烃类及其衍生物闪点、沸点的定量构效关系

基于定量结构一性质相关性（QSPR）原理,研究了烃类及其衍生物闪点、沸点与其分子结构间的内在定量关系。应用CODESSA软件计算384种烃类及其衍生物的分子结构描述符,建立了闪点和沸点的QSPR模型。用最佳多元线性回归（B．MLR）方法筛选得到的分子描述符建立了线性回归模型。用B-MLR方法所选择的5个描述符作为支持向量机（SVM）的输入建立了非线性模型。所有的化合物被分为训练集和测试集,对每个模型的训练集和测试集的复相关系数、交互验证系数、均方根误差等进行了计算,并用测试集对模型的预测能力进行检验,预测结果表明：预测值与实验值均符合良好,所建立的闪点模型稳健,泛化能力强,预测误差小,预测的效果令人满意,但沸点的模型预测效果有待加强。相比烃类物质的模型,加了衍生物的模型性能均有所下降。     

The variations of exergies and structural exergies along eutrophication gradients in Chinese and Italian lakes

Taking 29 Chinese lakes and 29 Italian lakes as two separate case studies, the paper presented the variations of exergies and structural exergies along eutrophication gradients in Chinese and Italian lakes. The exergies (Ex) and structural exergies (Exst) were calculated based on phytoplankton biomass (BA) and zooplankton biomass (BZ). A trophic state index (TSI) scaling from 0 to 100 was developed to classify trophic status for Chinese and Italian lakes based on three indicators, chlorophyll-a concentration (Chl-a, in mg/m³), total phosphorus (TP in mg/m³) and transparency in Secchi disk depth (SD in m). The relationships between TSI and Ex, Exst, total biomass, BZ/BA ratios were analyzed. The following results were obtained: (1) with the increase of TSI in Chinese and Italian lakes, there is an increasing trend for Ex, and a decreasing trend for Exst, generally. The obvious negative correlations exist between TSI and Exst, at the significant level of 0.01 for Italian lakes, and 0.05 for Chinese lakes. The obvious positive correlations exist between TSI and Ex, at the significant level of 0.01 for Chinese lakes, and for Italian lakes in Spring, Autumn and the all-year. (2) The structural exergy is more dependent on the ratio of phytoplankton biomass to zooplankton biomass (BZ/BA) than the exergy, and the exergy is more dependent on total biomass than the structural exergy. (3) The phytoplankton biomass (BA) and zooplankton biomass (BZ) are increased with the increasing TSI in Chinese and Italian lakes, and phytoplankton biomass (BA) increases more rapidly then zooplankton biomass (BZ) does. This results in the definite decrease of BZ/BA ratio with the increasing trophic status index. Such changes of BA, BZ and BZ/BA ratio could explain successfully the variations of exergies and structural exergies along eutrophication gradients in Chinese and Italian lakes. From the two separate case studies of Chinese lakes and Italian lakes, it could be concluded that exergy and structural exergy are feasible to serve as the system-level ecological indicators to give appropriate information on the trophic status of different lakes.     

Residual levels and health risk of polycyclic aromatic hydrocarbons in freshwater fishes from Lake Small Bai-Yang-Dian, Northern China

The residual levels of polycyclic aromatic hydrocarbons (PAHs) in the liver, brain, gill and muscle tissues of four common edible freshwater fish species including crucian carp, snakehead fish, grass carp and silver carp collected from Lake Small Bai-Yang-Dian in northern China were measured by GC-MS. The distribution and composition pattern of PAHs in the fish tissues, and the effects of lipid contents in fish tissues and the octanol-water partition coefficient (Kow) of PAHs congeners on them were analyzed. The human health risk of PAHs though fish consumptions was estimated. The following results were obtained: (1) The average residual levels of total PAHs (PAH₁₆) on wet weight base in the different tissues of each fish species ranged from 4.764 to 144.254 ng/g ww. The differences in the average residual levels on wet weight base for PAH₁₆ within four fish species were not statistically significant (P > 0.05); however, these within four fish tissues were statistically significant (P < 0.01). (2) There were very similar distribution patterns of PAH congeners among both the fish tissues and the fish species, as indicated by statistically significant positive interrelationships (R = 0.58-0.97, P < 0.01 or P < 0.05). Low molecular weight (LMW) PAHs predominated the distribution in the fish tissues, accounting for 89.97% of total PAHs. Phe was the most dominant component, according for 37.79% of total PAHs, followed by Ant (18.59%), Flo (12.59%), Nap (10.79%), Fla (9.82%) and Pyr (6.43%). (3) The PAHs residues and distribution in the fish tissues are dependent on both the Kow of PAH congeners and the lipid contents in the fish tissues. There was a significant positive relationship (R = 0.7116, P < 0.0001) between lipid contents and PAHs residual levels. The statistically significant negative relationships (P < 0.05) were found between LogKow and log-transformed PAHs contents on wet weight base for all fish tissues except for the muscle tissue of snakehead fish, the brain and liver tissues of crucian carp. (4) The risk levels of total PAHs were lower than 10⁻⁵ for the muscle tissues of four studied fish species and for the brain tissues of grass carp and snakehead fish; while these were higher than 10⁻⁵ for the brain tissues of crucian carp and silver carp. The risk levels of total PAHs in the liver tissues of four studied fish species except for snakehead fish exceeded 10⁻⁵ for 2-4.5 times. However, the potency equivalent concentration (PEC) of total PAHs in four studied fish tissues were still lower than the maximum permissible BaP limits for crops and baked meat and for plants in the national criterions. The distributions of PAH congeners in fish were well simulated by a level III fugacity model, especially for low molecule weight PAHs.     

