Fe2+/Fe3+和Mn2+对低氧曝气过程总氮去除与转化途径的影响

为短期快速实现实际生活污水自养脱氮,采用含有厌氧氨氧化菌的实际污水处理厂活性污泥,针对Fe²⁺/Fe³⁺和Mn²⁺对低氧曝气过程中氮的去除效果进行了研究,分析确定了氮素转化的途径。研究结果表明,Fe²⁺/Fe³⁺和Mn²⁺均可提高活性污泥中厌氧氨氧化菌（AnAOB）丰度,但由于Fe²⁺/Fe³⁺对氨氧化菌（AOB）也存在一定抑制作用,因此,短期投加Fe²⁺/Fe³⁺条件下,低氧曝气过程中总无机氮去除率为25%,但投加Mn²⁺条件下总无机氮去除率可达44%。通过氮素平衡分析,发现投加Fe²⁺/Fe³⁺条件下,氮素主要通过反硝化作用去除;而投加Mn²⁺条件下,氮素主要通过厌氧氨氧化（anammox）作用去除。因此,传统活性污泥可通过短期投加Mn²⁺增强厌氧氨氧化活性,促进低氧曝气过程中氮的去除,利于快速实现一体化自养脱氮。     

Simultaneous removal of NO and SO2 using aqueous peroxymonosulfate with coactivation of Cu2+/Fe3+ and high temperature

A novel process on simultaneous removal of NO and SO₂ using aqueous peroxymonosulfate (PMS) with synergic activation of Cu²⁺/Fe³⁺ and high temperature in an impinging stream reactor is developed for the first time. Effects of PMS concentration, Cu²⁺/Fe³⁺ concentration, reaction temperature, solution pH, flue gas flow, liquid–gas ratio, gas components, and inorganic ions on NO/SO₂ removals were investigated. Active species and products were determined by electron spin resonance spectroscopy and ion chromatography. Removal pathways of NO/SO₂ were revealed, and mass transfer‐reaction kinetics of NO removal was studied. The optimal experimental conditions are obtained. H₂SO₄ and HNO₃ are the main products. It is found that there is a clear synergy between Cu²⁺/Fe³⁺ and high temperature for activating PMS. and ·OH are found to be the main oxidants for NO removal. NO removals belong to pseudo‐first fast reactions in the two investigated oxidation systems. Besides, the kinetic parameters are also measured. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1287–1302, 2017     

氨水中Fe~ (2+)、Fe~(3+)含量的控制及分析方法

介绍了氨水中Ｆｅ２＋、Ｆｅ３＋含量的控制指标及其分析原理和分析方法     

Effects of Fe2+/Fe3+ Binding to Human Frataxin and Its D122Y Variant,as Revealed by Site-Directed Spin Labeling (SDSL) EPR Complemented by Fluorescence and Circular Dichroism Spectroscopies

Frataxin is a highly conserved protein whose deficiency results in the neurodegenerative disease Friederich’s ataxia. Frataxin’s actual physiological function has been debated for a long time without reaching a general agreement; however, it is commonly accepted that the protein is involved in the biosynthetic iron-sulphur cluster (ISC) machinery, and several authors have pointed out that it also participates in iron homeostasis. In this work, we use site-directed spin labeling coupled to electron paramagnetic resonance (SDSL EPR) to add new information on the effects of ferric and ferrous iron binding on the properties of human frataxin in vitro. Using SDSL EPR and relating the results to fluorescence experiments commonly performed to study iron binding to FXN, we produced evidence that ferric iron causes reversible aggregation without preferred interfaces in a concentration-dependent fashion, starting at relatively low concentrations (micromolar range), whereas ferrous iron binds without inducing aggregation. Moreover, our experiments show that the ferrous binding does not lead to changes of protein conformation. The data reported in this study reveal that the currently reported binding stoichiometries should be taken with caution. The use of a spin label resistant to reduction, as well as the comparison of the binding effect of Fe²⁺ in wild type and in the pathological D122Y variant of frataxin, allowed us to characterize the Fe²⁺ binding properties of different protein sites and highlight the effect of the D122Y substitution on the surrounding residues. We suggest that both Fe²⁺ and Fe³⁺ might play a relevant role in the context of the proposed FXN physiological functions.     

