Nutrient removal and energy production in a urine treatment process using magnesium ammonium phosphate precipitation and a microbial fuel cell technique

Urine pretreatment has attracted increasing interest as it is able to relieve the nitrogen and phosphorus overloading problems in municipal wastewater treatment plants. In this study, an integrated process, which combines magnesium ammonium phosphate (MAP) precipitation with a microbial fuel cell (MFC), is proposed for the recovery of a slow-release fertilizer and electricity from urine. In such a two-step process, both nitrogen and phosphorus are recovered through the MAP process, and organic matters in the urine are converted into electricity in the MFCs. With this integrated process, when the phosphorus recovery is maximized without a dose of PO(4)(3-)-P in the MAP precipitation process, removal efficiencies for PO(4)(3)-P and NH(4)(+)-N of 94.6% and 28.6%, respectively, were achieved with a chemical oxygen demand (COD) of 64.9% accompanied by a power output of 2.6 W m(-3). Whereas removal efficiencies for PO(4)(3)-P and NH(4)(+)-N of 42.6% and 40%, respectively, and a COD of 62.4% and power density of 0.9 W m(-3) were obtained if simultaneous recovery of phosphorus and nitrogen was required through dosing with 620 mg L(-1) of PO(4)(3-)-P in the MAP process. This work provides a new sustainable approach for the efficient and cost-effective treatment of urine with the recovery of energy and resources.     

Influence of Operational Parameters and Low Nickel Concentrations on Partial Nitrification in a Submerged Biofilter

The effect of Ni(2+) concentrations on ammonium oxidation was studied in a batch and partial bionitrification reactor (PBNR). The nitrification rates up to the concentration of 0.1 mg Ni(2+)/l were close to those without Ni(2+). After testing the operational conditions in the PNBR, the highest NO(2)-N/NO( x )-N ratio was achieved at the DO concentrations of 2.0 mg/l and pH 9.00. The PNBR was operated at steady state (NH(4)-N loading rate and NO(2)-N/NO( x )-N ratio were 405?g m(-3) day(-1) and 0.74, respectively) before exposure to Ni(2+). The removal efficiency of NH(4)-N and NO(2)-N/NO( x )-N ratio in the effluent waters was increased by adding low concentrations of heavy metals to the PBNR. The average number of aerobic mesophilic bacteria at the biofilm surface and in the water in the void volume of PNBR were 1.0?×?10(4) CFU/g and 1.4?×?10(5) CFU/ml, respectively.     

杂多酸水溶液脱除烟气中SO2新方法的研究

在孔板式吸收器（孔板孔径：50μm-70μm）中对杂酸水溶液脱除烟气中SO2的新方法进行了研究。在所考察的几种杂多酸中,H3PW12O40和H2SiW12O40对SO2的脱除率较为接近,H7PMo2W12O49和Na2HPMo12O40对SO2的脱除率相对较高,其中后者对SO2的脱除率最高。杂多酸（HPA）对SO2的脱除率随HPA浓度的提高而增高,随进气中SO2的浓度或吸收温度提高而减低。常温有利于HPA对SO2的脱除。NaCl,NH4VO3,CuSO4及H3PO4这四种添加剂均能提高HPA对SO2的脱除率。复配体系中,以上添加剂对HPA的最优配比为：NaCl/HPA:H3PO4/HPA:NH4VO3/HPA:CuSO4/HPA=1/6:1/8:1/2:1/4。进气中有NOx存在下HPA对SO2的脱除反应式,这些反应式能够很好地说明NOx的作用效果。以上结果表明：HPA水溶液具有很好的烟气脱硫应用前景。     

Optimization of ammonium removal from waste water by natural zeolite using central composite design approach

