Peak identification for PCDD/Fs in environmental samples at different temperature programs

A method has been developed for peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at different temperature programs. Their retention behaviours are predicted on the basis of an identification database of retention values (A, B) of gas chromatography. By the retention times of C-13 labelled 2,3,7,8-substituted PCDD/F internal standards, the retentions of all PCDDs and PCDFs can be calculated. After comparison with the retentions of practical environmental samples, the predicted values have been proved to be very accurate. (C) 2000 Elsevier Science Ltd. All rights reserved.

Sol-gel method for the preparation of solid-phase microextraction fibers

A novel sol-gel method is applied for the preparation of solid-phase microextraction (SPME) fibers. Scanning electron microscopy experiments suggested a porous structure for the poly(dimethylsiloxane) (PDMS) coating. SPME-GC analysis provided evidence that the sol-gel fibers have some advantages, such as high thermal stability, efficient extraction rates, high velocities of mass transfer, and spacious range of application.

Cleanup and quantification of polychlorinated dibenzo-p-dioxins/furans and polychlorinated biphenyls

By using modern techniques of isotope dilution, high-resolution gas chromatography/high-resolution mass spectrometry and multiple ions detection, an effective cleanup, qualitative and quantitative method was developed for polychlorinated dibenzo-p-dioxins/furans (PCDD/F) and polychlorinated biphenyls analysis. Based on the chromatographic relative retentions of PCDD/F, a software was established for automatic peak recognition of all the isomers from tetra- to octachlorine PCDD/F. It ensured good reliability and accuracy of the analytical data.

Computer assisted peak recognition for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in environmental samples

A software has been developed for the peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) after high resolution gas chromatography coupled with mass spectrometry (HRGC/HRMS). Based on the retention times of C-13 labelled 2,3,7,8-substituted PCDD/F internal standards, the retention times of all PCDD and PCDF can be calibrated automatically and accurately. Therefore, it is very convenient to identify the peaks by comparing the retention of samples and the calibrated retention times of their chromatograms. Hence, this approach is very significant because it is impossible to obtain always a standard chromatogram and PCDD/F analysis are very expensive and time consuming. The calibration results can be transferred to Excel for calculation. The approach is a first step to store costly and environmentally relevant data for future application.

Upgrading bio-oil over different solid catalysts

Solid acid 40SiO(2)/TiO2-SO42- and solid base 30K(2)CO(3)/Al2O3-NaOH were prepared and compared with catalytic esterification activity according to the model reaction. Upgrading bio-oil by solid acid and solid base catalysts in the conditioned experiment was investigated, in which dynamic viscosities of bio-oil was lowered markedly, although 8 months of aging did not show much viscosity to improve its fluidity and enhance its stability positively. Even the dehydration by 3A molecular sieve still kept the fluidity well. The density of upgraded bio-oil was reduced from 1.24 to 0.96 kg/m(3), and the gross calorific value increased by 50.7 and 51.8%, respectively. The acidity of upgraded bio-oil was alleviated by the solid base catalyst but intensified by the solid acid catalyst for its strong acidification. The results of gas chromatography-mass spectrometry analysis showed that the ester reaction in the bio-oil was promoted by both solid acid and solid base catalysts and that the solid acid catalyst converted volatile and nonvolatile organic acids into esters and raised their amount by 20-fold. Besides the catalytic esterification, the solid acid catalyst carried out the carbonyl addition of alcohol to acetals. Some components of bio-oil undertook the isomerization over the solid base catalyst.

原状土通气培养法测定黄土高原土壤供氮能力的研究

评价原状土通气培养法在反映黄土高原土壤供氮能力方面的效果。【方法】以采自于黄土高原差异较大的11个农田耕层土壤为供试土样,以包括和不包括土壤起始NO3--N原状土盆栽黑麦草累积吸氮量为参比,进行室内原状土通气培养法测定土壤供氮能力的研究。【结果】以包括土壤起始NO3--N盆栽试验植物吸氮量为参比,通气培养前CaCl2所淋洗起始NO3--N和起始矿质氮与5期黑麦草地上部氮素累积量密切相关,相关系数分别为0.856和0.862,达1%显著水平;与此相反,通气培养30周所矿化氮素、土壤起始矿质氮+通气培养30周矿化氮素、氮素矿化势(N0)及N0+起始矿质氮与5期黑麦草地上部氮素累积量间无显著相关关系,相关系数分别仅为0.410、0.553、0.492和0.419。以不包括土壤起始NO3--N盆栽试验植物吸氮量为参比,通气培养前CaCl2淋洗起始NO3--N和起始矿质氮与五期黑麦草地上部氮素累积量间的相关性尽管有所降低,但相关性仍达5%显著水平,相关系数分别为0.613和0.607;而通气培养30周矿化氮素、土壤起始矿质氮+通气培养30周矿化氮素、N0及N0+起始矿质氮与五期黑麦草地上部吸氮量的相关系数却明显...

