区域大气环境模式RegAEMS中二次气溶胶的改进模拟研究

为了提升二次气溶胶的模拟精度,在区域大气环境模式RegAEMS中加入了硫酸盐气溶胶的两种新生成机制（NO₂+SO₂化学过程和过渡金属催化氧化（TMI））以及二次有机气溶胶（SOA）生成的挥发性有机物基集（VBS）方法.模拟了2020年1月上海市两次中度污染过程,并与观测数据进行对比验证.研究发现,两次污染过程硫氧转化率（SOR）均大于0.4,PM_2.5主要组分为SO₄^2-、NO₃^-、NH₄⁺等水溶性离子,占比为61.25%~63.85%.SOA占比为2.92%~3.0%.加入NO₂+SO₂化学过程和过渡金属催化氧化（TMI）后,硫酸盐模拟精度明显提升（相关系数（R）从0.49~0.63提升至0.58~0.67,相对标准偏差（NMB）从-35.0%~-36.5%提升至-17.3%~-14.2%）.两种化学过程在污染发展阶段平均贡献占比为23.3%~27.9%,这可能是造成污染条件下SO₄^2-浓度迅速增加的主要原因.VBS机制能够较好地模拟出SOA的变化趋势（相关系数为0.53~0.56）,由于硫酸盐和SOA生成机理的改进,RegAEMS在PM_2.5的模拟精度上有所提升（相对标准偏差（NMB）从-13.5%~-6.0%提升至-9.0%~-3.3%）.     

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.     

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.     

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。     

钯/泡沫镍电极对水体中2-氯联苯的电催化脱氯作用

采用两室流通式隔膜电解池,研究了钯修饰泡沫镍电极对纯水相中2-氯联苯(2-CB)的电催化还原脱氯作用,考察了电流密度、pH 值和溶液流速对2-CB 脱氯率的影响.结果表明,当电流密度为1.5mA/cm²、阴极液pH 值为5.5、阴极液流速为7.4mL/(min·cm²)时,脱氯反应30min,2-CB 脱氯率达91.4%.脱氯产物包括联苯和苯基环己烷,根据脱氯过程碳平衡关系可确定该过程为逐步氢化反应.     

土壤中锁定残留芘在体外消化系统中的生物可给性（Oral Bioaccessibility of Bound Residue of Pyrene in Contamination Soils Determined by an in Vitro Gastrointestinal Model）

体外消化过程可能导致土壤中憎水有机污染物提取量增加.论文采用3种有机质含量不同的土壤进行体外消化实验,目的在于验证如下假设:土壤中部分锁定残留芘可以在人体消化系统中释放出来,若不考虑这部分贡献,常规提取方式获得的土壤污染浓度可能低估污染土壤口摄风险.研究结果证实:经体外消化的土壤的总芘提取量显著高于未经消化样品,其差别与土壤有机质含量有关.消化液中的胆汁盐是造成锁定残留芘释放的关键成份.在特定范围(2~20mg·mL-1)内,提取效率不受胆汁盐浓度影响.胆汁盐作用下锁定残留芘的释放为一次动力学过程.     

胡敏酸对铜的鱼鳃生物有效性影响的计算机模拟

以彩虹方头鱼为模拟对象,用鱼鳃微环境测定装置和化学平衡计算方法(MINTEQA2),计算了含和不含胡敏酸的人工河水及暴露于其中的鱼鳃微环境中,不同pH条件下,铜的形态分布.研究了胡敏酸对鱼鳃内外的铜的形态分布及其生物有效性的影响,并讨论了pH对此的影响.计算结果表明,当胡敏酸存在时,胡敏酸络合态铜成为鱼鳃内外铜形态分布体系中的优势态,并引起铜生物有效性的降低.鱼鳃粘液和胡敏酸的共同作用使鱼鳃微环境中的生物有效铜含量低于外部水相.pH对铜形态分布及生物有效性的影响主要发生在碱性环境下.     

估算多氯联苯在鱼体内生物富集因子的分子连接性指数模型

根据 40个 PCB在鱼体内生物富集因子 ( BCF)的实测数据建立了分子连接性指数估算模型 .模型可决系数 0 .91 1 ,平均误差 0 .1 95个对数单位 .通过比较发现 ,对于单一类别化合物分子连接性指数模型比片段常数模型更精确 ,对分子整体结构特征的描述效率更高 ,但片段常数模型具有物理意义明确、变量选择及模型调整灵活的优点 .     

用片段常数法估算非极性有机化合物的生物富集因子

根据121种logKow（辛醇－水分配系数）值在1.45～8.19之间的非极性有机化合物在鱼体内生物富集因子（BCF）的实测数据,建立了非极性有机化合物在鱼体中生物富集因子（BCF的片段常数法估算模型．采用分类模型系数比较法对在分类模型中表现不同的同一个片段或结构因子重新确定划分原则,在此基础上模型得到进一步改进．最终模型的可换系数为0.993,平均误差为0239个对数单位．