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％.     

Spatial variation of otolith elemental signatures among juvenile gray snapper (<Emphasis Type="Italic">Lutjanus griseus</Emphasis>) inhabiting southern Florida waters

Juvenile gray snapper, Lutjanus griseus, are believed to use bays and estuaries in southern Florida as nurseries before moving out to the adjoining reef tract as adults. Using high-resolution sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS), the elemental chemistry of the otoliths of juveniles from five nursery regions was resolved by establishing elemental “signatures” for each region. In this study we simultaneously analyzed 32 elements including a suite of rare earth elements. A stepwise variable selection procedure retained a subset of eight elements that contributed substantially to separating otolith samples, including two rare earth elements; this is one of the first studies in which rare earth elements in otoliths have contributed to separation of fish stocks. The classification success rate in assigning fishes to the correct region of origin was 82%. Resolution of sites less than 10 km apart suggested high site fidelity in juvenile gray snapper and little mixing of water masses between sites. The juvenile nursery signatures will be used to determine the relative contribution of different nurseries to the adult population on an adjoining reef tract.     

Microenvironmental time-activity patterns in Chongqing, China

An investigation using recall questionnaires was conducted in winter and autumn 2006 to evaluate the time-activity patterns in Chongqing, China. The average time spent in seven microenvironments (MEs) including outdoors, transit, living room, bedroom, kitchen, classroom/office, and other indoors were found to be about 3.5, 1.1, 2.5, 9.7, 1.4, 4.2, and 1.7 h per day, respectively. According to the results of a nonparametric test, the sampling period and day of week were significant for the variation of the time spent in all MEs except for transit and outdoors. The time budget was analyzed using a general linear model (GLM), which exhibited significant variability by demographic factors such as gender, age, residence, education, and household income.     

Comparison of some homogeneity tests in analysis of over-dispersed binomial data

This paper compares the procedures based on the extended quasi-likelihood, pseudo-likelihood and quasi-likelihood approaches for testing homogeneity of several proportions for over-dispersed binomial data. The type I error of the Wald tests using the model-based and robust variance estimates, the score test, and the extended quasi-likelihood ratio test (deviance reduction test) were examined by simulation. The extended quasi-likelihood method performs less well when mean responses are close to 1 or 0. The model-based Wald test based on the quasi-likelihood performs the best in maintaining the nominal level. The score test performs less well when the intracluster correlations are large or heterogeneous. In summary: (i) both the quasilikelihood and pseudo-likelihood methods appear to be acceptable but care must be taken when overfitting a variance function with small sample sizes; (ii) the extended quasi-likelihood approach is the least favourable method because its nominal level is much too high; and (iii) the robust variance estimator performs poorly, particularly when the sample size is small.     

濒危植物疏花水柏枝种子萌发的生态学特性

疏花水柏枝Myricaria laxiflora分布于我国三峡从宜昌至重庆段长江干流的消落带,分布区十分狭小.三峡工程兴建后,疏花水柏枝将失去绝大部分的生境而成为濒危物种.通过设置一系列控制实验测试了土壤水质量分数,温度和土壤类型对疏花水柏枝种子萌发的生态学的影响.实验结果表明,土壤水质量分数、温度和土壤类型对种子萌发率都有显著影响.其中种子萌发率随土壤水质量分数增加而增大,土壤水质量分数达到饱和程度时萌发率达到最大值;高温条件下的种子萌发率高于低温,种子萌发率在21～27℃达到最大值;种子在河沙基质上萌发好于在沙土基质上.结合分布区萌发季节的环境条件分析,土壤水质量分数是限制该物种分布于消落带的关键作用因子.据此就该物种的种群保护与重建提出了一些建议.     

典型有机磷酸酯阻燃剂分析方法研究进展

有机磷酸酯(OPEs)是一类重要的有机磷阻燃剂,近些年逐渐取代了溴代阻燃剂,广泛应用于各行各业,也因此导致在多种环境介质中有较高的暴露量和潜在风险。已有研究表明,OPEs具有一定的毒理效应,对人体及其他生物均有潜在危害。本文综述了近年来国内外OPEs的检测技术,详述了不同环境介质OPEs的前处理方法。结果表明,目前固相萃取(SPE)和固相微萃取(SPME)仍是水样前处理的主要方法;对于固体样品,加速溶剂萃取/加压液相萃取(ASE/PLE)和微波辅助萃取(MAE)应用较多;虽然大气样品仍以固体吸附剂方式为主,但已向在线一体化方向发展;而生物样品的前处理方法多与水样和固体样品方法相似;但是对于复杂环境介质中OPEs样品的前处理较为困难,方法有待改善;气相色谱-质谱联用(GC-MS)和气相色谱-氮磷检测器(GC-NPD)对弱极性和易挥发的OPEs分析效果好,而强极性和难挥发的OPEs多用液相色谱-质谱联用(LCMS);气相色谱-质谱串联(GC-MS/MS)、液相色谱-质谱串联(LC-MS/MS)和高效液相色谱-质谱串联(UPLC-MS/MS)等对多种复杂的环境介质中的OPEs均有较好的检测分析效果,但并未普及。最后,对OPEs分析测试方法的发展趋势提出了展望。     

