内质网应激在氟暴露致小鼠睾丸损伤中的作用

探讨了内质网应激在亚慢性氟暴露致小鼠睾丸损伤中的作用及分子机制.选用健康初断乳ICR雄性小鼠30只,随机分为对照组（C）、低氟组（LF）和高氟组（HF）,分别饮用自来水、5、30 mg·L^-1氟化钠水溶液90 d.亚慢性氟暴露结束后,以睾丸脏器系数、睾丸组织氧化/抗氧化酶和形态结构、精子质量、睾丸细胞凋亡、葡萄糖调节蛋白78（GRP78）、CCAAT/增强子结合蛋白同源蛋白（CHOP）、半胱氨酸天冬氨酸蛋白酶12（CASPASE-12）、半胱氨酸天冬氨酸蛋白酶3（CASPASE-3）为观测点.结果表明,与对照组比,LF组和HF组LDH、SOD、T-AOC活性下降,MDA含量上升,HF组GSH-PX活性下降,差异有统计学意义（p<0.05或p<0.01）;LF组可见细胞层次减少、间隙变大,成熟精子数量减少,HF组细胞溶解、层次紊乱,空泡化严重,少见成熟精子;LF组和HF组小鼠的精子活力降低,HF组小鼠精子数量下降,畸形率上升,差异有统计学意义（p<0.05或p<0.01）;LF组和HF组睾丸细胞凋亡指数上升,差异有统计学意义（p<0.01）;LF组和HF组Grp78、Caspase-12、Caspase-3基因表达水平上升,差异有统计学意义（p<0.05或p<0.01）.结果提示,除氧化应激以外,Caspase-12和Caspase-3基因表达异常可能是氟暴露致小鼠睾丸细胞凋亡异常的分子机制之一.     

基于AIS轨迹修复的船舶排放空间表征改进方法与应用

基于船舶自动识别系统（Automatic Identification System,AIS）数据表征船舶排放是目前船舶排放空间表征的主流方法,但AIS船舶轨迹点缺失会造成船舶排放量低估和船舶空间分布表征错误,进而影响船舶排放控制区的划分.为改进船舶排放空间表征,本研究以2013年广东省AIS船舶数据为例,采用基于时间和经纬度的三次样条方法对AIS船舶轨迹进行修复,结合动力法计算船舶排放,分析对比AIS轨迹修复前后船舶排放表征的差异,并利用空气质量模型和卫星观测评估AIS轨迹修复对船舶排放表征和广东沿海空气质量模拟的改进效果.结果表明：轨迹修复后广东省海域船舶轨迹点总数由4685773个增至5746664个,船舶NO_x排放量增加了0.6%.对于轨迹点与排放缺失集中的粤东海域,轨迹修复后船舶轨迹点数增加了88%,NO_x排放量在广东省船舶排放量的占比提升至22%,特别是在粤东重点修复海域NO_x排放量增加了2.7倍.原始轨迹在广东省海域较为稀疏,在粤东海域有明显轨迹缺失;轨迹修复后广东省海域船舶轨迹更为密集,粤东海域船舶轨迹得以补充,船舶排放空间分布更连贯.对比模拟结果与卫星观测结果,轨迹修复后粤东重点修复海域船舶模拟浓度与观测浓度的偏差由51%减至6%,总体上船舶排放模拟结果更接近卫星观测结果.     

金属改性对SAPO-34低温还原NO性能的影响

采用浸渍法制备金属改性SAPO-34分子筛催化剂,分析比较了不同单金属（Cu或Co）及不同比例双金属（Cu：Co=1：1、3：1、5：1,质量比）改性催化剂对NO的催化还原性能,评价了不同催化剂的N₂选择性,并采用扫描电子显微镜（SEM）、比表面积测试、X射线衍射分析（XRD）、NH₃-程序升温脱附（NH₃-TPD）等表征手段对催化剂的物化性能进行了分析.结果表明,单金属Cu改性催化剂具有较宽的温度区间,在250~450℃范围内NO的转化率始终保持在100%;双金属改性使NO转化率保持为100%的最低温度下降了25~50℃,显著拓宽了低温段窗口,其中,Cu₃Co₁/SAPO-34催化剂的低温催化还原性能最好,200℃即可实现100%的NO转化率,175℃下的转化率也高达80%以上.Cu-Co双金属改性SAPO-34分子筛催化剂具有优异的低温催化还原NO性能,具有在机动车尾气、工业废气的低温脱硝治理领域应用的潜力.     