The aims of the present study are to investigate removal of ammonium ion from wastewater using natural Western Azarbaijan zeolite and to optimize effective parameters by experimental design. In order to remove ammonium ions from aqueous solutions, experiments were carried out using column method as functions of the initial ammonium concentration, flow rate and pH of the solution. The results clearly confirmed that all mentioned parameters have vital affects on removing ammonium ions from wastewater and effluents, so got optimized. Central composite design with response surface methodology was applied for the optimization of main experiment parameters. The significance of the independent variables and their interactions were tested by the analysis of variance ANOVA and f-test statistics. Optimization of the variables for maximum removal efficiency by natural zeolite was performed using the quadratic model. The model predicted maximum removal efficiency under the optimum conditions including initial ammonium concentration of 30?mg?l^?1; flow rate of 1?ml?min^?1 and pH 6, which was very close to the experimental value determined in column experiment. The cation exchange capacity of natural Western Azarbaijan zeolite was found to be 1.79?meq?g^?1. Based on the experimental results, it can be concluded that the natural Western Azarbaijan zeolite has an excellent potential for removing ammonium ions from aqueous solutions and it is suggested as a suitable material for wastewater treatment.     

Removal of aqueous ammonium with magnesium phosphates obtained from the ammonium-elimination of magnesium ammonium phosphate

In order to recycle magnesium ammonium phosphate (MgNH4PO4.6H2O: MAP) obtained from MAP process, which is one of the attractive processes for removal of aqueous ammonium and phosphate from wastewater, ammonium elimination from MAP to magnesium phosphates and ammonium incorporation into the magnesium phosphates have been investigated in the present study. It is confirmed that magnesium hydrogen phosphate (MgHPO4) is favorably obtained from the ammonium elimination from MAP at temperatures greater than 353 K, although magnesium phosphate (Mg3(PO4)2) and magnesium pyrophosphate (Mg2P2O7) have been suggested as possible candidates. Based on the dissolution-precipitation mechanism for the removal of aqueous ammonium with magnesium phosphates, three magnesium phosphates were employed for the removal of aqueous ammonium. The order of the removal rate of the aqueous ammonium was MgHPO4>Mg3(PO4)2>Mg2P2O7, as expected from the solubility of those magnesium phosphates. The removability of the solid obtained from ammonium elimination of MAP is also confirmed. The present results show that MAP can be employed as an advanced material for the removal/recovery of ammonium, although it is generally accepted that an excess of MAP obtained from the wastewater treatment can be only used as a slow-acting fertilizer.     

Measurement of ascorbic acid and dehydroascorbic acid in gastric juice by HPLC

New methods are presented for measuring total vitamin C and the ascorbic acid/dehydroascorbic acid ratio in gastric juice. Extracts are prepared from a gastric juice which are suitable for direct injection onto a Waters Nova-pak C18 Radial-pak cartridge for high performance liquid chromatography (HPLC) using ultraviolet absorbance at 270 nm for detection. Both enable removal of interfering mucus and mucopolysaccharide breakdown products in a novel way. The first uses mini-columns of Sephadex G-50, run in acidic conditions to remove large molecular weight material while maintaining the ascorbic acid/dehydroascorbic acid ratio as it was in the fresh sample. Addition of dithiothreitol converts the dehydroascorbic acid quantitatively to ascorbic acid, thus enabling measurement of both components. The second method converts all the dehydroascorbic acid to ascorbic acid at the outset. A perchloric acid extract is neutralized and passed through a Sep-Pak C18. A new internal standard, reductic acid, is introduced for ascorbic acid analysis which behaves identically on Sep-Pak C18. Samples are analysed by ion-pair chromatography using 0.02 M NH4H2PO4 buffer (pH 7.1): methanol (80:20 v/v) containing 0.62 g/L tetrapentylammonium bromide. The detection limit was 1 ng ascorbic acid, and chromatography was completed in 5 min. The values obtained by the two independent HPLC methods were in good agreement with each other and with those obtained by the 2,4-dinitrophenylhydrazine colorimetric method.     

不同Ｎａ／Ｐ比磷酸钠盐催化剂对乳酸转化反应的影响

将NaH2PO4与不同比例的Na2CO3或H3PO4混合,通过浸渍法负载在硅胶上,经过焙烧,制备了Na/P比不同的磷酸钠盐催化剂.利用所制备的催化剂考察了乳酸生成丙烯酸的脱水反应.运用XRD、Raman以及31PNMR等手段对所制备的催化剂结构进行了表征,并使用NH3-TPD对磷酸钠盐催化剂的酸强度和酸性位密度进行了测量.结合催化剂的结构表征结果,对磷酸钠盐的表面酸性进行了探讨.基于磷酸钠催化剂的结构和酸性,讨论了它们的催化性能.     

