Fabricating Fe3O4-schwertmannite as a Z-scheme photocatalyst with excellent photocatalysis-Fenton reaction and recyclability

Here we reported an effective method to solve the rate-limiting steps, such as the reduction of Fe³⁺ to Fe²⁺ and an invalid decomposition of H₂O₂ in a conventional Fenton-like reaction. A magnetic heterogeneous photocatalyst, Fe₃O₄-schwertmannite (Fe₃O₄-sch) was successfully developed by adding Fe₃O₄ in the formation process of schwertmannite. Fe₃O₄-sch shows excellent electrons transfer ability and high utilization efficiency of H₂O₂ (98.5%). The catalytic activity of Fe₃O₄-sch was studied through the degradation of phenol in the heterogeneous photo-Fenton process. Phenol degradation at a wide pH (3 - 9) was up to 98% within 6 min under visible light illumination with the Fe₃O₄-sch as heterogeneous Fenton catalyst, which was higher than that using pure schwertmannite or Fe₃O₄. The excellent photocatalytic performance of Fe₃O₄-sch is ascribed to the effective recycling between Fe³⁺ and Fe²⁺ by the photo-generated electron, and also profit from the formation of the “Z-Scheme” system. According to the relevant data, photocatalytic mechanism of Fe₃O₄-sch for degrading phenol was proposed. This study not only provides an efficient way of enhancing heterogeneous Fenton reaction, but also gives potential application for iron oxyhydroxysulfate mineral.     

Tracking the reactivity of ozonation towards effluent organic matters from WWTP using two-dimensional correlation spectra

The characteristics of effluent organic matter (EfOM) from a wastewater treatment plant (WWTP) during ozonation were investigated using excitation and emission matrix (EEM) spectra, Fourier transform infrared spectroscopy (FT-IR) and high-performance size exclusion chromatography (HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra (2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC. The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution (MWD). According to 2D-COS analysis, microbial humic-like substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence: phenolic and alcoholic CO groups?>?aromatic structures containing CC double bonds?>?aliphatic CH. X-ray photoelectron spectroscopy (XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.     

Efficient capture of aqueous humic acid using a functionalized stereoscopic porous activated carbon based on poly(acrylic acid)/food-waste hydrogel

Stereoscopic porous carbons have shown good potential in humic acid (HA) removal. In this work, a novel stereoscopic porous activated carbon (SPAC) was designed and synthesized via the self-assembly of a hydrogel based on food waste during in-situ polymerization, vacuum drying, carbonization, and activation. Then, the SPAC was functionalized with 3-aminopropyltriethoxysilane (APTES) and the adsorption behavior of the modified SPAC (SPAC-NH₂) was studied systematically. The effects of pH, contact time, initial concentration of HA, and adsorbent dose were investigated, showing that optimal HA removal efficiency (> 98.0%) could be achieved at an initial HA concentration of 100?mg/L. The experimental adsorption isotherm data was fitted to the Langmuir model with a maximum adsorption capacity of 156.0?mg?HA/g SPAC-NH₂. Analysis of the mechanism indicated that the removal of HA was mainly realized through the amidization reaction between the COOH groups of HA and the NH₂ groups of APTES. All of the above results showed that SPAC-NH₂ powder is an efficient, eco-friendly, and reusable adsorbent which is suitable for the removal of HA from wastewater.     

A theoretical study of hydrogen-bonded molecular clusters of sulfuric acid and organic acids with amides

Amides, a series of significant atmospheric nitrogen-containing volatile organic compounds (VOCs), can participate in new particle formation (NPF) throught interacting with sulfuric acid (SA) and organic acids. In this study, we investigated the molecular interactions of formamide (FA), acetamide (AA), N-methylformamide (MF), propanamide (PA), N-methylacetamide (MA), and N,N-dimethylformamide (DMF) with SA, acetic acid (HAC), propanoic acid (PAC), oxalic acid (OA), and malonic acid (MOA). Global minimum of clusters were obtained through the association of the artificial bee colony (ABC) algorithm and density functional theory (DFT) calculations. The conformational analysis, thermochemical analysis, frequency analysis, and topological analysis were conducted to determine the interactions of hydrogen-bonded molecular clusters. The heterodimers formed a hepta or octa membered ring through four different types of hydrogen bonds, and the strength of the bonds are ranked in the following order: SOH???O > COH???O > NH???O > CH???O. We also evaluated the stability of the clusters and found that the stabilization effect of amides with SA is weaker than that of amines with SA but stronger than that of ammonia (NH₃) with SA in the dimer formation of nucleation process. Additionally, the nucleation capacity of SA with amides is greater than that of organic acids with amides.     