冻融交替对高寒草甸土壤微生物量氮和有机氮组分的影响

采用Bremner氮素分级方法,研究冻融交替对高寒草甸土壤微生物量氮和有机氮组分的影响.结果表明:随着冻融时间的变化,微生物量氮含量先减少后增加,在冻融1 d后达到最小值,4℃、-4℃、-4～4℃和-20～4℃处理下分别下降了50.37%、57.47%、37.79%和37.51%;氨基酸氮和氨基糖氮变化趋势相同,先增加后减少,均在冻融1 d后达到最大值,各处理氨基酸氮含量分别为处理前的1.6倍、1.47倍、1.44倍和1.5倍,氨基糖分别为处理前的1.66倍、1.58倍、1.65倍和1.91倍;氨态氮含量先增加后减少,-20～4℃处理在冻融1 d后为处理前的1.25倍,其余3个处理在冻融3 d后达到最大值;各处理酸解未知氮的变化趋势大体相同,在冻融25 d后达到最小值.研究表明冻融时间对微生物量氮和有机氮组分影响显著,微生物量氮含量是有机氮组分变化的主要原因.     

Nitrous oxide fluxes from the littoral zone of a lake on the Qinghai-Tibetan Plateau

Nitrous oxide (N(2)O) fluxes were measured in six littoral mirco-zones of Lake Huahu on Qinghai-Tibetan Plateau in the peak growing season of years of 2006 and 2007. The weighted mean N(2)O flux rate was 0.08 mg N m(-2) h(-1) (ranged from -0.07 to 0.35 mg N m(-2) h(-1)). The result was relatively high in the scope of N(2)O fluxes from boreal and temperate lakes. Emergent plant zones (Hippuris vulgaris and Glyceria maxima stands) recorded the highest N(2)O flux rate (0.11 ± 0.24 and 0.08 ± 0.17 mg N m(-2) h(-1), respectively). Non-vegetated lakeshore recorded the lowest N(2)O flux (0.03 ± 0.11 mg N m(-2) h(-1)), lower than that from the floating mat zone of Carex muliensis (0.05 ± 0.18 mg N m(-2) h(-1)), the floating-leaved plant zone of Polygonum amphibium (0.07 ± 0.11 mg N m(-2) h(-1)), and the wet meadow (0.07 ± 0.15 mg N m(-2) h(-1)). Standing water depths were important factors to explain such spatial variations in N(2)O fluxes. Significant temporal variations in N(2)O fluxes were also found. Such temporal variation in N(2)O flux in the littoral zone may be dependent on the interaction of water regime and thermal conditions, instead of the latter solely. These results showed the importance of the littoral zone of lake, especially the emergent plant zone, as a hotspot of N(2)O fluxes in such grazing meadows.     

基于固相萃取及高效液相色谱-荧光检测分析的污泥中氟喹诺酮类抗生素研究方法的开发

氟喹诺酮类抗生素(FQs)作为常见的药品和个人护理用品(PPCPs)在环境中广泛存在.由于在生物体内很难被代谢,FQs会通过粪尿排泄等途径进入城市污水处理系统并最终富集到污泥中.并且,由于其在环境中的累积效应,FQs的存在极易增强致病菌的耐药性,限制了污泥的后续资源化利用.为得到适用于污泥中FQs的分析方法,进一步把握FQs在污水及污泥处理过程中的固/液分配及降解规律,研究中选择4种代表性FQs:氧氟沙星(OFL)、诺氟沙星(NOR)、环丙沙星(CIP)和洛美沙星(LOM)为研究对象,并通过所设计的正交试验,考察了固相萃取材料、萃取体系p H、洗脱剂对FQs的固相萃取效率的影响,在此基础上进一步优化了固相样品中FQs的提取方法,最终建立了细胞破碎,碱式提取(三乙胺/甲醇/水以5/25/75混合),固相萃取富集(SPE),磷酸-三乙胺溶液为缓冲盐流动相,甲醇为有机流动相,梯度荧光扫描的高效液相色谱-荧光(HPLCFLD)检测方法.液态样品中4种FQs的加标回收率采用新方法后可达到82%~103%;固态样品中4种FQs的加标回收率也可达到71%~101%.同时,为进一步确认不同运行条件对污泥吸附FQs能力的影响,针对好氧、缺氧和厌氧污泥分别进行了吸附试验研究,发现处于不同活性状态的污泥(厌氧、缺氧和好氧污泥)对FQs的吸附能力呈现出递减的趋势,但对FQs的吸附率都达到90%以上.该结论也证实了实际污水处理厂所去除的50%的FQs主要是通过污泥吸附这一途径实现的.     

