平流层CH4的时空变化特征及其与O3的关系

 利用1991年10月到2005年11月的HALO₃E卫星观测资料,对全球70°S～70°N范围内平流层100hPa到1 hPa的大气CH₄混合比进行了时空特征分析.结果表明:①CH₄混合比在平流层是随高度上升而逐渐减小的.平流层中上层CH₄变化存在年循环,而平流层中下层CH₄变化存在半年振荡(SAO₃),且南半球平流层CH₄的季节变化振幅要大于北半球,特别是平流层中上层.平流层各个高度上的CH₄基本呈纬向分布,但是不同高度上分布特征有所差异;②平流层CH₄混合比变化存在3个月,10个月,准25个月和准45个月左右时间尺度的周期,但是3个月的短期变化和10个月的年循环只在1996年之前明显;③不同高度上,CH₄和O₃变化的相关关系是不同的,CH₄对O₃的破坏作用并不是存在于整个平流层,似乎是在有的高度上相关关系明显,有的高度上相关关系不明显.     

Identification of an AFLP marker linked to the stripe rust resistance geneYr10 in wheat

AFLP analysis of near-isogenic lines of the stripe rust resistance gene Yr10 was carried out with 6 PstⅠ- primers and 10 TaqⅠ-primers with the donor parent of Yr10 gene as the check. A total of about 4200 distinguishable bands were amplified, of which 5 were stable. The genetic linkage of the 5 polymorphic DNA fragments with the target gene were tested preliminarily on a segregating F₂ population derived from a cross between the gene donor parent “Moro” and susceptible cultivar “Mingxian 169”. The DNA fragment PT0502 was found closely linked to the Yr10 gene and cloned and sequenced. Based on the sequence specific primers for PCR were designed and synthesized. Genetic linkage analysis with 195 segregating F₂ plants indicated that the genetic distance was 0.5 cM between the main product SC₂₀₀ fragment produced by PCR with the primers and the Yr10 gene. The primers can be used to detect the Yr10 gene quickly, effectively and exactly.     

2015-2019年广西近地面大气臭氧污染特征分析

为了解广西臭氧（O₃）污染形成条件及来源,通过分析2015-2019年44个广西城市环境空气自动监测站点的近地面臭氧观测数据及城市气象数据,并结合2019年9月华南区域278个自动监测站点的O₃监测数据,探讨广西近地面O₃的污染特征及其与气象要素的关系。结果表明：近5年来广西O₃质量浓度逐年增加,平均增长率为2.64 μg/（m³·a）,春秋季增长较快;广西全年均会出现O₃超标现象,O₃日超标率逐年增长,各城市间差异逐年减小,广西南部沿海城市日超标率总体高于其他城市;O₃污染易发生于气温高于10℃、湿度在40%-70%的环境区域;广西区域O₃特征有6个主成分,第1主成分即可解释64.58%的O₃质量浓度;区域臭氧传输对广西高浓度臭氧污染事件有重大贡献,其中低浓度臭氧污染主要为本地生成。     

Carbon isotopic composition,turnover and origins of soil CO<Subscript>2</Subscript> in a monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir,South China

Carbon isotopic compositions of soil CO2 in rainy season (July) from two natural soil profiles (DHLS & DHS) in the monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir (DBR), South China, are presented. Turnover and origins of soil CO₂ are preliminarily discussed in this paper. Results show that the content of soil CO2 varies between 6120 and 18718 ppmv, and increases with increasing depth until 75 cm, and then it declines. In DHLS, soil CO₂ δ¹³C ranges from −24.71‰ to −24.03‰, showing a significant inverse correlation (R²＝0.91) with the soil CO₂ content in the same layer. According to a model related to soil CO₂ δ¹³C, the soil CO₂ is mainly derived from the root respiration (>80%) in DHLS. While in DHS, where soil CO₂ ? 13C ranges from −25.19‰ to −22.82‰, soil CO₂ is primarily originated from the decomposition of organic matter (51%–94%), excluding the surface layer (20 cm, 90%). Radiocarbon data suggest that the carbon in soil CO₂ is modern carbon in both DHLS and DHS. Differences in ¹⁴C ages between the “oldest” and “youngest” soil CO₂ in DHLS and DHS are 8 months and 14 months, respectively, indicating that soil CO₂ in DHLS has a faster turnover rate than that in DHS. The ¹⁴C values of soil CO₂, which range between 100.0‰ and 107.2‰ and between 102.5‰ and 112.1‰ in DHLS and DHS, respectively, are obviously higher than those of current atmospheric CO₂ and SOC in the same layer, suggesting that soil CO₂ is likely an important reservoir for Bomb-¹⁴C in the atmosphere.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

Preparation of alumina supported on carbon nanotubes and its application in fluoride adsorption from an aqueous solution

