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.     

Scenario-based assessment and multi-objective optimization of urban development plan with carrying capacity of water system

• Impact of urban development on water system is assessed with carrying capacity. • Impacts on both water resource quantity and environmental quality are involved. • Multi-objective optimization revealing system trade-off facilitate the regulation. • Efficiency, scale and structure of urban development are regulated in two stages. • A roadmap approaching more sustainable development is provided for the case city. Environmental impact assessments and subsequent regulation measures of urban development plans are critical to human progress toward sustainability, since these plans set the scale and structure targets of future socioeconomic development. A three-step methodology for assessing and optimizing an urban development plan focusing on its impacts on the water system was developed. The methodology first predicted the pressure on the water system caused by implementation of the plan under distinct scenarios, then compared the pressure with the carrying capacity threshold to verify the system status; finally, a multi-objective optimization method was used to propose regulation solutions. The methodology enabled evaluation of the water system carrying state, taking socioeconomic development uncertainties into account, and multiple sets of improvement measures under different decisionmaker preferences were generated. The methodology was applied in the case of Zhoushan city in South-east China. The assessment results showed that overloading problems occurred in 11 out of the 13 zones in Zhoushan, with the potential pressure varying from 1.1 to 18.3 times the carrying capacity. As a basic regulation measure, an environmental efficiency upgrade could relieve the overloading in 4 zones and reduce 9%‒63% of the pressure. The optimization of industrial development showed that the pressure could be controlled under the carrying capacity threshold if the planned scale was reduced by 24% and the industrial structure was transformed. Various regulation schemes including a more suitable scale and structure with necessary efficiency standards are provided for decisionmakers that can help the case city approach a more sustainable development pattern.     

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.     

快速城市化背景下的思雅河流域水环境分析

通过对思雅河流域连续3年的水环境质量监测,结合遥感影像获得其土地利用类型变化,据此研究城市化对水环境的影响。结果表明:2012—2014年间思雅河流域自然、农业景观面积占比减少,而建设用地面积持续增加;研究期间除TDS年均值略微下降外,其余水质指标的年均值几乎均呈递增趋势,尤以TSS和COD增加最显著;TSS、COD、NH 3-N和TP的相对标准偏差均>0.1,显著高于其余参数,说明其波动程度较大。主成分分析表明水环境变化最主要的影响因子为第一主成分(TSS、COD、NH 3-N和TP)。贵安新区大学城建设活动加重了思雅河流域水体污染趋势。     

整合消费与增加值视角的中国行业碳排放变动分解研究

在研究影响我国CO 2排放因素领域,基于投入产出技术的分解模型已成为主要的分析工具,现有研究多分别基于消费视角或收益视角展开分析。为全面评估各行业收益与消费对其上游、下游行业碳排放的综合影响,整合基于收益与基于消费两个视角,运用2012年与2015年我国投入产出表,构建两层嵌套式结构分解分析模型(SDA),比较分析消费规模效应、收益规模效应、行业流入、流出增加值变动效应、增加值结构变动效应等14个影响各行业碳排放变动的关键因素,并借助对消费者原则碳排放估算公式的重构,更准确地实现从增加值视角对各行业消费者原则碳排放变动的关键影响因素分析。研究发现:①研究期内,我国在总产出增长29.14%的同时碳排放量上升1.46%,各行业碳排放强度下降是主要的减排因素,其中建筑业减排贡献最大。②增排效应方面,影响从大到小依次为消费规模、收益规模、完全投入结构与完全消费结构四项效应,且前两个规模效应的影响是后两个结构效应的2倍以上,尤其建筑业消费规模效应、煤炭采选产品业收益规模效应增排较大。③消费规模扩大导致增排的原因并非行业本身生产规模扩大,而主要在于建筑业、服务业等行业规模扩张时吸收其他行业流入的增加值量增多。④收益规模扩大导致的增排效应方面,细分来说从大到小依次为劳动者报酬、生产税净额、固定资产折旧、营业盈余四项效应,且行业差异显著,如煤炭采选产品业的劳动者报酬效应,石油、炼焦产品和核燃料加工品业的生产税净额效应以及电力、热力生产和供应业的营业盈余效应增排贡献较大,而煤炭采选产品业的营业盈余效应、批发、零售业和住宿、餐饮业的生产税净额效应则减排贡献较大。     

“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。