Fe3+在A2O工艺缺氧区的转化规律及其对污泥絮凝性的影响

为了研究铁元素对A²O工艺污泥絮凝性的影响,考察Fe³⁺在污泥上清液、胞外聚合物（extracellular polymeric substances,EPS）与底泥（Pellet）中的分布和迁移转化规律,结合三维荧光光谱（3D-EEM）、原子吸收和X射线衍射仪（XRD）分析Fe的存在形态和结构特征,揭示Fe³⁺与微生物代谢产物的作用机制,探索Fe³⁺对脱氮除磷效率的影响。结果表明：低浓度Fe³⁺（<10 mg·L^-1）能够提高COD和TN去除率,促进微生物活性,增强污泥生物絮凝性;高浓度Fe³⁺（10~40 mg·L^-1）则抑制微生物活性,使EPS总量升高,污泥絮体脱稳,LB、TB层PN/PS是影响污泥絮凝性的关键因素;Fe³⁺的投加强化生物除磷效率,当Fe³⁺浓度为40 mg·L^-1时,TP去除率为93%。Fe³⁺在污泥混合液中的分布规律为TB>上清液>LB>SMP,Fe³⁺在生物体内富集累积,能够改变EPS各层的组分。     

A computational investigation on the molecular structure,electronic properties and intramolecular hydrogen bonding interaction of 1,1,1-trifluoro-4-mercaptobut-3-ene-2-thione in ground and electronic excited state

The hydrogen bond (HB) strength, geometry optimization, vibrational frequencies and several well-established indices of aromaticity in 1,1,1-trifluoro-4-mercaptobut-3-ene-2-thione and its 15 derivatives in two positions, R1 and R2, have been investigated by means of the density functional theory (DFT) method with 6-311++G** basis set in the gas phase. The obtained results show that the HB strength is mainly governed by resonance variations inside the chelate ring induced by the substituent groups. The following substituents have been taken into consideration: NO₂, SCF₃, Ph, PhOCH₃, SCOCH₃, CH₂OCH₃ and CH₂OH. The strongest S–H···S HBs belong to PhOCH₃-substituted system in both positions, whereas NO₂ and H substitutions in R1 and R2 positions, respectively, produce the weakest S–H···S hydrogen bridges. The excited-state properties of intramolecular hydrogen bonding in substituted systems have been investigated theoretically using the time-dependent DFT method. Natural bond orbital analysis is also performed for a better understanding of the nature of intramolecular interactions. The electron density and Laplacian (?²ρ) properties, estimated by atoms in molecule calculations, indicate that the H···S bond possesses low ρ, positive ?² ρ and H_C<0, which are in agreement with the partially covalent character of HBs.     

Coexistence mechanism of Eu2+/Eu3+ ions in YAl3(BO3)4: Crystal structure,luminescence property,and substitution defects

The coexistence mechanism of Eu²⁺ and Eu³⁺ ions in YAl₃(BO₃)₄ host under different reducing conditions is investigated and confirmed in great detail, which can be described by three aspects as following. First, Eu³⁺ is protected by the layered structure of YAl₃(BO₃)₄. Second, the number of the interstitial defects ((Al)_i^…,(Y)_i^…) increases with increasing Eu²⁺ to maintain the charge balance of the system. And these defects can capture free electrons which are used for the reduction of Eu³⁺. Finally, free holes become more and more with the number of nonequivalent substitution defects (Eu_Y') increasing, which make the 5d electrons of Eu²⁺easily escape to the conduction band and Eu²⁺ convert to Eu³⁺. This work will be of great significance to research coexistence of multiple valence ions in the structure of borate and defect motion with nonequivalent substitution.     

Local coordination,electronic structure,and thermal quenching of Ce3+ in isostructural Sr2GdAlO5 and Sr3AlO4F phosphors

Sr₂GdAlO₅:Ce and Sr₃AlO₄F:Ce are isostructural phosphors in which the Ce³⁺ 4f-5d₁ transition can be efficiently excited by a photon with energy lower than 3.1 eV. Herein, we analyze the crystal chemistry of the Ce³⁺ local coordination, compare the thermal quenching behavior and construct the electronic structure of Ce³⁺ in them. The Rietveld refinement on two occupancy models suggests that Gd³⁺ only occupies the 8h site in Sr₂GdAlO₅; this provides a hint on the preferred occupancy of dopant Ce³⁺ in this site. The large crystal filed splitting of Ce_8h is mainly due to the fact that the 8h site is bonded to two oxygen with relatively short d_Sr/Gd-O and forms a quasi-square antiprism which experiences a large distortion. The Ce³⁺ 5d-4f luminescence in Sr₃AlO₄F is much more stable against thermal quenching than that in Sr₂GdAlO₅, as evidenced by the temperature-dependent luminescence intensity and luminescence decay studies. The energy of the O²⁻-Eu^3+/2+ and O²⁻-Ce^4+/3+ charge transfer as well as bandgap were estimated and the electronic structure of Ce³⁺ were constructed. A larger energy barrier ΔE_dC between the Ce³⁺ 5d₁ level and the conduction band bottom in Sr₃AlO₄F is seen from the Vacuum Referred Binding Energy (VRBE) diagrams which explains the higher thermal quenching temperature by thermal ionization model.