In situ formation of bimetallic FeNi nanoparticles on sand through green technology: Application for tetracycline removal

• In situ preparation of FeNi nanoparticles on the sand via green synthesis approach. • Removal of tetracycline using GS-FeNi in batch and column study. • Both reductive degradation and sorption played crucial role the process. • Reusability of GS-FeNi showed about 77.39±4.3% removal on 4th cycle. • TC by-products after interaction showed less toxic as compared with TC. In this study, FeNi nanoparticles were green synthesized using Punica granatum (pomegranate) peel extract, and these nanoparticles were also formed in situ over quartz sand (GS-FeNi) for removal of tetracycline (TC). Under the optimized operating conditions, (GS-FeNi concentration: 1.5% w/v; concentration of TC: 20 mg/L; interaction period: 180 min), 99±0.2% TC removal was achieved in the batch reactor. The removal capacity was 181±1 mg/g. A detailed characterization of the sorbent and the solution before and after the interaction revealed that the removal mechanism(s) involved both the sorption and degradation of TC. The reusability of reactant was assessed for four cycles of operation, and 77±4% of TC removal was obtained in the cycle. To judge the environmental sustainability of the process, residual toxicity assay of the interacted TC solution was performed with indicator bacteria (Bacillus and Pseudomonas) and algae (Chlorella sp.), which confirmed a substantial decrease in the toxicity. The continuous column studies were undertaken in the packed bed reactors using GS-FeNi. Employing the optimized conditions, quite high removal efficiency (978±5 mg/g) was obtained in the columns. The application of GS-FeNi for antibiotic removal was further evaluated in lake water, tap water, and ground water spiked with TC, and the removal capacity achieved was found to be 781±5, 712±5, and 687±3 mg/g, respectively. This work can pave the way for treatment of antibiotics and other pollutants in the reactors using novel green composites prepared from fruit wastes.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

氧化镁烟气脱硫反应特性研究

利用实验室规模的鼓泡式反应装置,对比了碳酸钙、氧化镁和氧化镁/硫酸镁脱硫剂的反应活性,证实脱硫液中高浓度硫酸镁的存在是保证镁法脱硫效率高于钙法的重要因素,并考察了硫酸镁浓度、脱硫剂(氧化镁)浓度、烟气量、SO2浓度和吸收液温度等因素对脱硫效率的影响。结果表明,脱硫反应可以根据pH分为2个不同阶段;反应过程中脱硫效率随着硫酸镁浓度的增加而显著升高;烟气量增加将会导致脱硫效率有所下降;入口SO2浓度升高,脱硫效率下降;氧化镁浓度、温度对脱硫效率影响不显著。结合实验现象进行推断,氧化镁脱硫的反应过程受SO2在气液两相界面的传质扩散和其水解产物在液相的扩散控制。     

CaH2对Cu-Ce-La-ZSM-5催化分解NO性能的影响

实验采用一步离子交换法制备Cu-Ce-La-ZSM-5催化剂,然后采用共混法制得Cu-Ce-La-ZSM-5/CaH2催化剂。采用扫描电镜（SEM）,电感耦合等离子体发射光谱（ICP-AES）,X射线衍射（XRD）,红外（FTIR）以及NO吸脱附（NO-TPD）对催化剂进行表征。结果显示CaH2的加入使得催化剂中铜离子存在形式发生变化,催化剂表面变光滑洁净,并且吸附NO能力增强。NO催化分解实验的结果表明CaH2提高了催化剂活性和抗氧性。CaH2助催性是由于其受热分解过程中产生的H2能将Cu^2＋还原为具有催化活性的Cu^＋,同时使催化剂表面洁净光滑更容易吸附NO。     

Ecotoxicity of nanoparticles of CuO and ZnO in natural water

The acute toxicity of CuO and ZnO nanoparticles in artificial freshwater (AFW) and in natural waters to crustaceans Daphnia magna and Thamnocephalus platyurus and protozoan Tetrahymena thermophila was compared. The L(E)C₅₀ values of nanoCuO for both crustaceans in natural water ranged from 90 to 224 mg Cu/l and were about 10-fold lower than L(E)C₅₀ values of bulk CuO. In all test media, the L(E)C₅₀ values for both bulk and nanoZnO (1.1-16 mg Zn/l) were considerably lower than those of nanoCuO. The natural waters remarkably (up to 140-fold) decreased the toxicity of nanoCuO (but not that of nanoZnO) to crustaceans depending mainly on the concentration of dissolved organic carbon (DOC). The toxicity of both nanoCuO and nanoZnO was mostly due to the solubilised ions as determined by specific metal-sensing bacteria.     

