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.     

“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。     

农地整治权属调整中农户认知对行为响应的作用机制--基于改进TPB及多群组SEM

农地整治权属调整是实现农业规模化和现代化的重要手段,而农户有效参与是推动权属调整的内在动力,研究农地整治权属调整中农户认知对其行为响应的作用机制,有助于高效引导农户参与权属调整,并为制定农地整治权属调整的政策提供科学依据。基于改进计划行为理论和湖北省11个县(市、区)1044份农户抽样调查数据,采用多群组结构方程模型探究了农地整治权属调整中不同类型农户认知对其行为响应的作用机制。结果表明:农地整治权属调整中农户行为逻辑符合改进计划行为理论,农户的行为态度、主观规范、知觉行为控制交互影响行为意愿,进而转换为行为响应,政府支持在行为意愿和行为响应之间起到部分中介作用。总体上,农户行为响应是"自发性""诱发性"和"约束性"三重行动逻辑的结合,且"自发性"占主导地位。多群组结构方程估计结果表明,纯农型与兼业Ⅰ型农户的行为响应受到"自发性""诱发性"和"约束性"三重影响,兼业Ⅱ型农户受到"自发性"和"诱发性"双重影响,非农型农户仅受到"诱发性"单一影响。因此,为引导农户积极参与农地整治权属调整,应该分别针对各类农户相应地提高其参与的"自发性"和"诱发性",降低"约束性",充分发挥农村社会经济组织的作用,将四种不同类型农户的利益需求统筹考虑,降低权属调整过程中利益协调难度。     

Cancer and Non-Cancer Health Risk from Eating Cassava Grown in Some Mining Communities in Ghana

Food crops such as cassava, cocoyam and other tuber crops grown in mining communities uptake toxic or hazardous chemicals such as arsenic, and cadmium, from the soil. Cassava is a stable food for Ghanaians. This study evaluated human health risk from eating cassava grown in some mining communities in Ghana such as Bogoso, Prestea, Tarkwa and Tamso, which are important mining towns in the Western Region of Ghana. The study evaluated cancer and non-cancer health effects from eating cassava grown in the study areas in accordance with US Environmental Protection Agency’s Risk Assessment guidelines. The results of the study revealed the following: cancer health risk for Tamso, 0.098 (RME – Reasonable Maximum Exposure) and 0.082 (CTE – Central Tendency Exposure). This means that approximately 10 and 8 out of 100 resident adults are likely to suffer from cancer related cases by RME and CTE parameters respectively. For Prestea, we have 0.010 and 0.12, which also means that approximately 1 out of 100 and 10 resident adults out of 100 are also likely to suffer from cancer related diseases by RME and CTE parameters. The results of the study obtained were found to be above the acceptable cancer risk range of 1× 10⁻⁶ to 1× 10⁻⁴, i.e., 1 case of cancer out of 1 million or 100,000 people respectively.     

Dissipation of Endosulfan and Dichlorvos Residues In/On Cauliflower Curds

Dissipation behaviour of endosulfan and dichlorvos in/on cauliflower, variety Snowball-16, was studied during rabi season (Sep.–March) 2003–2004. Endosulfan and dichlorvos were sprayed @ 350 and 110g a.i. with 115 g a.i., respectively, 80 days after transplanting. Samples were taken at the interval of 0 (1h after spray), 3, 5, 7, and 10 days after spray (DAS) in triplicate and residues were estimated on GC-ECD system equipped with capillary column. The initial deposits of 3.452 and 0.295μgg⁻¹ of endosulfan and dichlorvos dissipated to 0.084 (97.56%) and 0.009 (96.95%), respectively after 10 DAS. Residues of endosulfan reached below maximum residue limit of 2μgg⁻¹ one day after spray and of dichlorvos were below MRL value of 0.5μgg⁻¹ even on 0 day. Dissipation pattern followed first order kinetics for both the insecticides with half life periods of 1.81 and 2.08 days for endosulfan and dichlorvos, respectively.