全氟辛烷磺酸盐(PFOS)对半滑舌鳎(Cynoglossus semilaevis)免疫相关基因表达的影响

为了解全氟辛烷磺酸盐(perfluorooctane sulfonate, PFOS)暴露对半滑舌鳎(Cynoglossus semilaevis)免疫功能的影响,在实验室条件下,运用RT-PCR方法分析了PFOS暴露对半滑舌鳎热休克蛋白hsp70、hsp90、C型凝集素(c-type lectin)和细胞色素c氧化酶(cytochrome c oxidase, cox)等4种免疫相关基因表达水平的影响。实验测定了上述4种基因在半滑舌鳎肝、鳃、肠及肌肉4种不同组织中随时间(0、24 h、48 h、96 h和7 d)的表达变化情况。结果表明,在4种组织中,hsp70基因的表达与对照相比为上调,其中,肝组织hsp70基因的表达量显著高于其他各组织,且表达高峰值的出现也早于其他各组织;hsp90基因在肝和鳃组织中表达量随时间不同而波动,在肠组织中表达上调,在肌肉中表达显著下调;c-type lectin基因表达量与对照组相比表达显著下调或无明显差异;cox基因在肝组织和肠组织中表达下调,在鳃和肌肉中表达上调。上述研究结果表明,PFOS能引起免疫相关基因的表达变化,对半滑舌鳎具有潜在的免疫毒性。肝组织中各免疫基因对PFOS胁迫的响应高于其他组织。本研究可为阐明全氟辛烷磺酸盐对半滑舌鳎的免疫毒性提供基础数据。     

Zn2+对黄瓜发芽期生理特性的影响

锌是植物必需的营养元素,同时也是一种常见的环境有毒重金属元素.以黄瓜(Cucumis sativus L.)为试验材料,设置不同Zn2 处理(0、25、50、100、200、300 mg·L-1),利用发芽和出苗试验,研究了Zn2 对黄瓜发芽期生理特性的影响.结果显示,低处理(0～25 mg·L-1)对黄瓜种子萌发和幼苗生长有促进作用,当为25 mg·L-1时最有利于黄瓜种子萌发和幼苗生长,其种子发芽率、发芽势、发芽指数、活力指数、根长、下胚轴长、下胚轴粗度和相对含水量均高于对照及其他浓度处理;幼苗相对电导率、丙二醛含量、可溶性糖含量、游离脯氨酸含量、SOD活性及POD活性均在此浓度得到最低.但从50 mg·L-1开始,随着增加,黄瓜种子萌发的各项指标开始下降,幼苗生长的各项生理指标开始上升,对黄瓜种子发芽和幼苗生长产生抑制作用,并在300 mg·L-1时抑制作用得到最大.该研究为进一步研究农业生态整治与安全高效利用提供理论基础.     

PDMS半透膜采样装置的制作研究

水中痕量持久性有机污染物的监测是经典的分析化学难题,传统分析方法既费时又费材料,且只能测定某一时间点的浓度.三油酸甘油脂半透膜被动采样器虽能克服传统方法的一些缺点,但对膜的要求较高.通过在一个固定于不锈钢网上,扁平、密封的商品低密度聚乙烯(LDPE)膜袋夹层中均匀涂布聚二甲基硅氧烷(PDMS),制作出一种新的半透膜被动采样器.用此被动采样器在混合多氯联苯(PCBs)的过饱和水溶液中反复模拟采样,测得半透膜最佳富集时间、时间和富集量的关系曲线以及其它特性.使用气质联用仪测得的数据证明此装置可用于水体中多氯联苯等痕量持久性有机污染物的采集和定量分析,其线性富集时间可达 9 d,富集率大约为3×103 ~ 6×103倍,为今后的环境监测提供了一种制作简单、使用方便、富集率好、费用低廉的新方法.     

秸秆还田和免耕对水稻土微形态特征的影响

在四川盆地的平原区和丘陵区,通过4年8作的田间定位试验,研究了秸秆还田免耕和翻耕两种方式对土壤的微形态特征的影响,这对了解秸秆还田对土壤特性演化及生态环境的影响有重要意义.分别采制各处理的0～10 cm和10～20 cm土层的原状土样,制取土壤薄片,进行土壤微形态学比较研究.结果表明:两个试验区秸秆还田翻耕与免耕处理后,在土壤基本组成成分、形成物、土壤粗粒质和细粒质、土壤垒结及微结构等微形态特征方面均有一定的特点和明显变化.从这些土壤微形态特征得知,秸秆还田形成了良好的微结构趋势,促进了有机质腐殖化,能显著改善土壤的理化特性.