Analysis of oligodeoxynucleotides by negative-ion matrix-assisted laser desorption mass spectrometry

Thirty compounds were tested in combination with ammonium acetate for the ability to desorb and ionize oligodeoxynucleotides by ultraviolet matrix-assisted laser desorption mass spectrometry. Negative ion yields using matrices such as 2,5-dihydroxybenzoic acid and 3-hydroxy-4-methoxybenzaldehyde are enhanced by the addition of ammonium salts at a molar ratio of 1:1, pH 7. 3-Hydroxy-4-methoxybenzaldehyde was tested with 12 different ammonium, alkylammonium, and pyridinium salts for the ability to cocrystallize with oligodeoxynucleotides and to improve desorption and ionization. Ions of oligodeoxynucleotides 9, 10, and 11 nucleotides in length were observed with a matrix of 3-hydroxy-4-methoxybenzaldehyde and ammonium acetate, pH 7, at a mass resolution of 100–150 (fwhm). A small oligodeoxynucleotide (11-mer) was observed at the femtomole level with a combination of 2,5-dihydroxybenzoic acid and ammonium acetate as the matrix. Ions from single stranded DNA (60 nucleotides in length) were also observed using this same matrix combination. The results of these studies have shown that both sensitivity and desorption conditions need to be further improved before complex mixtures of large pieces of DNA can be effectively analyzed.     

CdS/TiO2光催化去除水体中氨氮的研究

利用溶胶-凝胶法制备了不同比率的CdS掺杂TiO₂复合纳米颗粒催化剂,并用其进行了紫外光、日光灯和太阳光全波长光催化去除水中氨氮和其它形式无机氮的对比实验研究.考察了添加催化剂的量、CdS复合比率、有氧化态氮亚硝酸根或硝酸根与氨氮共存时光催化脱氮的耦合效果、外加光源等对脱除氨氮效率的影响,并研究了后3个因素对CdS光腐蚀程度的影响.对于氨氮初始质量浓度为50mg/L的模拟废水,在通空气搅拌条件下,n(CdS):n(TiO₂)=0.17的CdS/TiO₂催化剂脱氮效果最佳,此时经紫外光照2h后脱除氨氮效率达41.5%.实验结果表明:复合催化剂中CdS的含量是影响光催化活性和光腐蚀程度的重要因素.     

热分解法制备纳米氧化钕

采用热分解法以2-硝基苯甲酸和硝酸钕为原料制备了纳米氧化钕微粉,利用正交设计对合成条件进行了优化,得出了最佳的合成条件,即原料2-硝基苯甲酸与硝酸钕物质的量比2.5∶1,溶液pH值5.5,反应时间3h、干燥时间8 h,在此条件下制得了平均粒径为15 nm的氧化钕微粉,并利用XRD和TEM对制得的纳米微粉进行了结构表征.     

负载零价铁膨胀石墨的合成及对水中NO3-去除的效果与机制

以网络状孔型结构发达的膨胀石墨（EG）为载体,采用化学沉积法制备了负载零价铁（ZVI）的膨胀石墨（EG-ZVI）.利用扫描电子显微镜（SEM）、X射线衍射（XRD）仪及X射线光电子能谱仪（XPS）等对负载及反应前后的EG-ZVI进行表征,探究了EG-ZVI对硝酸根（NO₃^-）的去除效果并对其反应产物及机理进行了分析.结果表明,亚微米级零价铁已负载到EG石墨表面,且分布均匀;与EG相比,EG-ZVI对NO₃^-的去除能力显著提升,其去除率是EG的2.3倍.得益于铁碳原电池效应,EG-ZVI对pH依赖性比零价铁低,即使在pH=9的条件下,NO₃^-去除率依然能达到65%以上,是单独用零价铁处理时的1.83倍;EG-ZVI去除NO₃^-是吸附和还原过程共同作用的结果,符合三级动力学模型,其还原过程由负载在EG表面的零价铁发生腐蚀提供电子,从而还原NO₃^-产生以NH₄⁺-N为主的含氮化合物;EG-ZVI对NO₃^-具有较强的还原吸附作用,并能解决零价铁在反应过程中生成惰性层或金属氢氧化物导致去除效率低的缺陷,使其在含NO₃^-废水的处理中具有较高的应用潜力.     