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.     

Preparation of hydrophobic hierarchical pore carbon–silica composite and its adsorption performance toward volatile organic compounds

Carbon–silica materials with hierarchical pores consisting of micropores and mesopores were prepared by introducing nanocarbon microspheres derived from biomass sugar into silica gel channels in a hydrothermal environment.The physicochemical properties of the materials were characterized by nitrogen physical adsorption(BET),scanning electron microscopy(SEM),and thermogravimetric(TG),and the adsorption properties of various organic waste gases were investigated.The results showed that microporous carbon materials were introduced successfully into the silica gel channels,thus showing the high adsorption capacity of activated carbon in high humidity organic waste gas,and the high stability and mechanical strength of the silica gel.The dynamic adsorption behavior confirmed that the carbon–silica material had excellent adsorption capacity for different volatile organic compounds(VOCs).Furthermore,the carbon–silica material exhibited excellent desorption characteristics:adsorbed toluene was completely desorbed at 150℃,thereby showing superior regeneration characteristics.Both features were attributed to the formation of hierarchical pores.     

Aerosol optical properties under different pollution levels in the Pearl River Delta (PRD) region of China

To clarify the aerosol hygroscopic growth and optical properties of the Pearl River Delta(PRD)region,integrated observations were conducted in Heshan City of Guangdong Province from October 19 to November 17,2014.The concentrations and chemical compositions of PM_(2.5),aerosol optical properties and meteorological parameters were measured.The mean value of PM_(2.5) increased from less than 35(excellent) to 35-75 μg/m~3(good) and then to greater than 75 μg/m~3(pollution),corresponding to mean PM_(2.5) values of 24.9,51.2,and 93.3 μg/m~3,respectively.The aerosol scattering hygroscopic growth factor(f(RH = 80%)) values were 2.0,2.12,and 2.18 for the excellent,good,and pollution levels,respectively.The atmospheric extinction coefficient(σext)and the absorption coefficient of aerosols(σ_(ap)) increased,and the single scattering albedo(SSA)decreased from the excellent to the pollution levels.For different air mass sources,under excellent and good levels,the land air mass from northern Heshan had lower f(RH) and σ_(sp) values.In addition,the mixed aerosol from the sea and coastal cities had lower f(RH) and showed that the local sources of coastal cities have higher scattering characteristics in pollution periods.     

Tuning the fill percentage in the hydrothermal synthesis process to increase catalyst performance for ozone decomposition

The performance of Ce-OMS-2 catalysts was improved by tuning the fill percentage in the hydrothermal synthesis process to increase the oxygen vacancy density. The Ce-OMS-2 samples were prepared with different fill percentages by means of a hydrothermal approach (i.e. 80%, 70%, 50% and 30%). Ce-OMS-2 with 80% fill percentage (Ce-OMS-2-80%) showed ozone conversion of 97%, and a lifetime experiment carried out for more than 20?days showed that the activity of the catalyst still remained satisfactorily high (91%). For Ce-OMS-2-80%, Mn ions in the framework as well as K ions in the tunnel sites were replaced by Ce⁴⁺, while for the others only Mn ions were replaced. O₂-TPD and H₂-TPR measurements proved that the Ce-OMS-2-80% catalyst possessed the greatest number of mobile surface oxygen species. XPS and XAFS showed that increasing the fill percentage can reduce the AOS of Mn and augment the amount of oxygen vacancies. The active sites, which accelerate the elimination of O₃, can be enriched by increasing the oxygen vacancies. These findings indicate that increasing ozone removal can be achieved by tuning the fill percentage in the hydrothermal synthesis process.     

Hygroscopicity measurement of sodium carbonate, β-alanine and internally mixed β-alanine/Na2CO3 particles by ATR-FTIR

