biogas production, decrease high and variable internal nitrogen loads, and improve sludge digestibility and dewaterability. In this research, two species of microalgae, Spirulina platensis and Chlorella sp., were grown on sludge centrate and a centrate and nitrified wastewater effluent mixture. Harvested algae were co-digested with waste activated sludge (WAS) at varying ratios. High-growth (6.8 g m(-2) x d(-1)), nitrogen (36.5 g m(-3) x d(-1)), and phosphorus (6.5 g m(-3) x d(-1)) uptake rates were achieved with Chlorella on centrate. No growth was observed with S. platensis under the same conditions; however, both organisms grew well on the centrate and effluent mixture. Co-digestion of algae with WAS improved volatile solids reduction. Although co-digestion with S. platensis improved biosolids dewaterability, Chlorella had a slight negative effect on dewaterability compared to WAS alone. The efficiency of energy conversion from photons to biogas generated from Chlorella was estimated at 1.4%.     

Phosphate recovery from greenhouse wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca5(PO4)3OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K-struvite, MgKPO4 x 6H2O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

MAP法沉淀回收装置的运行条件优化研究

采用一种简易的MAP回收装置,研究了间歇运行条件下反应时间和曝气量对MAP法除磷效果的影响,确定出最佳反应时间为90 min,最佳曝气量为1.2 L/min,相应的除磷率可达98.26%,沉淀回收率为74.54%。当增加一个漏斗形隔板分离反应区和沉淀区并连续运行时,除磷率和沉淀回收率分别为92.11%和63.66%。当不投加镁盐和铵盐而仅调控实际污泥脱水滤液的pH值为9.8时,其连续运行的平均除磷率和MAP回收率分别可达95.16%和70%,运行性能比较稳定。     

The Effects of Magnesium and Ammonium Additions on Phosphate Recovery from Greenhouse Wastewater

Phosphorus recovery from greenhouse wastewater, using precipitation-crystallization, was conducted under three levels of calcium concentration, 304 mg/L (7.6 mmol/L), 384 mg/L (9.6 mmol/L), and 480 mg/L (12 mmol/L), and also with additions of ammonium and magnesium into the wastewater. Jar test results confirmed high phosphate removal, with more than 90% of the removal achieved with a pH as low as 7.7. Under the low calcium concentration, ammonium addition affected the chemical reactions at pH lower than 8.0, where struvite was produced; when the pH was raised to 8.8, other calcium compounds dominated the precipitation. Under the medium calcium concentration, ammonium and magnesium addition helped struvite precipitation in the low pH range. Hydroxyapatite (HAP) was the main product. Under the high calcium concentration, ammonium addition showed no effects on the precipitation.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

The effects of magnesium and ammonium additions on phosphate recovery from greenhouse wastewater

Phosphorus recovery from greenhouse wastewater, using precipitation-crystallization, was conducted under three levels of calcium concentration, 304 mg/L (7.6 mmol/L), 384 mg/L (9.6 mmol/L), and 480 mg/L (12 mmol/L), and also with additions of ammonium and magnesium into the wastewater. Jar test results confirmed high phosphate removal, with more than 90% of the removal achieved with a pH as low as 7.7. Under the low calcium concentration, ammonium addition affected the chemical reactions at pH lower than 8.0, where struvite was produced; when the pH was raised to 8.8, other calcium compounds dominated the precipitation. Under the medium calcium concentration, ammonium and magnesium addition helped struvite precipitation in the low pH range. Hydroxyapatite (HAP) was the main product. Under the high calcium concentration, ammonium addition showed no effects on the precipitation.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

Fouling mechanisms in a laboratory-scale UV disinfection system.

The fouling of quartz sleeves surrounding UV disinfection lamps is a perennial problem affecting both drinking water and wastewater applications. The mechanisms of fouling are not fully understood, but factors promoting fouling are believed to include heat, high hardness and/or high iron concentrations, and hydrodynamic forces. The role of UV radiation itself is unclear. The goal of this paper is to attempt to isolate the fouling mechanisms and to provide key information about those induced by UV radiation, using a unique laboratory-scale continuous-flow UV reactor. Its design allowed for irradiated and nonirradiated zones and control of both temperature and UV intensity at the fouling surface. Synthetic wastewater samples were tested with two levels of calcium, iron, phosphorus, and biochemical oxygen demand (as beef broth), and constant levels of magnesium and nitrogen to assess the effects of the four key variables. Average UV fluence before fouling exceeded 35 mJ/cm2, based on collimated beam tests. Foulant accumulation was monitored by UV intensity measurements and by mass and composition of foulant collected after an average of 56 hours of continuous operation. Tests showed that relative UV intensity dropped by as much as 100% when iron was present. Detailed results were assessed and yielded support for the following three UV-induced fouling mechanisms: (a) precipitation of ferric hydroxide [Fe(OH)3], (b) release of calcium from calcium-organics complexes followed by precipitation of iron-organics complexes, and (c) calcium carbonate precipitation. Other fouling mechanisms, such as sedimentation of preformed particles and sorption of calcium onto preformed colloids of Fe(OH)3, occurred outside the zone of UV radiation. Hence, these could be confused with concurrent UV-induced mechanisms in full-scale reactors. Iron and/or calcium undoubtedly created the most favorable conditions for fouling to occur; in the absence of both, fouling would be unlikely. The rates of fouling were enhanced when organics were also present; however, when phosphorus was present, fouling in the UV section was reduced. Indeed, UV may be viewed as inhibiting the fouling caused by phosphate complexes.     

Repeated use of MAP decomposition residues for the removal of high ammonium concentration from landfill leachate

The residues of magnesium ammonium phosphate (MAP) decomposed by heating under alkali conditions were repeatedly used as the sources of phosphate and magnesium for the removal of high ammonium concentration from landfill leachate. Up to 96% of ammonium in MAP powder could be released under the following conditions: NH4(+):OH- molar ratio, 1:1; temperature, 90 degrees C; heating time, 2 h. Fourier transform infrared spectra and X-ray diffraction analysis of MAP before and after heating demonstrated that MAP was mainly transformed to amorphous magnesium sodium phosphate (MgNaPO4), which makes it possible for the NH4(+) to replace Na+ in MgNaPO4 to form more stable struvite. Successful ammonium removal was achieved by using the MAP decomposition residues as the sole phosphate and magnesium sources. The ammonium removal decreased gradually following the increase of MAP reuse cycles, and in the 6th cycle, ammonium removals of 84% and 62% were achieved for synthetic wastewater and landfill leachate, respectively. Analysis of the surfaces of MAP powders acquired at different reuse cycles using scanning electron microscopy with energy dispersive X-ray suggested that the existence of calcium, kalium and aluminum ions in landfill leachate might have inhibited the formation of MAP through competition with ammonium ions for phosphate ions. It is estimated that reuse of MAP for 3 cycles could save about 44% chemical costs.