Immobilization of non-point phosphorus using stabilized magnetite nanoparticles with enhanced transportability and reactivity in soils

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase.     

A/O工艺N_2O的产生与释放的影响因素

采用A/O工艺,在连续运行条件下,以DO、SRT和硝化液回流比(R)为影响因素,对A/O生物脱氮工艺处理模拟城市生活污水过程中N2O的释放进行了研究。实验结果表明,SRT对A/O工艺N2O释放的影响最大,其次是DO,R的影响最小。N2O转化率随着SRT的升高而降低,当SRT从10 d升高到20 d时,总N2O平均转化率从0.319%下降到0.002%。总N2O转化率随着好氧池DO的升高先降低后有所升高,当DO分别为0.6 mg O2/L、1.2 mg O2/L、2.5 mg O2/L时,反应器的总N2O平均转化率分别为0.306%、0.007%和0.013%。R对N2O释放的影响差异不明显,总N2O平均转化率在300%时最低,为0.007%。N2O释放量最低的工艺运行条件组合是SRT为20 d、DO为1.2 mg O2/L、R为300%。     

TiO2-Cu2O/蒙脱土复合光催化剂的制备与性能

以钠基蒙脱土（MMT）为载体,先采用溶胶-凝胶法将纳米TiO₂引入到MMT层间,再采用化学沉积法将纳米Cu₂O负载在TiO₂/MMT上,制备出TiO₂-Cu₂O/MMT纳米复合光催化剂。采用XRD、SEM、紫外-可见漫反射技术对催化剂进行了表征。以甲基橙为目标污染物,考察了催化剂的光催化性能。表征结果显示：TiO₂与Cu₂O均匀分布在MMT的表面与片层孔隙中;TiO₂-Cu₂O/MMT结合了TiO₂和Cu₂O的特性,拓宽了催化剂的光吸收范围。实验结果表明,在光源为可见光、初始甲基橙质量浓度为20 mg/L、光催化剂加入量为2 g/L的条件下,TiO₂-Cu₂O/MMT纳米复合光催化剂对甲基橙的光催化降解效果明显优于单一负载的Cu₂O/MMT和TiO₂/MMT,大幅提高了催化剂的光催化效率,反应300 min时TiO₂-Cu₂O/MMT对甲基橙溶液的脱色率达到93%。     

钛基金属氧化物电极的制备及性能

采用聚合物前驱体法制备了Ti/SnO₂-Sb₂O₃电极,再通过恒电流电沉积法制备了 Ti/SnO₂-Sb₂O₃/PbO₂和Ti/SnO₂-Sb₂O₃/MnO₂电极。采用SEM技术对3种金属氧化物电极表面的形貌进行了表征,并分别以3种电极为阳极进行了苯酚的电催化氧化实验。实验结果表明：电解时间为2.5 h时,Ti/SnO₂-Sb₂O₃电极、Ti/SnO₂-Sb₂O₃/PbO₂电极和Ti/SnO₂-Sb₂O₃/MnO₂电极对苯酚的降解率分别为85.9%,83.2%,44.6%;苯酚在3种电极上的电催化氧化反应均遵循一级反应动力学方程;苯酚在Ti/SnO₂-Sb₂O₃ 电极和Ti/SnO₂-Sb₂O₃/PbO₂电极上的反应速率较快,并具有较高的析氧电位;Ti/SnO₂-Sb₂O₃/PbO₂电极具有更好的耐腐蚀性和更长的使用寿命。