Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Biological conversion pathways of sulfate reduction ammonium oxidation in anammox consortia

• The SRAO phenomena tended to occur only under certain conditions. • High amount of biomass and non-anaerobic condition is requirement for SRAO. • Anammox bacteria cannot oxidize ammonium with sulfate as electron acceptor. • AOB and AnAOB are mainly responsible for ammonium conversion. • Heterotrophic sulfate reduction mainly contributed to sulfate conversion. For over two decades, sulfate reduction with ammonium oxidation (SRAO) had been reported from laboratory experiments. SRAO was considered an autotrophic process mediated by anammox bacteria, in which ammonium as electron donor was oxidized by the electron acceptor sulfate. This process had been attributed to observed transformations of nitrogenous and sulfurous compounds in natural environments. Results obtained differed largely for the conversion mole ratios (ammonium/sulfate), and even the intermediate and final products of sulfate reduction. Thus, the hypothesis of biological conversion pathways of ammonium and sulfate in anammox consortia is implausible. In this study, continuous reactor experiments (with working volume of 3.8L) and batch tests were conducted under normal anaerobic (0.2≤DO<0.5 mg/L) / strict anaerobic (DO<0.2 mg/L) conditions with different biomass proportions to verify the SRAO phenomena and identify possible pathways behind substrate conversion. Key findings were that SRAO occurred only in cases of high amounts of inoculant biomass under normal anaerobic condition, while absent under strict anaerobic conditions for same anammox consortia. Mass balance and stoichiometry were checked based on experimental results and the thermodynamics proposed by previous studies were critically discussed. Thus anammox bacteria do not possess the ability to oxidize ammonium with sulfate as electron acceptor and the assumed SRAO could, in fact, be a combination of aerobic ammonium oxidation, anammox and heterotrophic sulfate reduction processes.     

Enhanced debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by zero-valent zinc with ascorbic acid

• Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. • BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. • AA inhibits the formation of (hydr)oxide and accelerates the corrosion of ZVZ. • Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed. A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H₂O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.     

Metabolic uncoupler, 3,3′,4′,5-tetrachlorosalicylanilide addition for sludge reduction and fouling control in a gravity-driven membrane bioreactor

• Effects of metabolic uncoupler TCS on the performances of GDMBR were evaluated. • Sludge EPS reduced and transformed into dissolved SMP when TCS was added. • Appropriate TCS increased the permeability and reduced cake layer fouling. • High dosage aggravated fouling due to compact cake layer with low bio-activity. The gravity-driven membrane bioreactor (MBR)system is promising for decentralized sewage treatment because of its low energy consumption and maintenance requirements. However, the growing sludge not only increases membrane fouling, but also augments operational complexities (sludge discharge). We added the metabolic uncoupler 3,3′,4′,5-tetrachlorosalicylanilide (TCS) to the system to deal with the mentioned issues. Based on the results, TCS addition effectively decreased sludge ATP and sludge yield (reduced by 50%). Extracellular polymeric substances (EPS; proteins and polysaccharides) decreased with the addition of TCS and were transformed into dissolved soluble microbial products (SMPs) in the bulk solution, leading to the break of sludge flocs into small fragments. Permeability was increased by more than two times, reaching 60–70 L/m²/h bar when 10–30 mg/L TCS were added, because of the reduced suspended sludge and the formation of a thin cake layer with low EPS levels. Resistance analyses confirmed that appropriate dosages of TCS primarily decreased the cake layer and hydraulically reversible resistances. Permeability decreased at high dosage (50 mg/L) due to the release of excess sludge fragments and SMP into the supernatant, with a thin but more compact fouling layer with low bioactivity developing on the membrane surface, causing higher cake layer and pore blocking resistances. Our study provides a fundamental understanding of how a metabolic uncoupler affects the sludge and bio-fouling layers at different dosages, with practical relevance for in situ sludge reduction and membrane fouling alleviation in MBR systems.     

Degradation of polyacrylamide (PAM) and methane production by mesophilic and thermophilic anaerobic digestion: Effect of temperature and concentration

• PAM degradation in thermophilic AD in comparison with mesophilic AD. • PAM degradation and its impact on thermophilic and mesophilic AD. • Enhanced methane yield in presence of PAM during thermophilic and mesophilic AD. • PAM degradation and microbial community analysis in thermophilic and mesophilic AD. Polyacrylamide (PAM) is generally employed in wastewater treatment processes such as sludge dewatering and therefore exists in the sludge. Furthermore, it degrades slowly and can deteriorate methane yield during anaerobic digestion (AD). The impact or fate of PAM in AD under thermophilic conditions is still unclear. This study mainly focuses on PAM degradation and enhanced methane production from PAM-added sludge during 15 days of thermophilic (55°C) AD compared to mesophilic (35°C) AD. Sludge and PAM dose from 10 to 50 g/kg TSS were used. The results showed that PAM degraded by 76% to 78% with acrylamide (AM) content of 0.2 to 3.3 mg/L in thermophilic AD. However, it degraded only 27% to 30% with AM content of 0.5 to 7.2 mg/L in mesophilic AD. The methane yield was almost 230 to 238.4 mL/g VSS on the 8th day in thermophilic AD but was 115.2 to 128.6 mL/g VSS in mesophilic AD. Mechanism investigation revealed that thermophilic AD with continuous stirring not only enhanced PAM degradation but also boosted the organics release from the sludge with added PAM and gave higher methane yield than mesophilic AD.     

