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.     

重金属杂质对磷酸铵镁结晶法处理制药废水的影响

磷酸铵镁沉淀法处理废水时常受众多因素影响，其中重金属类杂质对该过程影响较大。实验研究了Mn²⁺、Cu²⁺杂质存在条件下，用该法去除制药废水中PO₄^3-、NH₄⁺污染物，同时，用XRD、XRF、SEM等手段研究了所得鸟粪石晶体特征。结果表明，pH为9.5时，Mn²⁺、Cu²⁺杂质存在条件下，PO₄^3-去除率分别为88%和85%，投加晶种有利于回收特定晶形鸟粪石，Cu²⁺对磷酸铵镁结晶过程的影响较Mn²⁺存在时显著。     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明，鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间，过高的pH会破坏鸟粪石晶体结构，导致固定氨从MgNH₄PO₄中游离出来，不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下，渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L，去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属，同时回收了氨氮，其沉淀产物鸟粪石是一种优良的缓释肥原料。     

Effect of culture conditions on the formation of struvite by Myxococcus xanthus

The amount of struvite (MgNH₄PO₄·6H₂O) produced by Myxococcus xanthus as well as the culture parameter values (pH, total phosphorus, total Kjeldahl nitrogen) were dependent on the culture medium used. Struvite formation started during the exponential phase and the maximum concentration was observed at the beginning of stationary growth phase. The addition of each medium component to the liquid culture influenced the amount of crystal produced. This amount did not depend on the pH increase during the culture period. The moment of the bacterial growth phase, at which each medium component was added, influenced the struvite formation.     

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。     

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.     

Phosphorus recovery from fosfomycin pharmaceutical wastewater by wet air oxidation and phosphate crystallization

Fosfomycin pharmaceutical wastewater contains highly concentrated and refractory antibiotic organic phosphorus (OP) compounds. Wet air oxidation (WAO)-phosphate crystallization process was developed and applied to fosfomycin pharmaceutical wastewater pretreatment and phosphorus recovery. Firstly, WAO was used to transform concentrated and refractory OP substances into inorganic phosphate (IP). At 200 °C, 1.0 MPa and pH 11.2, 99% total OP (TOP) was transformed into IP and 58% COD was reduced. Subsequently, the WAO effluent was subjected to phosphate crystallization process for phosphorus recovery. At Ca/P molar ratio 2.0:1.0 or Mg/N/P molar ratio 1.1:1.0:1.0, 99.9% phosphate removal and recovery were obtained and the recovered products were proven to be hydroxyapatite and struvite, respectively. After WAO-phosphate crystallization, the BOD/COD ratio of the wastewater increased from 0 to more than 0.5, which was suitable for biological treatment. The WAO-phosphate crystallization process was proven to be an effective method for phosphorus recovery and for fosfomycin pharmaceutical wastewater pretreatment.     

工艺条件对磷回收过程中鸟粪石沉淀颗粒粒径的影响

在鸟粪石沉淀法回收废水中磷的过程中,鸟粪石颗粒的大小将直接影响其沉淀的速率,进而影响鸟粪石的沉淀效果和磷的回收率。本文采用激光粒度分析仪测定鸟粪石的平均粒径,详细考察在小型连续搅拌反应-沉淀磷回收装置中不同的工艺条件下鸟粪石颗粒粒径的变化规律,并结合Stokes公式计算鸟粪石颗粒在废水出口处的沉降速率,为沉淀池的设计提供参考依据。结果表明:鸟粪石的平均粒径在12～25μm之间,沉降速率在5.46×10-5～2.37×10-4m/s之间。随着反应室水力停留时间的延长,鸟粪石颗粒的粒径逐渐增大,当停留时间超过18 min时,颗粒的粒径基本不变;随着沉淀室水力停留时间的延长,鸟粪石颗粒的平均粒径缓慢增大,当停留时间超过70 min后颗粒粒径的变化不大;鸟粪石颗粒的平均粒径在一定程度上受废水中磷初始浓度变化的影响,在磷初始浓度为62～128 mg/L时颗粒的粒径变化不大,当磷浓度为496 mg/L时粒径有较大增加,此时鸟粪石颗粒的沉降速率也大幅度增加;鸟粪石颗粒的平均粒径受pH值的影响不大;随氮磷摩尔比的增大,鸟粪石颗粒的平均粒径略有增加;随镁磷摩尔比的增大,鸟粪石颗粒的平均粒径逐渐减小,沉降速率则有明显的下降。     

Overcoming challenges to struvite recovery from anaerobically digested dairy manure

Recovering struvite from dairy manure has consistently posed problems for researchers. This study separated solids from anaerobically digested dairy manure using a filtration system. Filtrate was rich in free magnesium (160 to 423 mg/L), ammonium (320 to 1800 mg N/L) and orthophosphate (93 to 332 mg P/L). High concentrations of free calcium (128 to 361 mg/L) and alkalinity (3309 to 6567 mg/L as CaCO3), however, may hinder struvite precipitation. Batch precipitation tests were conducted to identify and overcome factors that interfere with struvite formation. Precipitation tests at pH 9 identified calcium and ionic strength as most probable interferences. Calcium addition did not significantly change phosphorus removal efficiency, but decreased struvite purity because of formation of calcium phosphates when Ca:P activity ratio was greater than 0.5 to 1. Batch tests demonstrated effective calcium removal from anaerobically digested dairy manure through precipitation of calcium carbonate at pH 9 to 10 while retaining magnesium and orthophosphate, lessening hindrance to struvite formation.     

