Catalytic degradation of toxic organic dye using an aluminum-doped Cu0.4Zn0.6-xAlxFe2O4 (x = 0.0, 0.2, 0.4, 0.6) spinel ferrite in a photo-Fenton system

Catalytic activity of spinel ferrite in breaking down toxic dye materials are promising due to their uniqueness. In this study, aluminum-doped copper zinc ferrite, Cu_0.4Zn_0.6-xAl_xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6), a catalyst for toxic dye degradation is synthesized through chemical co-precipitation route. The formation of the spinel ferrite catalyst is initially confirmed by Fourier transform infrared spectra, which shows the frequency of metal-oxygen bond vibration at 539 and 427 cm⁻¹ attributed to the tetrahedral and octahedral sites respectively. Higher intensity sharp peak of X-ray diffraction for (311) plane is the evidence for the phase purity and the formation of spinel ferrite. The crystallite size is found to decrease with the increase of Al³⁺ ion. The surface structure of the obtained particles is investigated using a scanning electron microscope. Analyses of the material's magnetic characteristics using a vibrating sample magnetometer (VSM) revealed that it is, in fact, a soft magnet, as evidenced by the loop of its hysteresis, which is narrow. The catalytic degradation of methylene blue dye under the mechanism of the photo-Fenton process is studied with the obtained spinel ferrites and the result is found to be as high as 96.5%. The process follows pseudo-second order kinetics and the Langmuir isotherm.     

不同低碳氮比废水中好氧颗粒污泥的长期运行稳定性

为了研究好氧颗粒污泥系统处理低碳氮比废水的长期运行稳定性,采用低碳氮比（C/N）条件下逐步增加碳氮负荷的进水方法,分别在反应器A和B中接种好氧颗粒污泥,考察其长期运行过程中的理化性质、处理性能及应对冲击负荷的稳定性.其中A反应器的碳氮比一直维持在2,而B则由4逐步降至2.结果表明,在4℃存储30d的好氧颗粒污泥,经过25d的培养,其活性基本恢复,A、B反应器化学需氧量（COD）和氨氮（NH₄⁺-N）的去除效率均达到90%以上.在其后的稳定阶段,B反应器COD和NH₄⁺-N去除率达到90%以上,实现了完全硝化;而A反应器COD去除率仅80%左右,虽然NH₄⁺-N去除率最终也达到90%以上,但仅实现短程硝化.在冲击负荷阶段,A和B反应器COD去除率仍维持在80%以上,但是NH₄⁺-N去除受到很大冲击.A反应器NH₄⁺-N去除效率恶化,B反应器仅实现了部分硝化.整个运行过程,好氧颗粒污泥的物理性质受到的影响不大,A和B反应器的污泥容积指数（SVI₃₀）分别维持在60 mL ·g^-1和75 mL ·g^-1左右,混合液悬浮固体（MLSS）在5g ·L^-1和3.7g ·L^-1左右.颗粒污泥微生物群落分析表明,B反应器相对于A反应器丰富度和多样性更高.同时B反应器具有更高丰度的Zoogloea属,在颗粒中能产生更多的胞外蛋白促使颗粒结构更稳定,保证系统的长期稳定运行.以上结果表明,与C/N为2的好氧颗粒污泥系统相比,C/N为4的系统脱碳硝化效果好,抗冲击负荷能力强,更有利于颗粒污泥的长期稳定运行.     

二溴硝基甲烷在紫外光照条件下的光降解

以二溴硝基甲烷为研究,采用单一控制变量法研究了光照强度、初始物浓度、自由氯、溴离子、pH值等影响因子对二溴硝基甲烷光降解的影响,探讨了二溴硝基甲烷的光降解动力学规律.结果表明：二溴硝基甲烷在紫外光条件下的降解遵循一级反应动力学规律,其光降解效率随二溴硝基甲烷初始浓度的增加而减小,随光照强度和pH值增加而增加;溴离子的存在能促进二溴硝基甲烷的光降解;添加自由氯能够显著加快二溴硝基甲烷的光降解效率,并且会使二溴硝基甲烷在光降解的过程中转化为以一溴一氯硝基甲烷为主的其他卤代硝基甲烷.此研究结果可为水处理过程中控制二溴硝基甲烷的形成、降低水质安全风险提供参考.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

