MnFe2O4磁性纳米棒非均相Fenton催化降解水中四环素的研究

采用水热合成法成功制备出MnFe₂O₄磁性纳米棒（s-MnFe₂O₄）,并考察了商品化的Fe₃O₄、MnFe₂O₄和合成的s-MnFe₂O₄纳米棒这3种磁性纳米颗粒作为非均相Fenton催化剂降解水中四环素抗生素的性能.同时,采用X射线衍射（XRD）、透射电镜（TEM）、N₂吸附-脱附、振动样品磁强计（VSM）及X射线光电子能谱（XPS）等技术对催化剂的理化性质进行了表征.非均相Fenton催化降解四环素的结果表明,s-MnFe₂O₄具有最高的催化活性,反应180 min,四环素的去除率可以达到87.6%,TOC的去除率达到47.5%.自由基捕获试验证实了羟基自由基（·OH）是非均相Fenton氧化过程中的主要活性物种.s-MnFe₂O₄磁性纳米棒的高催化活性归因于其表面拥有较高含量的Mn³⁺和Fe²⁺物种,它们的存在能加速界面电子的转移效率,从而促进·OH的生成.合成的s-MnFe₂O₄催化剂具有良好的稳定性,循环使用6次,四环素的去除率仅从87.6%降低到80.2%,且氧化过程中活性组分的流失很少.     

焦化废水处理过程中固相物质的形成及处置方法评价

焦化废水处理过程中产生的焦油、污泥和结晶杂盐等固相物质,既有资源属性,又有污染特性,但目前缺乏基于能源、经济及环境影响方面的评估.本研究阐述了3类固相物质的形成机制,建立了质量当量计算及处置方法评价模型.以宝武集团韶关钢铁股份有限公司焦化厂（二期）焦化废水处理工程的A/O/H/O（厌氧/好氧/水解/好氧）流化床工艺作为考察对象,利用工程运行参数和水质统计数据进行固相物质的产量推算,结果发现,焦油、物化污泥、生物污泥（含水率为80%）和工业杂盐的产率分别为0.186、5.80、4.24和1.97 kg·m^-3.通过处置方法评价模型明确了焦油焚烧、污泥热解、结晶杂盐分盐提纯后工业应用是最佳处置方案,在60 m³·h^-1废水处理规模的固相物质处置过程中,每年约产生1177 MWh的能源,获得135.0万元的经济效益,排放627.0 t CO₂,表明能源回收、经济效益和环境影响的协同存在.     

深圳市秋季大气臭氧立体分布特征

利用大气O₃探测激光雷达在深圳市东部生态区和西部城区同步开展垂直观测,探究了2018年深圳市O₃立体分布在秋季光化学污染活跃期至冬季非活跃期的演变过程.结果表明：光化学反应活跃的10月,东部地面O₃浓度相对于西部地面高出约128%;地面向上至450m,O₃浓度在东部生态区发生快速降低,而在西部城区由于存在“滴定效应”,O₃浓度随高度升高而升高;450m~2km,东、西部O₃浓度均随高度升高而降低,西部城区O₃浓度水平超过东部生态区约30%;2km以上高空,东、西部O₃浓度趋同（70μg/m³）,并保持稳定,为具深圳市秋季O₃污染过程提供了较高的大气背景浓度.高污染期间,深圳市大气边界层内O₃浓度变化较为一致,西部高空的O₃区域传输作用更加显著.秋季至冬季光化学反应逐渐减弱,深圳市O₃浓度的水平和垂直空间差异逐渐减小,冬季的深圳市O₃污染基本受大气背景控制.     

漓江流域δD和δ18O对蒸发的指示作用

以漓江流域为例查明不同水体之间氢氧稳定同位素组成特征,并探讨氢氧稳定同位素对漓江流域的蒸发过程指示作用.结果表明：流域内不同水体之间,氢氧稳定同位素表现出不同的组成特征,地表水和地下水,在丰水期δD值和δ¹⁸O值要比枯水期更容易富集,地下水的δD值和δ¹⁸O值分布范围较地表水小;随着水温的升高,δ¹⁸O的变化趋势比d-excess明显.从漓江上游到下游高程逐渐下降,河水线的斜率和截距也在逐渐减小,其中漓江下游河水线的斜率和截距要低于当地大气降水线,表明下游受到蒸发作用较强烈;地下河水线、地表河水线在一定程度上偏离当地大气降水线,但偏离程度较小,表明三者之间有很好的水力联系.受温度和湿度的共同影响,漓江干流丰水期河水的蒸发量占最初水体总量的0.7%~9.1%,枯水期河水的蒸发量占最初水体总量的2.6%~9.7%,丰水期的蒸发比例低于枯水期,从上游到下游蒸发比例在逐渐上升.研究区蒸发量估算值为959.40mm,与多年实测值少43.11mm,相对误差4.70%.氢氧稳定同位素对研究区降水、地表水、地下水之间的转换规律具有重要的实际意义,在今后的漓江流域水文研究中有着更加广阔的空间.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Fas/FasL途径在氟暴露致PC12细胞凋亡中的作用

