Comparing dark- and photo-Fenton-like degradation of emerging pollutant over photo-switchable Bi2WO6/CuFe2O4: Investigation on dominant reactive oxidation species

The extensive use of tetracycline hydrochloride (TCH) poses a threat to human health and the aquatic environment. Here, magnetic p-n Bi₂WO₆/CuFe₂O₄ catalyst was fabricated to efficiently remove TCH. The obtained Bi₂WO₆/CuFe₂O₄ exhibited 92.1% TCH degradation efficiency and 50.7% and 35.1% mineralization performance for TCH and raw secondary effluent from a wastewater treatment plant in a photo-Fenton-like system, respectively. The remarkable performance was attributed to the fact that photogenerated electrons accelerated the Fe(III)/Fe(II) and Cu(II)/Cu(I) conversion for the Fenton-like reaction between Fe(II)/Cu(I) and H₂O₂, thereby generating abundant ?OH for pollutant oxidation. Various environmental factors including H₂O₂ concentration, initial pH, catalyst dosage, TCH concentration and inorganic ions were explored. The reactive oxidation species (ROS) quenching results and electron spin resonance (ESR) spectra confirmed that ?O₂^? and ?OH were responsible for the dark and photo-Fenton-like systems, respectively. The degradation mechanisms and pathways of TCH were proposed, and the toxicity of products was evaluated. This work contributes a highly efficient and environmentally friendly catalyst and provides a clear mechanistic explanation for the removal of antibiotic pollutants in environmental remediation.     

Aging of PVDF and PES ultrafiltration membranes by sodium hypochlorite: Effect of solution pH

Sodium hypochlorite (NaClO) is a commonly applied cleaning agent for ultrafiltration membranes in water and wastewater treatment. Long-term exposure to NaClO might change the properties and performance of polymeric membranes, and ultimately shorten membrane lifespan. Active species in NaClO solution vary with solution pH, and the aging effects can change depending on the membrane material. In this study, the aging of polyvinylidene fluoride (PVDF) and polyethersulfone (PES) membranes by NaClO at pH 3–11 was investigated by examining variations in chemical composition, surface charge, surface morphology, mechanical strength, permeability, and retention ability. Polyvinyl pyrrolidone (PVP), which was blended in both membranes, was oxidized and dislodged due to NaClO aging at all investigated pH values, but the oxidation products and dislodgement ratio of PVP varied with solution pH. For the PVDF membrane, NaClO aging at pH 3–11 caused a moderate increase in permeability and decreased retention due to the oxidation and release of PVP. The tensile strength decreased only at pH 11 because of the defluorination of PVDF molecules. For the PES membrane, NaClO aging at all investigated pH resulted in chain scission of PES molecules, which was favored at pH 7 and 9, potentially due to the formation of free radicals. Therefore, a decrease in tensile strength and retention ability, as well as an increase in permeability, occurred in the PES membrane for NaClO aging at pH 3–11. Overall, the results can provide a basis for selecting chemical cleaning conditions for PVDF and PES membranes.     

Spatiotemporal variations of ambient air pollutants and meteorological influences over typical urban agglomerations in China during the COVID-19 lockdown

To investigate the air quality change during the COVID-19 pandemic, we analyzed spatiotemporal variations of six criteria pollutants in nine typical urban agglomerations in China using ground-based data and examined meteorological influences through correlation analysis and backward trajectory analysis under different responses. Concentrations of PM_2.5, PM₁₀, NO₂, SO₂ and CO in urban agglomerations respectively decreased by 18%–45% (30%–62%), 17%–53% (22%–39%), 47%-64% (14%–41%), 9%–34% (0%–53%) and 16%-52% (23%–56%) during Lockdown (Post-lockdown) period relative to Pre-lockdown period. PM_2.5 pollution events occurred during Lockdown in Beijing-Tianjin-Hebe (BTH) and Middle and South Liaoning (MSL), and daily O₃ concentration rose to grade Ⅱ standard in Post-lockdown period. Distinct from the nationwide slump of NO₂ during Lockdown period, a rebound (～40%) in Post-lockdown period was observed in Cheng-Yu (CY), Yangtze River Middle-Reach (YRMR), Yangtze River Delta (YRD) and Pearl River Delta (PRD). With slightly higher wind speed compared with 2019, the reduction of PM_2.5 (51%–62%) in Post-lockdown period is more than 2019 (15%–46%) in HC (Harbin-Changchun), MSL, BTH, CP (Central Plain) and SP (Shandong-Peninsula), suggesting lockdown measures are effective to PM_2.5 alleviation. Although O₃ concentrations generally increased during the lockdown, its increment rate declined compared with 2019 under similar sunlight duration and temperature. Additionally, unlike HC, MSL and BTH, which suffered from additional (> 30%) air masses from surrounding areas after the lockdown, the polluted air masses reaching YRD and PRD mostly originated from the long-distance transport, highlighting the importance of joint regional governance.     

A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m³ fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO₂, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.     

Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.     

Preparation and characterization of boron-doped corn straw biochar: Fe (Ⅱ) removal equilibrium and kinetics

Nowadays, iron ions as a ubiquitous heavy metal pollutant are gradually concerned and the convenient and quick removal of excessive iron ions in groundwater has become a major challenge for the safety of drinking water. In this study, boron-doped biochar (B-BC) was successfully prepared at various preparation conditions with the addition of boric acid. The as-prepared material has a more developed pore structure and a larger specific surface area (up to 897.97 m²/g). A series of characterization results shows that boric acid effectively activates biochar, and boron atoms are successfully doped on biochar. Compared with the ratio of raw materials, the pyrolysis temperature has a greater influence on the amount of boron doping. Based on Langmuir model, the maximum adsorption capacity of 800B-BC_1:2 at 25 °C, 40 °C, 55 °C are 50.02 mg/g, 95.09 mg/g, 132.78 mg/g, respectively. Pseudo-second-order kinetic model can better describe the adsorption process, the adsorption process is mainly chemical adsorption. Chemical complexation, ions exchange, and co-precipitation may be the main mechanisms for Fe²⁺ removal.     