A novel material, alumina supported on carbon nanotubes (Al₂O₃/CNT), was prepared from carbon nanotubes and Al(NO₃)₃.X-ray diffraction (XRD) spectra demonstrate that alumina is amorphous, and scanning electron microscope (SEM) images show that CNT and alumina are homogeneously mixed. Furthermore, the fluoride adsorption behavior on the surface of Al₂O₃ /CNT has been investigated and compared with other adsorbents. The results indicate that Al₂O₃/CNT has a high adsorption capacity, with a saturation adsorption capacity of 39.4 mg/g. It is also found that the adsorption capacity of Al₂O₃/CNT is 3.0—4.5 times that of g-Al₂O₃ while almost equal to that of IRA-410 polymeric resin at 25℃. The adsorption isotherms of fluoride on Al₂O₃/CNT fit the Freundlich equation well, and optimal pH ranging from 5.0 to 9.0.     

杭州市2014年城区大气污染物浓度变化特征观测分析

为了研究杭州市城区大气污染物的浓度变化特征,本文选取了2014年杭州市环境监测中心站空气质量自动监测站的大气污染物浓度数据,并结合地面气象要素资料进行分析,结果表明,在观测期间,杭州市城区大气中的PM_2.5污染状况最严重,日平均浓度的超标率达30.7%;各污染物全年分布呈现明显的季节变化：O₃浓度呈现与该季节气温和太阳辐射强度在全年中的排列相一致的夏、秋、春和冬季依次递减的分布,NO₂则呈现冬高夏低,春秋介于两者之间的分布,SO₂浓度从高到低依次为冬季>春季>秋季>夏季,CO、PM_2.5和PM₁₀浓度都呈现出冬高夏季、春秋季变化平缓的季节变化特征;各污染物浓度日变化呈现不同变化规律：O₃和O_x浓度四季的日变化都呈单峰型分布,浓度峰值都出现在13:00～15:00,SO₂也呈现单峰型分布,在09:00～10:00左右达到峰值,于次日04:00左右达到谷值,NO₂、CO、PM_2.5和PM₁₀浓度的日变化特征类似,呈现双峰型变化,且峰值都与早晚高峰时间基本重合,冬季相对于其他季节首峰值时间推迟一小时左右;利用成对样本T检验进行比较,结果表明：NO₂浓度在17:00～次日09:00工作日均明显高于周末,而在09:00～14:00工作日略低于周末,14:00～17:00浓度基本相等,O₃浓度则在工作日的各时刻均高于周末;气象要素是大气污染物分布的重要影响因子,O₃与气温和风速呈极显著正相关关系,与湿度呈极显著负相关关系,NO₂与之相反,SO₂、CO、PM_2.5和PM₁₀与风速呈现一致的显著负相关关系外,与其他气象要素在不同季节差异性较大,SO₂和PM₁₀与相对湿度呈现极显著负相关关系,CO和PM_2.5与气温和湿度的相关性在不尽相同。     

Nonlinear optical polyimide with high thermal stability prepared by simultaneous poling and polymerization

The high T_g polyimide embedded with a novel imidazol-typed chromophore 2-[5-(4-nitrostilbenyl)thienyl]- 4,5-di(4-aminophenyl)imidazole (NSTDAPI) was prepared using the “simultaneous poling and polymerization” technique. The glass transition temperature (T_g) is 304℃ and the initial decomposition temperature (T_d) is 330℃. The in-situ second harmonic generation (in-situ SHG) measurement was performed to study its poling behavior and the stability of the poling-induced orientation. The nonlinear optical (NLO) coefficient d₃₃ of poled polyimide film is 32.2 pm/V at 1064 nm fundamental wavelength. The SHG signal of the poled polymer film was quite stable below 200℃, and then began to decay rapidly above 220℃. The half-decay temperature of dipole orientation for the film is 250℃.     

O3/H2O2工艺控制太湖原水中致嗅氨基酸

针对太湖原水中氨基酸氯化消毒后可能引发的嗅味问题,采用太湖某水厂滤后水为研究对象,考察了O₃/H₂O₂深度处理工艺对水中致嗅氨基酸的去除效果及影响因素。结果表明滤后水中致嗅氨基酸占总游离氨基酸的81.6%,采用O₃/H₂O₂工艺降解致嗅氨基酸的最佳投量为1.5 mg·L^-1 O₃和0.06 mM H₂O₂,去除率91.28%,致嗅氨基酸浓度降至484.62 ng·L^-1,加氯消毒后几乎没有致嗅风险。水温10~30℃范围内,O₃/H₂O₂对致嗅氨基酸的去除率随温度升高而增大;pH=6~8范围内,去除率随pH的升高而增大。另外,该组合工艺较单独O₃/H₂O₂对溴酸盐的生成也有明显抑制作用。     