基于3S技术对太湖底质及水质总磷的研究

应用3S技术研究了太湖底质与水质总磷(TP)的分布情况,并结合水华频次分析了其相关性。结果表明:2016—2018年,太湖底质TP年均值在433~537 mg/kg波动,水质TP年均值从0.064 mg/L上升至0.087 mg/L。从空间分布来看,底质TP、水质TP和水华频次均呈现“西高东低”的规律,太湖西部区尤其是竺山湖区是需要开展治理的重点区域。3年间,太湖西部区水质TP上升,而底质TP与入湖河流TP下降,说明内源磷污染是太湖西部区水质TP升高的主要原因,须加强科学清淤。     

桂林市城区大气VOCs污染特征及对O3和SOA的生成潜势

对桂林市城区大气中挥发性有机物(VOCs)的污染特征,以及VOCs对臭氧(O3)和二次有机气溶胶(SOA)的生成潜势进行了研究。结果显示,研究期间,共检出VOCs物种78种,平均体积分数为21.32×10-9,表现为芳香烃(67.82%)烷烃(19.56%)卤代烃(7.50%)烯烃(2.86%)含氧挥发性有机物(1.41%)。VOCs体积分数空间分布呈现市中心和下风向郊区两个高值区。通过苯与甲苯的浓度比值发现,林科所VOCs主要来自交通源和生物源,师专甲山校区VOCs主要是来自交通源,其余测点VOCs主要来自交通源、工业源和外来传输源。分析乙苯和间/对二甲苯的浓度比值发现,电子科大尧山校区气团光化学年龄较大,光化学反应活性相对较强烈;旅游学院、华侨旅游经开区、大埠中心校气团光化学年龄较小,光化学反应活性相对较弱。VOCs对O3生成潜势最大的为芳香烃(93.81%),其次是烷烃(7.22%)和烯烃(4.75%);对SOA生成潜势最大的为芳香烃(97.45%),其次是烷烃(2.55%)。     

Environmental forensic investigation of the air pollution from a cement manufacturing unit

Abstract

Cement manufacturing is a process that results in the emission of significant quantities of suspended particulate matter (SPM) to the ambient air. An environmental forensic investigation was carried out in the surroundings of a major cement manufacturing unit at a place called Coimbatore in the southern Indian state of Tamil Nadu. The investigation was carried out to identify the contribution of the cement manufacturing unit to the SPM concentration of the surrounding air environment. The sampling points’ selection and sample collection were done following the principles outlined in the INTERPOL Manual for Pollution Crime Forensic Investigation. On-site monitoring of the air samples was carried out using Mini Laser Aerosol Spectrometer (GRIMM, Mini-LAS Model 11R). The instrument was capable of measuring particles ranging from 0.25 to 32 µm and classifying them into 31 size channels. The test results at majority of the monitoring locations were well above the limits specified in the National Ambient Air Quality Standards of India. Microscopic studies of the dust samples were carried out for surface texture and particle shape. The spatial distribution of particles was analysed using geographic information system (GIS) for the visual identification of the extent of the pollution by keeping the cement factory as the focal point. The results from the GIS and microscopic analysis established the role of the cement factory in the particulate matter pollution of its surroundings, specifically in the areas North-West of the factory. The successfully adopted procedure can serve as a guideline for the environmental forensic investigation of similar pollution incidences.     

“竞争申请制”:可持续发展政策试点与央地关系重构

可持续发展目标(SDGs)的提出,开启了人类可持续发展领域最宏大的政策实验,也为开展国际视野的比较公共政策研究提供了难得机遇。执行SDGs及国家可持续发展政策需要处理好中央政府与地方政府间关系,而政策试点是协调这一关系的重要政策工具。已有文献对经济政策试点做了较充分的研究,然而对旨在实现经济、社会与环境协调的可持续发展政策试点,现有研究尚缺乏成型理论。在复杂央地关系格局下,对于需持续投入成本且成果难以界定的可持续发展政策试点,其具有怎样的不同于经济政策试点的机制?此外,众多西方学者将美国作为政策试点研究的制度基础并视其为“民主实验室”。然而,政策试点在以中国为代表的不同体制国家中同样存在,并以多样的机制发挥作用。那么,不同国家体制内的可持续发展政策试点又有哪些异同?政策试点影响下中国既有的央地关系发生了怎样的重构?对此,本文基于最典型案例原则,选取中国与美国响应SDGs分别开展的政策试点进行比较研究。笔者识别了不同体制下试点机制的异同,指出中国基于“竞争申请制”开展的可持续发展政策试点强化了中央部委与地方政府间关系,形成了地方官员的可持续发展激励,保障了政策试点的实施。