Aluminum formate (AF): Synthesis, characterization and application in dye wastewater treatment

Aluminum formate (AF), a degradable and non-corrosive coagulant, was synthesized from aluminum hydroxide and formic acid. Polyamidine (PA), as a coagulation aid, was combined with AF for dye wastewater treatment. AF was characterized by XPS, FT-IR, viscosity, zeta potential, mass spectrum and XRD, and the flocculation properties of the dual-coagulation system were characterized by FT-IR and SEM. The results showed that COOH, Al₂O₃-Al and O₂-Al bonds were formed in the AF synthesis process, and AF had a higher molecular weight and higher charge neutralization ability than PAC. The hydrolysates of AF were determined to contain Al₁₃ Al₁₁ and Al₂, and the components of AF were confirmed to comprise a mixture including aluminum formate (C₃H₃AlO₆) and its hydrate. When the color removal efficiency reached 100% in jar tests, the optimized dosage of AF/PA was 18.91/0.71 mg/L, while the optimized dosage of PAC/PA was 21.19/0.91 mg/L. According to the variance analysis, the interaction between AF/PA and PAC/PA were insignificant in macroscopic view. FT-IR spectrum indicated AF captured pollutant by means of CCO bond, PAC captured pollutant by δ CH, CC and δ CH. Overall, although the coagulation mechanism of AF was different from that of PAC, AF/PA showed better coagulation efficiency than PAC/PA in dye wastewater treatment.     

Probing and understanding interaction of Eu(III) with γ- alumina in presenceof malonic acid

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions. With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid, in the present study, Eu(III), malonic acid (MA) and γ-alumina are considered as representatives of trivalent actinides, low molecular weight natural occurring organic acid and aluminol sites, respectively. The influence of MA on sorption of Eu(III) by γ-alumina was elucidated by batch sorption, spectroscopic techniques and surface complexation modeling, for the first time. Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed on γ-alumina revealed the presence of two inner-sphere surface complexes. Batch sorption for binary (alumina-Eu(III)) and ternary (alumina-Eu(III)-MA) systems were investigated as a function of pH, Eu(III) concentration and sequential addition of Eu(III)/MA. The pH edge for Eu(III) sorption shifts to higher pH with increasing Eu(III) concentration. In ternary systems, Eu(III) sorption is significantly enhanced at pH < 4.5. Eu(III) speciation on γ-alumina is independent of addition sequence of Eu(III)/MA. Time resolved fluorescence spectroscopy of Eu(III) sorbed on γ-alumina exhibited two surface species, XOEu²⁺ and (YO)₂Eu⁺. The enhancement in I₆₁₆/I₅₉₂ and lifetime for ternary systems, as compared to binary system, at low pH, indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems. The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems, using code FITEQL 4.0, by considering the surface species identified by spectroscopic techniques.     

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O₃) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br^?). Considering the risk of bromate (BrO₃^?) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H₂O₂) and ammonia (NH₃) on BrO₃^? formation during ozonation process were compared. The addition of H₂O₂ effectively inhibited BrO₃^? formation at an initial Br^? concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H₂O₂/O₃ was 0.25 and > 0.5, respectively. The UV₂₅₄ and total organic carbon (TOC) also decreased after adding H₂O₂, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H₂O₂. To control the formation of both BrO₃^? and THMs, a relatively large dose of O₃ and a high ratio of H₂O₂/O₃were generally needed. NH₃ addition inhibited BrO₃^? formation when the background ammonia nitrogen (NH₃N) concentration was low. There was no significant correlation between BrO₃^? inhibition efficiency and NH₃ dose, and a small amount of NH₃N (0.2 mg/L) could obviously inhibit BrO₃^? formation. The oxidation of NOM seemed unaffected by NH₃ addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH₃. Considering the formation of BrO₃^? and THMs, the optimal dose of NH₃ was suggested to be 0.5 mg/L.     