CoFe2O4-Al2O3复合材料的制备及其在含日落黄废水处理中的应用

制备了铁酸钴-氧化铝（CoFe₂O₄-Al₂O₃）复合材料,并采用扫描电子显微镜（SEM）、X射线衍射（XRD）、比表面积和孔径分析仪对多孔CoFe₂O₄-Al₂O₃复合材料的物相和形貌进行了分析. 利用制备的CoFe₂O₄-Al₂O₃复合材料活化过硫酸氢钾（PMS）来降解废水溶液中的日落黄（SY）,通过研究CoFe₂O₄-Al₂O₃材料制备过程中Co²⁺,Fe³⁺和Al³⁺的物质的量之比、煅烧温度和时长对材料催化性能的影响,发现Co²⁺,Fe³⁺和Al³⁺的最佳物质的量之比为1:2:12,最佳煅烧温度为400 ℃和最佳煅烧时长为3 h. 对采用在最优条件下制得的CoFe₂O₄-Al₂O₃复合材料作为催化剂,PMS氧化降解含日落黄废水进行研究,考察了pH值、温度、不同体系、PMS用量、CoFe₂O₄-Al₂O₃材料用量和一些阴离子对日落黄降解的影响. 结果表明：在pH=7,温度为55 ℃条件下,用0.1 g催化剂和0.125 g PMS能使100 mL质量浓度为0.6 g·L^-1的日落黄溶液在30 min内降解率达到99.5%. 同时,碳酸氢根负离子（HCO₃^-）和硝酸根负离子（NO₃^-）的加入抑制了日落黄的降解,而Cl^-则能促进日落黄的降解. 此外,在进行4次循环使用后,CoFe₂O₄-Al₂O₃仍表现出很好的催化性能,日落黄去除效果仍能达到90%以上.     

纳米Al2O3颗粒对Cu-Al2O3性能的影响

采用溶胶-凝胶法制备纳米Al₂O₃颗粒,通过粉末冶金法制备氧化铝铜（Cu-Al₂O₃）。采用X射线光电子能谱仪、扫描电子显微镜、洛氏硬度仪和涡流计分别测试了Cu-Al₂O₃的结合能、微观组织、硬度和导电率。结果表明：随Al₂O₃颗粒含量的增加,Cu-Al₂O₃的硬度先升高后降低,当Al₂O₃颗粒的质量分数达到0.084%时,Cu-Al₂O₃的硬度达到最大值75.73（HRB）。Cu-Al₂O₃的导电率随着Al₂O₃颗粒含量的增加逐渐下降。Al₂O₃颗粒的质量分数为0.084%时为最佳值,Cu-Al₂O₃的硬度达到最大值,导电率达到69.1% IACS。     

上海市2013年以来空气污染物变化特征

根据上海市环境监测中心网站发布的2013年1月?2015年9月上海市空气污染监测结 果，对PM_2.5、PM₁₀、O₃、NO₂、SO₂、CO共6种污染物的变化特征进行了研究.结果表明：上海空气 污染物PM_2.5、PM₁₀、O₃、NO₂、SO₂、CO浓度在逐年降低，显现出近年来上海空气污染治理初见成 效；在每年的12月前后或冬季，PM_2.5、PM₁₀、NO₂、SO₂、CO浓度最高，在每年的8月前后或夏季浓 度最低；O3浓度在每年的12月或冬季最低，7月前后或夏季最高；PM_2.5、PM₁₀、NO₂、SO₂、CO与O₃之间的互为消长关系，在很大程度上取决于环境条件.     

Regularities of formation of binary intermetallic compounds between transition and non-transition elements

A four-parameter model based on the extended Miedema’s cellular model of alloy phases and pattern recognition methods has been used to study the regularities of the formation of binary intermetallic compounds between transition element and non-transition element. The formation criterion can be expressed as some inequities of electronegativity ∮, the valence electron density in Wagner-Seitz cell n_ws^1/3, Pauling’s metallic radius R and the number of valence electrons in atom Z or their functions. According to these empirical criterions, the “unknown” binary alloy system can be predicted, the predicted result is better than that of Miedema’s two-parameter model.     

TEM observation on nucleation of Ca α-Sialon

Ca α -Sialon compacts pressurelessly-sintered to the intermediate temperature (1 450℃) were investigated with TEM for an overall composition Ca_1.8Si_6.6Al_5.4O_1.8N_14.2. It was found that in most cases, the newly-formed α -Sialon grains had no epitaxial orientation relationship with the Si₃N₄ particles; only occasionally heteroepitaxial nucleation of α -Sialon on α -Si₃N₄ was detected. Further EDAX analysis revealed a much higher Ca concentration in the non-epi- taxially nucleated α -Sialon than in the heteroepitaxially nucleated α -Sialon. Thus a possible correlation between the concentration of metal cations in the α -Sialon structure and the nucleation mechanism has been proposed, i.e. α -Sialon compositions with higher Ca concentration show a stronger trend of non-epitaxial nucleation.     

