不同粒径纳米TiO2对大型溞的毒性效应及腐殖酸的调控作用

为评估纳米TiO₂在环境水体中的暴露风险,选用大型溞作为模式生物,研究了不同粒径纳米TiO₂（20、40、60和100 nm）对大型溞毒性效应的影响,并探究了腐殖酸对不同粒径纳米TiO₂毒性效应的调控作用.结果表明,粒径是影响纳米TiO₂颗粒毒性效应的重要因素,以大型溞半数致死时间（LT₅₀）为指标,不同粒径纳米TiO₂对大型溞的毒性作用强弱顺序依次为：20 nm颗粒 > 40 nm颗粒 > 60 nm颗粒 > 100 nm颗粒（p<0.05）.腐殖酸的存在可以显著降低纳米TiO₂颗粒对大型溞的毒性作用,腐殖酸对小尺寸纳米TiO₂颗粒的毒性抑制作用更为明显（p<0.05）.大型溞体内ROS水平与抗氧化系统相关酶活分析表明,纳米TiO₂导致大型溞体内活性氧自由基（ROS）浓度升高是其产生毒性作用的重要原因,腐殖酸的存在可以显著降低大型溞体内由于纳米TiO₂暴露而引起的ROS浓度上升（p<0.05）,进而减轻纳米TiO₂对大型溞的毒性作用.此外,腐殖酸可以减小不同粒径纳米TiO₂之间的毒性差异.本研究结果可为纳米TiO₂在环境水体中的暴露风险评估提供参考依据.     

Biotoxicity evaluation of zinc oxide nanoparticles on bacterial performance of activated sludge at COD,nitrogen, and phosphorus reduction

• ZnO-NP disrupted metabolic/catabolic balance of bacteria by affecting DHA activity. • ZnO-NPs toxicity was related to Zn²⁺ ion, interaction with cell and ROS generation. • Exposure to ZnO-NPs resulted in changed bacterial community structure at sludge. • The change in the EPS content was observed during exposure to ZnO-NPs. The unique properties and growing usage of zinc oxide nanoparticles increase their release in municipal wastewater treatment plants. Therefore, these nanoparticles, by interacting with microorganisms, can fail the suitable functioning of biological systems in treatment plants. For this reason, research into the toxicity of ZnO is urgent. In the present study, the toxicity mechanism of ZnO-NPs towards microbial communities central to granular activated sludge (GAS) performance was assessed over 120-day exposure. The results demonstrate that the biotoxicity of ZnO-NPs is dependent upon its dosage, exposure time, and the extent of reactive oxygen species (ROS) production. Furthermore, GAS performance and the extracellular polymeric substances (EPS) content were significantly reduced at 50 mg/L ZnO-NPs. This exposure led to decreases in the activity of ammonia monooxygenase (25.2%) and nitrate reductase (11.9%) activity. The Field emission scanning electron microscopy images confirmed that ZnO-NPs were able to disrupt the cell membrane integrity and lead to cell/bacterial death via intracellular ROS generation which was confirmed by the Confocal Laser Scanning Microscopy analysis. After exposure to the NPs, the bacterial community composition shifted to one dominated by Gram-positive bacteria. The results of this study could help to develop environmental standards and regulations for NPs applications and emissions.     

Semi-closed synthesis of nitrogen and oxygen Co-doped mesoporous carbon for selective aqueous oxidation

Heteroatom-doped meso/micro-porous carbon materials are conventionally produced by harsh carbonization under an inert atmosphere involving specific precursors, hard/soft templates, and heteroatom-containing agents. Herein, we report a facile synthesis of N and O co-doped meso/micro-porous carbon (NOMC) by template-free carbonization of a small-molecule precursor in a semi-closed system. The semi-closed carbonizaiton process yields hydrophilic NOMCs with large surface area in a high yield. The porous structure as well as the elemental composition of NOMCs can be modulated by changing the holding time at a particular temperature. NOMCs as metal-free heterogeneous catalysts can selectively oxidize benzyl alcohol and its derivatives into aldehydes/ketones with>85％conversion in aqueous solution, which is much higher than that of the control sample obtained in tube furnace (21％conversion), mainly due to their high N content, high percentage of pyridinic N, and large surface area. The presence of O-containing moieties also helps to improve the hydrophilicity and dispersion ability of catalysts and thus facilitates the mass transfer process during aqueous oxidation. The NOMC catalysts also dispayed excellent activity for a wide range of substrates with a selectivity of>99％.     

SO2在水和有机溶剂中的化学形态及其脂/水分配系数：SO2生理学研究新模式

为了探讨内源性SO2生理作用和毒理作用的化学机制,采用真空减压法、超声波法、通气法、光谱扫描法及摇瓶法等对SO2在水和有机溶剂中的化学形态及其脂/水分配系数进行了研究.研究结果表明:1)气态SO2不仅易溶于水,而且更易溶于有机溶剂;2)SO2在水和有机溶剂中的溶解主要是物理性溶解,其主要以SO2分子状态存在于溶液中,在饱和溶液中90%以上是以自由分子状态存在,在较低浓度下也有50%左右以自由分子状态存在;3)SO2的脂/水分配系数仅为0.16～0.20,使存在于生物膜(脂相)系统的内源性SO2很容易进入水相并转化为亚硫酸盐,这将导致其在组织细胞内的半寿期很短,这符合信号分子的特征.由此结论:1)以SO2生理盐水溶液作为SO2供体,可作为研究内源性SO2生理作用和毒理作用的新模式;2)内源性SO2在组织细胞内的失活途径是:SO2→SO32-/HSO3-→SO42-.此外,论文认为亚硫酸钠和亚硫酸氢钠混合液并不能作为"SO2供体"用以处理生物组织.     