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.     

Plant uptake of phosphorus and nitrogen recycled from synthetic source-separated urine

Urine contains about 50 % of the phosphorus (P) and about 90 % of the nitrogen (N) excreted by humans and is therefore an interesting substrate for nutrient recovery. Source-separated urine can be used to precipitate struvite or, through a newly developed technology, nitrified urine fertilizer (NUF). In this study, we prepared ³³P radioisotope- and stable ¹⁵N isotope-labeled synthetic NUF (SNUF) and struvite using synthetic urine and determined P and N uptake by greenhouse-grown ryegrass (Lolium multiflorum var. Gemini) fertilized with these products. The P and N in the urine-based fertilizers were as readily plant-available in a slightly acidic soil as the P and N in reference mineral fertilizers. The ryegrass crop recovered 26 % of P applied with both urine-based fertilizers and 72 and 75 % of N applied as struvite and SNUF, respectively. Thus, NUF and urine-derived struvite are valuable N and P recycling fertilizers.     

Microwave pretreatment for enhancement of phosphorus release from dairy manure

Both the advanced oxidation process (AOP) using a combination of hydrogen peroxide addition and microwave heating (H2O2/microwave), and the microwave heating process were used for solubilization of phosphorus from liquid dairy manure. About 80% of total phosphate was released into the solution at a microwave heating time of 5 min at 170 degrees C. With an addition of H2O2, more than 81% of total phosphate could be released over a reaction period of 49 h at ambient temperature. The AOP process could achieve up to 85% of total phosphate release at 120 degrees C. The results indicated that both the microwave, and the AOP processes could effectively release phosphate from liquid dairy manure. These processes could serve as pretreatments for phosphorus recovery from animal wastes, and could be combined with the struvite crystallization process to provide a new approach in treating animal wastes.     

Adsorption and precipitation of tetracycline with struvite.

The interaction of tetracycline with struvite during adsorption and precipitation processes was investigated. Tetracycline removal by adsorption was affected by solution pH, contact time, and struvite concentration. The lowest tetracycline removal (8.4%) was observed at pH 7.7, the dissociation constant (pKa2) of tetracycline. Because of the electrostatic repulsion, the amount of tetracycline adsorbed on the surface was low. The small amount of adsorption was the result of surface complexation between tetracycline ions and metal ions. Calcium (Ca2+) ions in the adsorbent enhanced the binding of tetracycline. Freundlich (KF: 0.04, n: 1.49) and Redlich-Peterson (KR: 0.08, alphaR: 0.98, betaR: 0.49) models best defined the equilibrium data. In the case of struvite precipitation, approximately 22% of tetracycline was removed as a result of binding to struvite alongside struvite formation.     

Struvite precipitation by the dissolved CO2 degasification technique: impact of the airflow rate and pH

In the present work, struvite precipitation was provoked by the dissolved CO(2) degasification technique where precipitation occurred following the degassing of the CO(2) by atmospheric air. The impact of the airflow rate and initial solution pH on struvite precipitation were assessed. For initial solution pH<6.5, no precipitation was observed. For initial solution pH>6.5, the phosphorus removal through struvite precipitation could be improved by increasing the airflow rate up to 25 L min(-1), or by increasing the initial pH for higher airflow rates. Compared to traditional techniques of struvite precipitation such as stirring and aeration, the dissolved CO(2) degasification technique is promising since a high amount of phosphorus (approximately 78%) could be removed at relatively short experiment time.     

Biotransformation and antioxidant response in Ceratophyllum demersum experimentally exposed to 1,2- and 1,4-dichlorobenzene

We report the effects of 1,2- and 1,4-dichlorobenzene (1,2-DCB and 1,4-DCB) on the aquatic macrophyte Ceratophyllum demersum. We evaluated the response of the antioxidant system through the assay of glutathione reductase (GR), guaiacol peroxidase (POD) and glutathione peroxidase (GPx). Additionally, the effect of DCBs on the detoxication system by measuring the activity of glutathione-S-transferase (GST) was evaluated.

C. demersum showed elevated GST activities when exposed to 10 and 20 mg l⁻¹ 1,2-DCB, and at 10 mg l⁻¹ for 1,4-DCB. These results show that glutathione conjugation take place at relatively high concentrations of both isomers. Significantly increased activities of POD were also detected in C. demersum exposed to concentrations above 5 mg l⁻¹ of the corresponding isomer.