为了探讨Fas/FasL途径在氟暴露致PC12细胞凋亡中的作用及其机制,采用含20、40、80、160mg/L NaF培养液处理PC12细胞.结果表明,所有剂量NaF处理12、24、36、48h,PC12细胞活性升高;上述不同剂量NaF处理24h后,与对照组比,PC12细胞的活性氧水平、细胞凋亡率、细胞内Fas/FasL信号转导通路Fas和FasL、Caspase8、FADD、Caspase3基因和蛋白表达水平均呈显著上升（P < 0.05）,而Bid基因和蛋白表达水平显著下降（P < 0.05）,且呈氟暴露剂量依赖性.结果提示Fas/FasL途径在氟暴露致PC12细胞凋亡中起重要作用,其中FADD可能是Fas/FasL凋亡途径中的重要靶分子.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Will polycentric cities cause more CO2 emissions? A case study of 232 Chinese cities

From 2000 to 2010 China experienced rapid economic development and urbanization. Many cities in economically developed areas have developed from a single-center status to polycentricity. In this study, we used exploratory spatial data analysis (ESDA) to identify the population centers, which identified 232 cities in China as having urban centers. COMP was used to represent urban agglomeration, and POLYD (representing how far is the city's sub-centers to the main center), POLYC (representing the number of a city's centers), and POLYP (representing the population distributed between the main center and the sub-centers) were used to indicate urban polycentricity. Night light data were used to determine the CO₂ emissions from various cities in China. A mixed model was used to study the impact of urban aggregation and polycentric data on the CO₂ emission efficiency in 2000 and 2010. The study found that cities with higher compactness were distributed in coastal areas, and the cities with higher multicentricity were distributed in the Yangtze River Delta and Shandong Province. The more compact the city was, the less conducive it was to improving CO₂ emission efficiency. Polycentric development of the city was conducive to improving the CO₂ emission efficiency, but the number of urban centers had no significant relationship with the CO₂ emission efficiency. Our research showed that the compactness and multicentricity of the city had an impact on the CO₂ emission efficiency and provided some planning suggestions for the low carbon development of the city.     

某垃圾焚烧厂投产前后周边土壤二英类化合物的分布

为研究垃圾焚烧厂运行对周边土壤二英类化合物（PCDD/Fs）含量的影响,采集了珠三角地区某垃圾焚烧厂投产前和投产后周边土壤样品,分析研究了该垃圾焚烧厂运行对周边土壤中PCDD/Fs含量和组分的变化.结果表明:①2012年（投产前）珠三角地区某垃圾焚烧厂周边土壤PCDD/Fs含量较低,范围为163~591 ng/kg（毒性当量范围为0.198~0.863 ng I-TEQ/kg,I-TEQ为国际毒性当量因子折算的毒性当量值）;2017—2019年（投产后）周边土壤PCDD/Fs含量范围为151~1.75×103 ng/kg（毒性当量范围为0.812~3.88 ng I-TEQ/kg）,与其他研究相比处于较低的水平.②投产后,距该垃圾焚烧厂较近（1.5 km）的采样点（S1）土壤PCDD/Fs含量逐年增长,在较远（5.2 km）但人口较密集的采样点（S3）土壤PCDD/Fs含量整体较高,但呈逐年下降趋势.③投产后,土壤中的17种PCDD/Fs单体组分中,毒性当量贡献率最高的单体为八氯二苯并二英（OCDD）和2,3,4,7,8-五氯二苯并呋喃（2,3,4,7,8-PeCDF）,二者毒性当量贡献率范围为15.7%~45.4%.④在同一采样点土壤PCDD/Fs单体组分年间差异不明显,但同一年份不同采样点差异明显.研究显示,目前该垃圾焚烧厂周边土壤PCDD/Fs含量较低,但仍需要长期监测其可能带来的风险.