Sources, distribution, and risk assessment of organochlorine pesticides in Nairobi City, Kenya

The distribution and sources of organochlorine pesticides (OCPs) in air and surface waters were monitored in Nairobi City using triolein-filled semipermeable membrane devices (SPMDs). The SPMDs were extracted by dialysis using n-hexane, followed by cleanup by adsorption chromatography on silica gel cartridges. Sample analysis was done by GC-ECD and confirmed by GC–MS. Separation of means was achieved by analysis of variance, followed by pair-wise comparison using the t-test (p≤ 0.05). The total OCPs ranged between 0.018 – 1.277 ng/m³ in the air and <LOD – 1391.000 ng/m³ in surface waters. Based on the results, the means of Industrial Area, Dandora and Kibera were not significantly different (p≤ 0.05), but were higher (p≤ 0.05) than those of City square and Ngong’ Forest. The results revealed non-significant (p≤ 0.05) contribution of long-range transport to OCP pollution in Nairobi City. This indicated possible presence of point sources of environmental OCPs in the city. The water-air fugacity ratios indicated that volatilization and deposition played an important role in the spatial distribution of OCPs in Nairobi City. This indicated that contaminated surface waters could be major sources of human exposure to OCPs, through volatilization. The incremental lifetime cancer risks (ILCR) determined from inhalation of atmospheric OCPs were 2.3745  ×  10^?13 – 1.6845  ×  10^?11 (adult) and 5.5404  ×  10^?13 – 3.9306  ×  10^?11 (child) in the order: Dandora > Kibera > Industrial Area > City Square > Ngong’ Forest. However, these were lower than the USEPA acceptable risks, 10^?6 – 10^?4. This study concluded that atmospheric OCPs did not pose significant cancer risks to the residents.     

微生物菌剂对堆肥功能微生物重构的影响

堆肥产品不仅可以作为有机肥或土壤改良剂,还可以在包气带土层防护地下水污染的过程中起到微生物载体的作用.在堆肥中接种菌剂能够加速堆肥进程,促进堆肥材料的腐熟,但是也有研究认为接种剂与堆肥土著微生物的竞争会导致菌剂无法发挥作用.为了阐明菌剂与土著微生物之间的相互作用,采用宏蛋白质组学方法,分析餐厨垃圾堆肥接菌组（木质纤维素混合菌剂）和对照组（未接菌）中功能微生物群落和碳水化合物代谢途径的变化.结果表明:接菌组中假单胞菌目（Pseudomonadales）和散囊菌纲（Eurotiomycetes）菌群的相对丰度比对照组分别提高了12.5%和22.0%,成为优势细菌和真菌,二者在碳水化合物代谢活性上也成为优势菌群.菌剂主要是由芽孢杆菌目（Bacillales）和散囊菌纲的曲霉（Aspergillus）组成,曲霉因具有堆肥系统所需的木质纤维素分解能力而成为优势真菌,而菌剂中的芽孢杆菌虽然数量较多,但是缺乏堆肥系统所需的功能而无法成为优势细菌.餐厨垃圾中易降解物质分解过程中产生的有机酸会导致酸性环境,对照组中能够适应酸性环境的芽孢杆菌目和酵母菌纲（Saccharomycetes）是优势群落,添加菌剂后,堆肥系统中土著的假单胞菌目和散囊菌纲具有较高的碳水化合物代谢活性和多种有机酸转化通路,因此在与菌剂中的芽孢杆菌目和土著的芽孢杆菌及酵母菌的竞争中成为优势菌群.研究显示,外源菌剂与土著微生物之间以及各土著微生物之间都会发生竞争作用,能否成为优势菌群取决于是否适应堆肥底物新陈代谢的变化,因此只要选择好菌剂的功能和接种时机,菌剂就能够发挥原有的作用.      