高密度TeO2-Gd2O3-WO3闪烁玻璃颜色调控的研究

采用传统高温熔融法制备了不同玻璃组成的碲钆钨酸盐玻璃（TeO₂-Gd2O₃-WO₃），通过紫外—可见分光光度计研究了碲钆钨酸盐玻璃在分别固定Gd₂O₃浓度为10 mol%（xTeO₂-10Gd₂O₃-(90-x)WO₃）和20 mol%（yTeO₂-20Gd₂O₃-(80-x)WO₃）时，玻璃光学透过性随WO₃浓度和熔制温度的依赖关系，并借助光碱度理论进行了解释。结果表明，xTeO₂-10Gd₂O₃-(90-x)WO₃玻璃随着玻璃中WO₃浓度由0 mol%增加到60 mol%，碲钆钨酸盐玻璃的颜色由浅黄（低于20 mol%）逐渐变为深棕色（40 ~ 60 mol%）。另一方面，yTeO₂-20Gd₂O₃-(80-y)WO₃（y=40）玻璃随着玻璃熔制温度从1000 ℃升高到1200 ℃，碲钆钨酸盐玻璃的颜色从浅黄（低于1050 ℃），变为深棕色（1100 ℃）甚至黑色（1200 ℃）。这种颜色变化是由于随WO₃浓度升高，玻璃的光碱度单调增加，导致玻璃截止吸收边红移及玻璃光学透过率降低的共同作用效果。     

A12O3在一次烧结BaTiO3中的作用探讨

 探索了掺微量Al₂O₃和SiO₂的BaTiO₃的一次烧结工艺,该工艺有效降低了烧结温度.应用电子探针、光学显微镜、X射线衍射仪,TN-524能谱等设备对样品进行分析.BaTiO₃瓷体电阻随Al₂O₃掺杂量的变化关系及Al在BaTiO₃中分布情况等实验事实,表明在BaTiO₃烧结过程中Al可能是一种半导化元素,起施主的作用.通过新工艺,得到了性能较好的BaTiO₃热敏电阻.     

Al2O3对Mo-W-Co高温合金力学性能的影响

通过改变Mo-W-Co高温合金中Al₂O₃的含量,研究Al₂O₃对Mo-W-Co高温合金硬度和耐磨性能的影响.采用球磨、压制成形和真空烧结等工艺制备Mo-W-Co-Al₂O₃高温合金,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和金相显微镜(OM)对制备好的合金的相结构、形貌和粒度进行分析,并测试合金的硬度和耐磨性能.结果表明:添加Al₂O₃能提高Mo-W-Co高温合金的硬度和耐磨性能,当w_Al2O3为5%时,Mo-W-Co高温合金的硬度和耐磨性能达到最佳效果;在真空烧结时,Al₂O₃在合金中形成了γ-Al₂O₃相,是影响合金组织和性能的关键相.     

Al2O3/WO3/ZrO2催化剂的制备及在酯交换反应中的研究

以松木为模板,采用模板法将不同含量的Al₂O₃添加到WO₃/ZrO₂复合氧化物中,采用X射线衍射、BET比表面积分析、拉曼光谱和NH₃等温吸附测试等手段对其进行表征,以评估其改进结果。将Al₂O₃/WO₃/ZrO₂催化剂应用到甲醇与乌桕油（非食用油）的酯交换反应中,在其他反应条件相同,Al₂O₃质量分数为3%时,生物柴油最高产率达到83.1%。结果表明：添加Al₂O₃稳定了ZrO₂的四方相结构,使得催化剂比表面积更大、孔数量增加;模板法制备的催化剂孔径分布均匀,WO₃呈高度分散无定型状态;引入Al₂O₃增加了WO₃/ZrO₂催化剂的中强酸性,对弱酸性和强酸性无明显改变。     

高压水射流技术清洗刀具的研究

刀具是机械制造中用于切削加工的工具,表面热处理后易形成一层覆盖物影响其使用性能.主要研究了高压水射流技术清洗刀具,通过SEM、XRD测试得出刀具表面覆盖物为NaNO₃、Na₃H（CO₃）₂·2H₂O、Fe₂O₃、Fe₃O₄,形貌呈棒状、颗粒状等.为了清除这些覆盖物,采用DBG-1850Fg3型清洗机进行试验,发现在高压水压强为60 MPa、喷头直径为1.4 mm、清洗时间为60 s的条件下,表面的覆盖物可被清除.高压水射流清洗技术具有高效、环保等特点,是刀具表面清洗的发展方向.