Denitrification of simulated nitrate-rich wastewater using sulfamic acid and zinc scrap

An enhanced chemical denitrification process was studied as an alternative treatment of nitrate-rich wastewater which cannot be easily treated using conventional biological methods. To accelerate denitrification and to reduce the conversion to ammonia, nitrite reductants were added. In a batch test with the initial nitrate concentration of 500 mg NO ₃ ^? -N per L, sulfamic acid and zinc were found to be the best nitrite and metal reductants, respectively. In a column test with the initial nitrate concentration of 500 mg NO ₃ ^? -N per L, optimum results were experimentally obtained over a zinc scrap column with a 1.0 molar ratio of [NH₂SO₃H]/[NO ₃ ^? -N] and the recirculating flow rate of 6 L min^?1 at pH 2.5. Approximately 98.8 % of nitrate anions were removed, and the observed reaction rate constant (k) was 0.135 min^?1. Zinc consumption was reduced to 46.6 % compared to the procedure without sulfamic acid, and sulfamic acid consumption was reduced to 40 % compared to the results of our previous study. Based on these experimental results, it was concluded that chemical nitrate denitrification using sulfamic acid and zinc scrap is an effective alternative treatment protocol for nitrate-rich wastewater.     

Surface modification of calcium hydroxyapatite with pyrophosphoric acid

The surface of synthetic colloidal calcium hydroxyapatite (Ca(10)(PO(4))(6)(OH)(2); CaHap) was treated with pyrophosphoric acid (H(4)P(2)O(7); PP) in acetone and the materials were characterized by XRD, thermal analysis, N(2) adsorption, TEM, and FTIR. No remarkable change in XRD patterns or in particle morphology by the modification was observed. The additional amount of PO(4) of CaHap was increased with an increase in PP concentration. The Ca/P molar ratio of CaHap was decreased from 1.62 to 1.35 by the modification. IR results indicated that the PP reacts with surface P-OH groups of CaHap to form additional surface P-OH groups as follows: surface P-OH+H(4)P(2)O(7)--> surface P-O-PO(OH)(2) + H(3)PO(4). When the modified CaHap with Ca/P molar ratio less than 1.50 was treated at 850 degrees C in air, the materials transformed into beta-Ca(3)(PO(4))(2).     

Treatment of wastewater to remove ammonium ions by precipitation

The process of wastewater treatment to remove ammonium ions by precipitation in the form of ammonium magnesium phosphate was studied. The fundamental aspects of the chemical precipitation process were examined. The effect of various factors on the efficiency of wastewater treatment was experimentally analyzed.     

Linear alkyl diamine-uranium-phosphate systems: U(VI) to U(IV) reduction with ethylenediamine

Mild-hydrothermal reactions in acidic medium using 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane as structure directing agents led to three-dimensional (3D) uranyl phosphates (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C3U5P4), (CH?)?(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C4U5P4) and (CH?)5(NH?)?{[(UO?)(H?O)][(UO?)(PO?)]?} (C5U5P4). The structures of (C4U5P4) and (C5U5P4) were solved in the space group Cmc2? using single-crystal X-ray diffraction data. The compounds are isostructural to the corresponding uranyl vanadates and contain the same 3D inorganic framework built from uranyl-phosphate layers of uranophane-type anion topology pillared by [UO?(H?O)] pentagonal bipyramids. In neutral or basic medium the alkyl diamines decompose to give ammonium uranyl phosphate trihydrate. In the same conditions by using ethylenediamine, unexpected reduction of uranium(VI) to uranium(IV) occurs leading to the formation of (CH?)?(NH?)?[U(PO?)?] (C2UP2) single crystals. C2UP2 undergoes a reversible phase transition from triclinic to monoclinic symmetry at about 230 °C. The structure of the two forms results from the stacking of inorganic layers (∞)1[U(PO?)?]2?, and organic layers containing ethylene diammonium ions, the two layers being linked by hydrogen bonds. Single crystals of (CH?)?(NH?)?[PO?OH] (C2HP) are formed by evaporation of the solution after filtering of C2UP2 single crystals. The structure of C2HP contains infinite (∞)1[PO?OH]2? chains connected by (CH?)?(NH?)?2? ions through hydrogen bonds.     