过硫酸钠缓释材料的释放性能及其对2, 4-二硝基甲苯的降解效果

针对原位化学氧化技术修复土壤和地下水时氧化剂因释放过快而导致的利用率低等问题,通过熔化成型法制备过硫酸钠缓释材料,分析石蜡、硅砂和过硫酸钠不同配比对材料成型度和释放性能的影响,研究缓释过程中溶液pH的变化,探讨其在水溶液中的缓释行为及其对2,4-二硝基甲苯（2,4-DNT）的降解效果.结果表明:当固定过硫酸钠质量为6 g、硅砂质量为18 g、蜡砂比（石蜡、硅砂质量之比）为1:4~1:8时,过硫酸钠缓释材料成型度适中,且过硫酸钠的累积缓释量随着时间的延长而逐渐增大,第31天时过硫酸钠累积释放百分比为74.67%~88.40%,可实现过硫酸钠的持续可控释放.当硅砂质量为18 g、蜡砂比为1:1~1:6时,过硫酸钠累积释放百分比随着过硫酸钠质量的增加而增大,且溶液中的pH呈先降低后上升的变化规律.缓释材料缓释前后实物图和显微镜分析结果显示,过硫酸钠缓释材料的释放是一个由外到内、速率由快变慢最终趋于平稳的过程.过硫酸钠质量为12 g、硅砂质量为18 g、蜡砂比为1:4的缓释材料对2,4-DNT具有较好的降解效果,第16次置换浓度为0.2 mg/L的2,4-DNT水溶液时,2,4-DNT的降解率为56.38%.研究显示,改变制备材料的配比可有效实现缓释材料中过硫酸钠的缓慢释放及对污染物的有效降解,可为原位化学氧化修复土壤和地下水提供理论支撑.      

尕海湿地植被退化过程中有机碳及相关土壤酶活性变化特征

以青藏高原东缘尕海湿地不同植被退化程度样地为研究对象,采用定位研究与室内试验相结合的方法,研究植被退化过程对土壤有机碳和土壤酶活性的影响。结果表明：植被退化显著影响土壤有机碳含量和土壤酶活性,降低了土壤有机碳的含量和酶促反应效率,且这种影响随土层深度变化有所不同。四种植被退化阶段有机碳含量和酶活性均值总体上（0~100 cm）表现为未退化>轻度退化>中度退化>重度退化。不同土层中,20~40 cm土层的有机碳含量中度退化>轻度退化;0~10 cm土层中淀粉酶和纤二糖酶中度退化阶段活性值较高;20~100 cm土层中蔗糖酶重度退化阶段活性值最高,纤二糖酶活性重度退化>中度退化。同一退化程度土壤有机碳含量、蔗糖酶和纤二糖酶活性随土层深度增加显著降低（P<0.05）;淀粉酶和纤维素酶活性在>40 cm土层中活性值有所上升,整体呈波动下降趋势。     

铁基质强化新型功能性化粪池高效处理黑水的试验

以铁基质生物载体为核心,将物理、生物和化学方法结合,对化粪池进行功能强化,实现黑水的原位深度处理.探究了溶解氧（DO）和碳氮比（C/N）等因素对黑水中污染物降解的影响,并在最佳运行参数下考察了氮素在系统中的转化机制.结果表明,当C/N为7.3~8.4时,好氧生物铁基质载体池DO为2.3~2.7mg/L时,系统氨氮（NH₄⁺-N）、总氮（TN） 、COD和总磷（TP）的平均去除率分别可达90.74%、85.81%、92.65%和95.78%;当进水C/N降至3.3~4.2时,系统NH₄⁺-N、TN、COD和TP的平均去除率仍可维持在81.16%、76.62%、93.87%和94.75%.铁基质生物载体内电解作用显著强化了化粪池内TN的脱除、COD的氧化和TP的固定.氮素转化机制分析表明,内电解与反硝化菌的耦合强化了反硝化作用,降低了反硝化过程对有机碳源的需求,强化了低C/N条件下TN、TP的脱除.