An assessment of how distance and diesel oxidation catalyst will impact thermal decomposition behaviors of particles

Decomposition mass loss and pyrolysis products analyses of particles sampled at various locations along the tailpipe of a Euro-IV diesel engine were performed using a thermogravimetry in conjunction with Fourier transformation infrared spectrometry-mass spectrum. Diesel particles were collected at the same location with and without diesel oxidation catalyst (DOC) mounted on the test engine separately. The three poles in thermal gravity-differential thermal gravity images suggested that the decomposition process of diesel particles could be divided into three stages which correspond to the decompositions of lower boiling substances, higher boiling substances and soot respectively. It is noticed that no matter whether DOC was mounted or not, the further the particles were sampled away from the engine block, the lower the peak temperatures and the heavier the mass losses within the first two stages, which indicated that the soluble organic fraction in the particle samples increased and therefore lowering the activation energy of thermal decomposition. Hydroxyl, ammonia, C_xH_y fragments, benzene, toluene, and phenol were found to be the primary products of particle decomposition, which didn't change with the location of particle sample point. The employment of DOC increased the activation energy for particle oxidation and resulted in a higher peak temperature and lower mass loss within the first-stage. Moreover, the CO stretching bands of aldehyde and ketone at 1771 cm^?1 was only detected without a DOC, while the NO₂ peak at 1634 cm^?1 was solely noticed with the presence of DOC. Compared to the first-stage pyrolysis products, more polycyclic aromatic hydrocarbons and less C_xH_y fragments were seen in the second-stage.     

Photoproducts of tetracycline and oxytetracycline involving self-sensitized oxidation in aqueous solutions: Effects of Ca2+ and Mg2+

Tetracyclines constitute one of the most important antibiotic families and represent a classic example of phototoxicity. The photoproducts of tetracyclines and their parent compounds have potentially adverse effects on natural ecosystem. In this study, the self-sensitized oxidation products of tetracycline (TC) and oxytetracycline (OTC) were determined and the effects of Ca²⁺ and Mg²⁺on self-sensitized degradation were investigated. The Ca²⁺ and Mg²⁺ in the natural water sample accounted for enhancement (pH 7.3) and inhibition (pH 9.0) of photodegradation of TC and OTC due to the formation of metal-ions complexes. The formation of Mg²⁺ complexes was unfavorable for the photodegradation of the tetracyclines at both pH values. In contrast, the Ca²⁺ complexes facilitated the attack of singlet oxygen (¹O₂) arising from self-sensitization at pH 7.3 and enhanced TC photodegradation. For the first time, self-sensitized oxidation products of TC and OTC were verified by quenching experiments and detected by LC/ESI-DAD-MS. The products had a nominal mass 14 Da higher than the parent drugs (designated M+14), which resulted from the ¹O₂ attack of the dimethylamino group on the C-4 atom of the tetracyclines. The presence of Ca²⁺ and Mg²⁺ also affected the generation of M+14 due to the formation of metal-ions complexes with TC and OTC. The findings suggest that the metal-ion complexation has significant impact on the self-sensitized oxidation processes and the photoproducts of tetracyclines.     

New insight into scale inhibition during tea brewing: Ca2+/Mg2+ complexing and alkalinity consumption

Scale not only affects the taste and color of water, but also increases the risks of osteoporosis and cardiovascular diseases associated with drinking it. As a popular beverage, tea is rich many substances that have considerable potential for scale inhibition, including protein, tea polyphenols and organic acids. In this study, the effect of tea brewing on scale formation was explored. It was found that the proteins, catechins and organic acids in tea leaves could be released when the green tea was brewed in water with sufficient hardness and alkalinity. The tea-released protein was able to provide carboxyl groups to chelate with calcium ions (Ca²⁺), preventing the Ca²⁺ from reacting with the carbonate ions (CO₃²⁻). The B rings of catechins were another important structure in the complexation of Ca²⁺ and magnesium ions (Mg²⁺). The carboxyl and hydroxyl groups on the organic acids was able to form five-membered chelating rings with Ca²⁺ and Mg²⁺, resulting in a significant decrease in Ca²⁺ from 100.0 to 60.0 mg/L. Additionally, the hydrogen ions (H⁺) provided by the organic acids consumed and decreased the alkalinity of the water from 250.0 to 131.4 mg/L, leading to a remarkable reduction in pH from 8.93 to 7.73. It further prevented the bicarbonate (HCO₃⁻) from producing CO₃²⁻ when the water was heated. The reaction of the tea constituents with the hardness and alkalinity inhibited the formation of scale, leading to a significant decrease in turbidity from 10.6 to 1.4 NTU. Overall, this study provides information to help build towards an understanding of the scale inhibition properties of tea and the prospects of tea for anti-scaling in industrial applications.     