The Effect of 2-Mercapto-5-Methyl-1,3,4-Thiadiazole on Enzymatic Synthesis of Cefazolin

The effect of unreacted residual 2-mercapto-5-methyl-l,3,4-thiadiazole (MMTD), the reagent for 3-[5-methyl-l,3,4-thiadiazole-2-yl]-7-aminocephalosporanic acid (M-7-ACA) synthesis, on the enzymatic acylation of M-7-ACA by the methyl ester of 1,2,3,4-tetrazol-1-acetic acid (MeTzAA) to produce cefazolin (CEZ) was studied. In the two-step process of synthesizing CEZ from 7-aminocephalosporanic acid (7-ACA), one of the key parameters controlling the overall CEZ yield was the ratio of MMTD to 7-ACA in M-7-ACA synthesis. The increase of the ratio showed opposing effects by increasing the M-7-ACA yield in the first step, while decreasing CEZ yield in the subsequent enzymatic reaction by the inhibitory effect of the increased content of MMTD as an impurity in the M-7-ACA preparation. It was revealed that the decrease of CEZ yield in the enzymatic reaction was caused by the selective retardation of the rate of CEZ synthesis reaction by a typical competitive inhibition, while not affecting the rate of MeTzAA hydrolysis reaction. The optimum MMTD-to-7-ACA ratio rendering the highest overall CEZ yield over 7-ACA was 1.2:1.     

Oxidative decarboxylation of levulinic acid by silver(I)/persulfate

The oxidative decarboxylation of levulinic acid (LA) by silver(I)/persulfate [Ag(I)/S?O?2?] has been investigated in this paper. The effects of buffer solution, initial pH value, time and temperature and dosages of Ag(I)/S?O?2? on the decarboxylation of LA were examined in batch experiments and a reaction scheme was proposed on basis of the reaction process. The experimental results showed that a solution of NaOH-KH?PO? was comparatively suitable for the LA decarboxylation reaction by silver(I)/persulfate. Under optimum conditions (temperature 160 °C, pH 5.0, and time 0.5 h), the rate of LA conversion in NaOH-KH?PO? solutions with an initial concentration of 0.01 mol LA reached 70.2%, 2-butanone (methyl ethyl ketone) was the single product in the gas phase and the resulted molar yield reached 44.2%.     

Coordination of copper(II) ions by the fragments of neuropeptide gamma containing D1, H9, H12 residues and products of copper-catalyzed oxidation