Isolation and characterization of a strain with high microbial attachment in aerobic granular sludge

Aerobic granule is a special microbial aggregate associated with biofilm structure. The formation of aerobic granular sludge is primarily depending on its bacterial community and relevant microbiological properties. In this experiment, a strain with high microbial attachment was isolated from aerobic granular sludge, and the detailed characteristics were examined. Its high attachment ability could reach 2.34 (OD_600nm), while other low attachment values were only around 0.06-0.32, which indicated a big variation among the different bacteria. The strain exhibited a very special morphology with many fibric fingers under SEM observation. A distinctive behaviour was to form a spherical particle by themselves, which would be very beneficial for the formation and development of granular sludge. The EPS measurement showed that its PN content was higher than low attachment bacteria, and 3D-EEM confirmed that there were some different components. Based on the 16S rRNA analysis, it was identified to mostly belong to Stenotrophomonas. Its augmentation to particle sludge cultivation demonstrated that the strain could significantly promote the formation of aerobic granule. Conclusively, it was strongly suggested that it might be used as a good and potential model strain or chassis organism for the aerobic granular sludge formation and development.     

绿色技术专利强制许可法律问题研究

绿色技术专利强制许可要求将环境利益明确纳入公共利益范围,而专门的绿色技术专利强制许可制度则进一步要求针对绿色技术构建特殊许可通道。功能主义观念以环境保护目标的必要性来证成绿色技术专利强制许可的正当性,但没有解释绿色技术、环境保护、公共利益之间的具体联系,从而不能证明绿色技术专利强制许可背后的法律逻辑。法治主义视角下,从强制许可事由、审查程序以及许可费三方面来看,该制度会引起一系列的正当性问题。未来需要将专门的绿色技术专利强制许可制度限定在政府实施的范围内,并依据权利人自认来确定绿色技术的范围。     

Comparison of macroinvertebrate community structure in urban (Shenzhen City) streams with typical habitat characteristics北大核心CSCD

2020年12月在深圳市城市区域典型生境特征溪流——城市山区源头溪流金龟河、国家地质公园保护区入海溪流杨梅坑河与黑臭水体治理后溪流石溪河,开展底栖动物多样性与生境质量状况取样,通过多元统计分析探明各溪流底栖动物群落结构差异及其主要环境影响因子.结果表明:(1)金龟河底质异质性(SI)最高;杨梅坑河水质最好且流态异质性(Fr)最优,石溪河水质最差且底质异质性(Fr)最低.(2)共采集鉴定大型底栖动物118个分类单元,隶属于3门6纲14目87科.水生昆虫均占绝对优势,其中金龟河67属(81.7%),杨梅坑河62属(95.4%),石溪河12属(52.2%).金龟河中底栖动物Shannon-Wiener多样性指数、改进的Shannon-Wiener多样性指数、Pielou均匀度均高于杨梅坑河与石溪河.(3)金龟河的主要功能摄食类群是滤食者(45.5%),杨梅坑河(38.3%)与石溪河(58.7%)的主要功能摄食类群均为收集者.(4)冗余分析(RDA)结果显示,氨氮、海拔、湿宽、水温、溶氧、底质异质性(SI)、电导率和流态异质性(Fr)为影响深圳市溪流的大型底栖动物群落结构的主要环境因子.研究表明:(1)深圳市的山区溪流可作为深圳市生物多样性保护的重点区域.(2)在城市溪流生态系统中,水环境化学因子并非为主要影响因子,生境多样性发挥了重要作用.(图6表3参43)     

Stoichiometric characteristics of carbon,nitrogen, and phosphorus in leaf litter soil of Pinus yunnanensis forest during different restoration stages in the karst plateau of eastern Yunnan北大核心CSCD

以滇东岩溶坡地不同恢复阶段云南松林(纯林、人工混交林、天然次生林)为研究对象,以元江栲原生林和小铁仔灌丛作为参照样地,对5种植被类型中的叶片-枯落物-土壤中的C、N、P含量和化学计量比特征进行研究.结果表明:(1)3种云南松林都呈现为高C(432.27 g/kg)、低N(10.28 g/kg)、P(0.96 g/kg)的格局,5种植被类型的叶片-枯落物-土壤C、N、P含量基本都表现为叶片>枯落物>土壤,C/N、C/P、N/P值则都表现为枯落物>叶片>土壤,叶片和枯落物的养分含量和化学计量比值与土壤间差异显著.(2)3种云南松林对于养分的吸收同化能力差异不大,但天然次生林的枯落物质量最好,人工混交林的土壤N、P有效性最高,云南松林内受N的胁迫作用强于原生林和灌丛.(3)植物叶片-枯落物-土壤中C、N、P及其化学计量比间相关性显著,互馈机制明显.研究区内土壤C、N、P化学计量特征受土壤pH、团聚体颗粒、含水率、容重和硝态氮影响显著.因此,滇东岩溶高原云南松植被恢复过程中主要受N胁迫作用,提高枯落物养分回流是云南松植被恢复与经营的关键要素.(图4表3参41)