吉阳核电厂址气象铁塔塔层风频规律及风速分布拟合研究

通过安徽吉阳核电厂址气象塔观测系统获取观测数据,研究了该地区的风频规律性,并按南沿江流、北沿江流对塔层风速分布进行幂函数近似拟合,估算了地表粗糙度。结果表明：本区主导风向多集中在偏东北风上,而且频率很高,次主导风向则略有差异;塔层风廓线分布基本符合幂函数关系,由廓线求出的n指数推荐值为：A类0.165,B类0.167,C类0.192,D类0.313,E类0.406,F类0.463;南沿江流方向的地表粗糙度为1.547 063 m,北沿江流方向的地表粗糙度为1.738 45 m。     

模具在工件反挤压过程中的变形模拟研究

模具在金属塑性成形过程中起着十分重要的作用。就一般而言,模具在金属成形过程中的变形被忽略,将之视为刚性体。然而在金属精密成形中,模具的变形对成形件的尺寸精度将产生较大的影响。利用SuperForm软件针对模具在工件挤压过程中的变形进行了有限元数值模拟,对这一问题作了初步分析与探讨,为工厂实际生产的工艺制定、模具设计提供理论参考与依据。     

区域尺度绿洲稳定性评价

论文在区域尺度上,探讨了绿洲稳定性的内涵,并以新疆三工河流域绿洲为例,从绿洲所处的地理位置、绿洲与外围荒漠和山地系统之间的相互作用等方面评价了绿洲的区域稳定性。结果表明:①冲洪积扇型绿洲稳定性最高,其次是位于地下水溢出带下方的冲积平原型绿洲,稳定性最差的是湖滨三角洲或散流干三角洲上发育的绿洲;②绿洲的冷岛效应和植被指数可较好地表征绿洲与外围荒漠和山地系统之间的相互作用和评价绿洲的区域稳定性的时间变化。绿洲规模的扩大及绿洲水分和植被的增加将加强绿洲的冷岛效应,提高绿洲的稳定性;归一化差异植被指数增加,表明绿洲内植被覆盖密度增大和植物生物量提高,绿洲的稳定性增强。     

包气带油污土层生物修复现场控制性因素的评价

包气带油污土层的生物修复涉及到石油降解微生物、石油污染物的可生物降解性和土壤环境三个方面.本文通过最或然计数法(MPN)、原油族组分柱层析分析方法和色质联机分析等实验手段,研究了淄河滩包气带油污土层的水力学特性、氮磷营养元素、微生物和石油污染物.结果表明,长期受石油污染的土层含有丰富的微生物,其中大部分具有降解石油烃的能力,且土层的渗透性极强,有利于开展油污土层的生物修复.同时,长期的挥发、淋失和转化造成土层中石油污染物主要由高分子、高沸点烃类组成,且油污土层的速效氮、速效磷含量太低,直接增加了生物修复的难度,成为不利于生物修复的影响因素.     

程海流域生态系统服务功能价值评估

以程海流域为研究对象,依据已有研究经验利用市场价值法、替代花费法、碳税法和造林成本法、成果参照法对程海流域生态系统服务功能价值进行评估。结果表明,程海流域总的生态系统服务功能价值为39.26亿元／a,其中,涵养水源价值最高,占总服务价值的32.0％,第二位是净化水体价值（占28％）,第三位是调节气候价值（占16％）,第四位是社会文化功能价值（占13％）,其次分别是：生物资源价值、科教旅游价值、生物栖息地价值和提供水资源价值。     

对原子结构教学中两个问题的讨论

中学原子结构的课堂教学中,容易产生一些缺乏严谨性的情况。针对能级交错与分裂、洪特规则等内容教学过程中出现的例子进行探讨。     

电力行业水-能耦合关系研究综述

电力行业消耗了全球约8%的水资源,电力生产与输配过程中消耗的能源与水资源之间的相关关系被定义为电力行业水-能耦合关系.本文从电力行业水耗和节水潜力研究、电力生产与水资源空间分布匹配研究、电力行业水-能耦合关系与其他环境问题的关系研究三个角度对国际上相关文献的研究内容、研究方法和主要结论进行梳理.研究结果表明：冷却技术选择对电力行业的水-能耦合关系影响较大,电力生产的需水量与各地水资源禀赋在空间上不匹配,电力行业水-能耦合系统管理体系尚未建立且面临迫切的实际需求.     

黄河断流对三角洲附近海域生态环境影响的研究

本文根据多年调查监测数据研究成果，以及经济和社会统计资料，论述了黄河断流的历史与现状，定性定量地评价了黄河断流对三角洲附近海域生态环境的影响，并提出了缓解和预警对策。     

论西部大开发中高等级公路建设与环境的协调发展问题——以西(宁)湟(源)一级公路为例

本文从目前我国西部大开发中所面临的各种约束条件出发，以青海省西宁市至湟源县一级公路工程为例，简要阐述了西部大开发中高等级公路在路线设计，施工过程中保护好沿线生态环境的重要性和紧迫性，初步讨论了在西部大开发中如何协调高等级公路建设与环境之间的关系。