A potentiometric, spectroscopic (UV-Vis, CD and EPR) and mass spectrometric (ESI-MS) study of Cu(II) binding to the (1-2,7-21)NPG, Asp(1)-Ala-Ile(7)-Ser-His(9)-Lys-Arg-His(12)-Lys-Thr-Asp-Ser-Phe-Val-Gly-Leu-Met(21)-NH(2), and Ac-(1-2,7-21)NPG, Ac-Asp(1)-Ala-Ile(7)-Ser-His(9)-Lys-Arg-His(12)-Lys-Thr-Asp-Ser-Phe-Val-Gly-Leu-Met(21)-NH(2), fragments of neuropeptide gamma were carried out. The results clearly indicate the stabilization of the 1 N {NH(2), β-COO(-)}, 2 N {NH(2), β-COO(-), N(Im)} and 3 N {NH(2), β-COO(-), 2N(Im)} complexes by the coordination of the β-carboxylate group of the D(1) residue. For the (1-2,7-21)NPG the CuH(2)L complex with 3 N {NH(2), β-COO(-), 2N(Im)}, the binding mode dominates in a wide pH range of 4-8.5. With the sequential increase of pH, deprotonated amide nitrogens are involved in copper coordination. For the Ac-(1-2,7-21)NPG peptide the imidazole nitrogen atoms are the primary metal binding sites forming macrochelates in the pH range 4 to 7. The CuHL complex with 4 N {N(Im), N(-), N(-), N(Im)} coordination mode is formed in pH range 6-9. Deprotonation and co-ordination of the third amide nitrogen were detected at pH ～8.6. Metal-catalyzed oxidation (MCO) of proteins is mainly a site-specific process in which one or a few amino acids at metal-binding sites on the protein are preferentially oxidized. To elucidate the products of the copper(II)-catalyzed oxidation of the (1-2,7-21)NPG and Ac-(1-2,7-21)NPG, the liquid chromatography-mass spectrometry (LC-MS) method and Cu(II)/hydrogen peroxide as a model oxidizing system were employed. In the presence of hydrogen peroxide with 1?:?4 peptide-H(2)O(2) molar ratio for the Ac-(1-2,7-21)NPG peptide the oxidation of the methionine residue to methionine sulfoxide and for (1-2,7-21)NPG to sulfone was observed. For the Cu(II)-peptide-hydrogen peroxide in 1?:?1?:?4 molar ratio systems, oxidation of the histidine residues to 2-oxohistidines was detected. Under experimental conditions the (1-2,7-21)NPG and Ac-(1-2,7-21)NPG undergo fragmentations by cleavage of the S(8)-H(9), H(9)-K(10), R(11)-H(12) and H(12)-K(13) peptide bonds supporting the participation of the H(9) and H(12) residues in the coordination of copper(II) ions. For the (1-2,7-21)NPG peptide chain the involvement of the D(1) residue in the coordination of metal ions is supported by the alkoxyl radical modification of this amino acid residue.     

Vapor-phase synthesis of mesoporous SiO2-P2O5 thin films

Mesoporous SiO2-P2O5 films were synthesized from the vapor phase onto a silicon substrate. First, a precursor solution of cetyltrimethylammonium bromide (C16TAB), H3PO4, ethanol, and water was deposited on a silicon substrate by a spin-coating method. Then, the C16TAB-H3PO4 composite film was treated with tetraethoxysilane (TEOS) vapor at 90-180 degrees C for 2.5 h. The H3PO4-C16TAB composite formed a hexagonal structure on the silicon substrate before vapor treatment. The TEOS molecules penetrated into the film without a phase transition. The periodic mesostructure of the SiO2-P2O5 films was retained after calcination. The calcined films showed a high proton conductivity of about 0.55 S/cm at room temperature. The molar ratio of P/Si in the SiO2-P2O5 film was as high as 0.43, a level that was not attained by a premixing sol-gel method. The high phosphate group content and the ordered periodic mesostructure contributed to the high proton conductivity.     

Speciation of arsenic by ion chromatography inductively coupled plasma mass spectrometry using ammonium eluents

A method based on ion chromatography (IC) and inductively coupled plasma MS (ICP-MS) was developed for the speciation of arsenic in water and soil extracts. An anion-exchange column (G3154A/101) was used to separate As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) with excellent resolution. Various ammonium salts, including NH4H2PO4, (NH4)2HPO4, (NH4)2CO3, and NH4HCO3, were examined as eluents to reduce matrix interference from chloride and to solve clogging problems. The best arsenic speciation was obtained within 9 min with excellent resolution and without interference from high chloride concentrations using an eluent containing 7.5 mM (NH4)2HPO4 at pH 7.9. The detection limits for the target arsenic species ranged from 0.1 to 0.4 microg/L with direct injection of sample without matrix elimination. The proposed method was effectively demonstrated by determining arsenic species in contaminated waters and soils of Bangladesh.