Water-uptakes of pure sodium carbonate(Na_2CO_3),pure β-alanine and internally mixedβ-alanine/Na_2CO_3 aerosol particles with different mole ratios are first monitored using attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR) technique.For pure Na_2CO_3 aerosol particles,combining the absorptions at 877 and 1422 cm-1 with abrupt water loss shows the efflorescence relative humidity(ERH) of 62.9%–51.9%.Upon humidifying,solid Na_2CO_3 firstly absorbs water to from Na_2CO_3·H2 O crystal at 72.0% RH and then deliquesces at 84.5% RH(DRH).As for pure β-alanine particles,the crystallization takes place in the range of 42.4%–33.2% RH and becomes droplets at ～ 88.2% RH.When β-alanine is mixed with Na_2CO_3 at various mole ratios,it shows no efflorescence of Na_2CO_3 whenβ-alanine to Na_2CO_3 mole ratio(OIR) is 2:1.For 1:1 and 1:2 β-alanine/Na_2CO_3 aerosols,the ERHs of Na_2CO_3 are 51.8%–42.3% and 57.1%–42.3%,respectively.While β-alanine crystal appears from 62.7% RH for 2:1 and 59.4% RH for both 1:1 and 1:2 particles and lasts to driest state.On hydration,the DRH is 44.7%–75.2% for Na_2CO_3 with the OIR of 1:1 and 44.7%–69.0%for 1:2 mixture,and those of β-alanine are 74.8% for 2:1 mixture and 68.9% for two others.After the first dehumidification–humidification,all the water contents decrease despite of constituent fraction.And at ～ 92% RH,the remaining water contents are 92%,89% and 82%at ～ 92% RH,corresponding to OIR of 2:1,1:1 and 1:2 mixed system,respectively.     

Dynamic nano-Ag colloids cytotoxicity to and accumulation by Escherichia coli: Effects of Fe3+, ionic strength and humic acid

Released Ag ions or/and Ag particles are believed to contribute to the cytotoxicity of Ag nanomaterials, and thus, the cytotoxicity and mechanism of Ag nanomaterials should be dynamic in water due to unfixed Ag particle:Ag⁺ ratios. Our recent research found that the cytotoxicity of PVP-Ag nanoparticles is attributable to Ag particles alone in 3 hr bioassays, and shifts to both Ag particles and released Ag⁺ in 48 hr bioassays. Herein, as a continued study, the cytotoxicity and accumulation of 50 and 100 nm Ag colloids in Escherichia coli were determined dynamically. The cytotoxicity and mechanisms of nano-Ag colloids are dynamic throughout exposure and are derived from both Ag ions and particles. Ag accumulation by E. coli is derived mainly from extracellular Ag particles during the initial 12 hr of exposure, and thereafter mainly from intracellular Ag ions. Fe³⁺ accelerates the oxidative dissolution of nano-Ag colloids, which results in decreasing amounts of Ag particles and particle-related toxicity. Na⁺ stabilizes nano-Ag colloids, thereby decreasing the bioavailability of Ag particles and particle-related toxicity. Humic acid (HA) binds Ag⁺ to form Ag⁺-HA, decreasing ion-related toxicity and binding to the E. coli surface, decreasing particle-related toxicity. HA in complex conditions showed a stronger relative contribution to toxicity and accumulation than Na⁺ or Fe³⁺. The results highlighted the cytotoxicity and mechanism of nano-Ag colloids are dynamic and affected by environmental factors, and therefore exposure duration and water chemistry should be seriously considered in environmental and health risk assessments.     

Development of a static test apparatus for evaluating the performance of three PM2.5 separators commonly used in China

PM_(2.5) separator directly affects the accuracy of PM_(2.5) sampling.The specification testing and evaluation for PM_(2.5) separator is particularly important,especially under China's wide variation of terrain and climate.In this study,first a static test apparatus based on polydisperse aerosol was established and calibrated to evaluate the performance of the PM_(2.5) separators.A uniform mixing chamber was developed to make particles mix completely.The aerosol concentration relative standard deviations of three test points at the same horizontal chamber position were less than 0.57%,and the particle size distribution obeyed logarithmic normal distribution with an R~2 of 0.996.The flow rate deviation between the measurement and the set point flow rate agreed to within ± 1.0% in the range of -40 to 50℃.Secondly,the separation,flow and loading characteristics of three cyclone separators(VSCC-A,SCC-A and SCC112) were evaluated using this system.The results showed that the 50% cutoff sizes(D_(50)) of the three cyclones were 2.48,2.47 and 2.44 μm when worked at the manufacturer's recommended flow rates,respectively.The geometric standard deviation(GSD) of the capture efficiency of VSCCA was 1.23,showed a slightly sharper than SCC-A(GSD = 1.27),while the SCC112 did not meet the relevant indicator(GSD = 1.2 ± 0.1) with a GSD = 1.44.The flow rate and loading test had a great effect on D_(50),while the GSD remained almost the same as before.In addition,the maintenance frequency under different air pollution conditions of the cyclones was summarized according to the loading test.