Spatio-temporal dissolved oxygen dynamics in the Orbetello lagoon by fuzzy pattern recognition

This paper models the dissolved oxygen (DO) dynamics in the Orbetello lagoon as a function of the physico-chemical and ecological system variables, including the submerged vegetation, nutrients, and hydrodynamics. It should be viewed as the concluding sequel to a previous paper describing the dynamics of the lagoon ecosystem [Giusti, E., Marsili-Libelli, S., 2006. An integrated model for the Orbetello lagoon ecosystem, Ecol. Model. 196, 379–394] by introducing the missing DO dynamics. The model considers the oxygen demand originating from the decay of carbonaceous and nitrogenous compounds, as well as photosynthesis and natural reaeration by winds and currents as the oxygen producing processes. With a fixed-parameter set the model could accurately reproduce each single circadian DO cycle, but in the long run it failed to extend this fit and could not accommodate the large DO fluctuations induced by the seasonal variability. In order to enhance the model flexibility, a fuzzy pattern recognition algorithm was designed to classify the circadian DO patterns into four typical behaviours, related to the season, and estimate the corresponding parameters, with the overall model output being a fuzzy combination of these sets. The paper discusses several methods to patch the parameter sets and compares their performance in tracking long-term DO variations. A final assessment of the model validity is obtained by incorporating the whole DO dynamics (model, fuzzy pattern recognition and parameter combination) into the general lagoon model and producing a consistently correct series of DO daily distributions over a yearly cycle. Thus the paper contains both a practical and a methodological aspect. The practical one is the linking of all the lagoon dynamics to the dissolved oxygen kinetics in order to clarify to what extent macroalgae and macrophytes influence the oxygen balance. The methodological aspect consists of extending the validity of short-term models to long time-horizons through a patching technique supported by fuzzy pattern recognition.     

氧和氮等离子体改性细旦涤纶的清洁工艺比较

该文对氧、氮低温等离子体改性细旦涤纶进行了研究,分别探讨了氧、氮等离子体放电参数对提高细旦涤纶上染率的影响,得出了2种工艺的最佳放电参数。实验结果表明:经氧、氮等离子体改性后,细旦涤纶的上染率分别提高了17%和5%,说明氧等离子体改性可显著减少印染废水中的污染物排放量,有利于环境治理,氮等离子体改性效果次之。      

皂素工业废水CODCr排放限值的研究

皂素工业是近几年来迅速发展的一个重要生物医药化工行业,我国皂素主产区位于南水北调中线工程水源汉江上游,其排放的大量高浓度含酸有机废水给水源保护带来严重威胁,急需制定我国的皂素工业水污染物排放标准.采用三段式两相厌氧为核心的二级生化组合工艺技术从实验室试验、现场工业性试验和示范工程三方面对皂素工业废水COD_Cr排放限值进行了研究,皂素废水二级生化处理出水中残留COD_Cr总量(以质量浓度计)约为400～500 mg/L,其中溶解性微生物代谢产物(SMP)质量浓度约为240～280 mg/L.综合考虑技术可达性和经济可行性,将现有企业COD_Cr排放限值规定为400 mg/L;为引导企业对废液综合利用,推进皂素行业清洁生产,规定新建企业和现有企业的第二时段的限值为300 mg/L.提出了丹江库区相应的COD_Cr总量指标及皂素规模限额.执行该标准后,全国每年可削减COD_Cr 71　400 t,其中南水北调中线工程水源汉江上游至少可削减60　690 t,可以满足中线调水水源区的环境保护要求.      

有机碳源和溶解氧对亚硝酸盐生物硝化的影响研究

从城市污水处理厂的活性污泥中纯化分离到高活性硝化菌株N-20（Nitrobacter sp．）,在一种新型材料Carbon Foam的表面挂膜;通过对菌株N-20进行摇瓶试验,选择添加有机碳源的种类,将其在pH7．5～8．0、温度28℃的条件下,分别以NaNO2和K2HPO4为氮源和磷源,通过生物滤塔中的液相连续试验,考察在不同DO的条件下有机碳源对硝化作用的影响规律。结果表明,以葡萄糖作为有机碳源,DO≥2mg／L,葡萄糖低于20mg／L时,生物滤塔内可进行正常硝化,NO2^--N的硝化去除率维持在90％左右,随着葡萄糖浓度的增加,硝化去除率下降到70％;DO≤2mg／L,葡萄糖对硝化作用的抑制增强,当葡萄糖为200mg／L时,生物滤塔中NO^2-—N的硝化去除率仅为32％。     

硬木地板材料和棉花秆的变氧浓度热解燃烧表观动力学的实验研究

本文采用TG-FTIR分析方法深入研究了火场中硬木地板材料和棉花秆变氧浓度燃烧过程,深入分析了氧浓度对纤维物质燃烧表观热失重影响;通过大量的动力学参数计算得出了可燃物的表观活化能与实际氧浓度成线性关系;分析了氧浓度对木材燃烧气体产物的影响,并探索了氧浓度影响热解和燃烧的机理。     

Pd/CZ/Al2O3催化剂的制备、表征与三效催化性能

以共浸渍法制得的氧化铝负载铈锆固溶体为载体,并浸渍贵金属Pd得到了Pd/CZ/Al2O3催化剂.实验结果表明,该催化剂在老化前后都表现出良好的三效催化活性,新鲜样品Pd/CZ/Al2O3活性与Pd/CZ相当,老化后样品前者优于后者.结合XRD,BET,TPR等表征手段,讨论了Pd/CZ/Al2O3的催化活性特别是高温老化后活性与其组成结构之间的内在关系,揭示了其老化后仍具有较高活性的主要原因在于保持了Pd与CZ/Al2O3复合载体之间的强相互作用(SMSI).