高比表面积铜藻基活性炭的制备及工艺优化

以铜藻为原料,在对其进行元素含量、生化组成分析的基础上,分别采用ZnCl2活化法和H3PO4活化法制备活性炭,并以活性炭得率、碘吸附值、焦糖脱色率为指标,采用正交法考察了升温速率、活化温度、浸渍比(活化剂/铜藻质量比)等因素的影响,得到最佳工艺条件.同时,采用扫描电镜(SEM)、Brunauer-Emmet-Tller(BET)比表面积等方法分析活性炭特征.结果表明,铜藻原料粒度对制得的活性炭性能影响显著,106～180μm的颗粒较为适合.ZnCl2活化法制得的活性炭吸附性能明显优于H3PO4活化法;ZnCl2活化法的最佳工艺条件为:升温速率10℃.min-1、活化温度600℃、活化时间2h、浸渍比4,在保证活性炭得率超过30%的基础上,制备的活性炭比表面积为2314.58m2.g-1,碘吸附值为835.3mg.g-1,焦糖脱色率为110%,性能明显优于其他大型海藻原料所制备的活性炭,是陆地传统活性炭原料的有效补充.     

安太堡露天矿复垦地不同人工植被恢复下的土壤酶活性和肥力比较

人工重建植被是露天矿复垦地植被恢复,提高土壤质量的主要途径之一.选择适宜的人工植被对快速恢复土壤质量具有重要意义.本文主要研究了安太堡露天矿复垦地油松-刺槐-柠条混交林、沙棘-刺槐-柠条-沙枣混交林和苜蓿地的土壤养分含量及酶活性,综合评价了这3种不同植被类型对土壤肥力恢复效果.结果表明,随着植被恢复的进行,土壤养分含量均有增加,油松-刺槐-柠条混交林的土壤养分含量显著高于其它样地.从以养分含量和酶活性权重计算的土壤综合肥力指标值(IFI)可知,油松-刺槐-柠条混交林IFI值最高.综合来看,对土壤重建效果最好的为油松-刺槐-柠条混交林,其次是沙棘-刺槐-柠条-沙枣混交林,再次为苜蓿.     

溢油应急浮式设备库设计方案

依据溢油应急浮式设备库配置设备的类型及数量,提出了设备库的设计方案;设备库将以趸船为基础,设计了底舱、设备库房、会议室、办公室、休息室和溢油处置辅助设备,设备库房和底舱配置了动力驱动系统、布放设备、溢油卸载、围控、回收、储存、油水分离及移驳过驳等设备,实现了设备库的平台承载、溢油应急处置和辅助三大功能。     

海洋微藻对游离氨基酸的利用特性研究

分别以4种游离氨基酸——丙氨酸、甘氨酸、谷氨酸和天冬氨酸为唯一氮源,采用实验室一次性培养的方法,研究典型赤潮藻——东海原甲藻(Prorocentrum donghaiense)、球形棕囊藻(Phaeoecystis globosa)和米氏凯伦藻(Karenia mikimotoi)及常见种类中肋骨条藻(Skeletonema costatum)的生长特性、光合特征及对氨基酸的吸收动力学特征,以无机氮源硝氮、氨氮作为对照.研究结果表明,在无菌条件下,东海原甲藻和球形棕囊藻可以利用多种游离氨基酸快速生长,而米氏凯伦藻和中肋骨条藻在以游离氨基酸为唯一氮源条件下不能维持生长.东海原甲藻和球形棕囊藻在丙氨酸中的生长速率最高,天冬氨酸和谷氨酸次之,甘氨酸最低.氨基酸处理组的Fv/Fm值在培养后期降幅小、降速慢,且高于无机氮处理组.东海原甲藻和球形棕囊藻对丙氨酸的最大吸收速率和半饱和常数分别为3.32、0.41pmol·cell-1·h-1和6.99和20.54pmol·L-1.因此,海洋微藻对游离氨基酸的吸收利用具有显著的种间差异,东海原甲藻和球形棕囊藻具有更广的氮营养生态位,在近海有机污染不断加剧的背景下,更容易形成优势甚至暴发赤潮.