The GR activity was enhanced in plants exposed to 1,2-DCB (5 mg l⁻¹) and 1,4-DCB (10 mg l⁻¹). GPx was also significantly increased in exposures to the corresponding isomer, each at a concentration of 10 mg l⁻¹. However, plants exposed to low doses of 1,4-DCB (1 mg l⁻¹) showed significantly decreased activities of both enzymes GR and GPx.

Consequently, it is clear that the exposure of the aquatic macrophyte C. demersum to DCBs is able to cause an activation of the antioxidant system, showing an isomer specific pattern, which suggests that the defence system of this plant is playing an important role in scavenging ROS, helping to protect the organism against adverse oxidative effects generated by the prooxidant action of the tested xenobiotics. Furthermore, increased GST activities give indirect evidence on the conjugation of either DCBs or the corresponding metabolites during phase II of detoxication, which supports the elimination process of toxic metabolites from cells of C. demersum.     

Greenhouse evaluation and environmental impact assessment of different urine-derived struvite fertilizers as phosphorus sources for plants

A selection of six urine-derived struvite fertilizers generated by innovative precipitation technologies was assessed for their quality and their effectiveness as phosphorus sources for crops. Struvite purity was influenced by drying techniques and magnesium dosage. In a greenhouse experiment, the urine fertilizers led to biomass yields and phosphorus uptakes comparable to or higher than those induced by a commercial mineral fertilizer. Heavy metal concentrations of the different struvite fertilizers were below the threshold limits specified by the German Fertilizer and Sewage Sludge Regulations. The computed loading rates of heavy metals to agricultural land were also below the threshold limits decreed by the Federal Soil Protection Act. Urine-derived struvite contributed less to heavy metal inputs to farmland than other recycling products or commercial mineral and organic fertilizers. When combined with other soil conditioners, urine-derived struvite is an efficient fertilizer which covers the magnesium and more than half of the phosphorus demand of crops.     

Contaminated sediments and bioassay responses of three macroinvertebrates, the midge larva Chironomus riparius, the water louse Asellus aquaticus and the mayfly nymph Ephoron virgo

Bioassays are widely used to estimate ecological risks of contaminated sediments. We compared the results of three whole sediment bioassays, using the midge larva Chironomus riparius, the water louse Asellus aquaticus, and the mayfly nymph Ephoron virgo. We used sediments from sixteen locations in the Dutch Rhine-Meuse Delta that differed in level of contamination. Previously developed protocols for each bioassay were followed, which differed in sediment pretreatment, replication, and food availability. The Chironomus bioassay was conducted in situ, whereas the other two were conducted in the laboratory. The measured endpoints, survival and growth, were related to contaminant levels in the sediment and to food quantity in water and sediment.

Only the response of A. aquaticus in the bioassay was correlated with sediment contamination. Food availability in overlying water was much more important for C. riparius and E. virgo, thereby masking potential sediment contaminant effects. We conclude that growth of A. aquaticus was depressed by sediment contamination, whereas growth of E. virgo and C. riparius was stimulated by seston food quantity. We discuss that the trophic state of the ecosystem largely affects the ecological risks of contaminated sediments.     

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.     

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。     

Phosphorus leaching in soils amended with piggery effluent or lime residues from effluent treatment

Phosphorus (P) in wastes from piggeries may contribute to the eutrophication of waterways if not disposed of appropriately. Phosphorus leaching, from three soils with different P sorption characteristics (two with low P retention and one with moderate P retention) when treated with piggery effluent (with or without struvite), was investigated using batch and leaching experiments. The leaching of P retained in soil from the application of struvite effluent was determined. In addition, P leaching from lime residues (resulting from the treatment of piggery effluent with lime to remove P) was determined in comparison to superphosphate when applied to the same three soils. Most P was leached from sandy soils with low P retention when effluent with or without struvite was applied. More than 100% of the filterable P applied in struvite effluent was leached in sandy soils with low P retention. Solid, inorganic forms of P (struvite) became soluble and potentially leachable at pH<7 or were sorbed after dissolution if there were sufficient sorption sites. In sandy soils with low P retention, more than 39% of the total filterable P applied in recycled effluent (without struvite) was leached. Soil P increased mainly in surface layers after treatment with effluent. Sandy soils pre-treated with struvite effluent leached 40% of the P retained in the previous application. Phosphorus decreased in surface layers and increased at depth in the soil with moderate P retention after leaching the struvite effluent pre-treated soil with water. The soils capacity to adsorb P and the soil pH were the major soil properties that affected the rate and amount of P leaching, whereas the important characteristics of the effluent were pH, P concentration and the forms of P in the effluent. Phosphorus losses from soils amended with hydrated lime and lime kiln dust residues were much lower than losses from soils amended with superphosphate. Up to 92% of the P applied as superphosphate was leached from sandy soils with low P retention, whereas only up to 60% of the P applied in lime residues was leached. The P source contributing least to P leaching was the lime kiln dust residue. The amount of P leached depended on the water-soluble P content, neutralising value and application rate of the P source, and the pH and P sorption capacity of the soil.