对间隙淋洗长期通气培养条件下黄土高原土壤供氮能力的评价

采用间隙淋洗长期通气培养法,通过对黄土高原物理化学性质差异较大的10种农田土样起始矿质氮、起始提取态总氮、起始可溶性有机氮,以及培养期间淋洗矿质氮、淋洗总氮、可溶性有机氮含量及其与作物吸氮量关系的研究,分析并评价黄土高原主要农田土壤氮素矿化能力以及包括和不包括培养淋洗可溶性有机氮对土壤供氮能力的影响。结果表明,供试土样起始可溶性有机氮平均为N 23.9 mg/kg,是起始提取态总氮的28.8%,土壤全氮的2.4%。在通气培养淋洗总氮中,可溶性有机氮所占比例不高,经过217 d通气培养,淋洗出的可溶性有机氮平均为N 28.8mg/kg,占淋洗总氮量的19.8%。相关分析表明,淋洗可溶性有机氮量与第l季作物吸氮量相关不显著,但与连续2季作物总吸氮量显著相关。淋洗矿质氮、淋洗总氮与两季作物总吸氮量的相关系数明显高于与第一季作物吸氮量的相关系数;与第一季作物吸氮量达显著相关水平,与连续两季作物吸氮量达极显著相关水平。总体上看,可溶性有机氮和土壤全氮、土壤微生物氮不能作为反映短期可矿化氮的指标;间隙淋洗通气培养淋洗液中淋洗矿质氮、淋洗总氮是评价可矿化氮的较好指标,不仅适宜于第一季作物,而且也适用于对连续两季作物土壤供氮...

石油污染土壤微生物多样性分析及芘降解菌的鉴定

石油污染是目前最严重的环境问题之一，我国有近千万亩的耕地受到程度不同的石油污染。沈抚灌区位于辽宁省沈阳市和抚顺市之间，全长70多千米，是我国最大的石油污染灌区之一，有四五十年的污灌历史，已对当地的生态环境造成了严重的影响。随着人们对污水灌溉危害的认识，从20世纪80年代起，逐步停止了污水灌溉，开始了清水灌溉和改为旱田耕作，但污染问题仍然存在。目前，由于对该地区污染土壤微生物类群、原位降解菌及它们对环境条件变化的响应等信息缺乏了解，限制了对该地区污染土壤的生物修复。 分子生物学研究手段及稳定同位素分析技术，为污染土壤微生物生态学研究提供了全新的研究手段，为突破当前石油污染土壤生物修复研究止步不前的局面指引了方向。本论文采用变性梯度凝胶电泳（Denaturing Gradient Gel Electrophoresis, DGGE）和磷脂脂肪酸分析（Phospholipid Fatty-acid Analysis, PLFA）分析技术，对沈抚灌区水改旱田石油污染土壤的微生物多样性与环境指标的相关规律进行了分析；以PLFA为生物标示物，结合气相色谱-稳定同位素比率质谱（Gas Chromatography Combustion Isotope Ratio Mass Spectrometry, GC-c-IRMS）分析技术，对石油污染土壤和相对清洁土壤中多环芳烃菲和芘的土著降解菌群进行了鉴定；并以不同的吸附性载体为介质，富集、筛选了芘的降解菌。 研究结果表明，石油污染土壤中的微生物群落结构主要与其相对地理位置有关，当污染物的浓度达到一定程度，土壤中的微生物群落结构会发生明显的改变。以13C标记的稳定同位素菲和芘为代谢底物，对污染土壤中菲和芘的土著降解菌群进行了鉴定。 13C-PLFA- GC-c-IRMS分析结果显示，参与菲降解的微生物有G-、G+细菌和放线菌，其中以G-细菌为主；污染土壤和相对清洁土壤两种土壤都未检出有真菌参与；参与芘降解的微生物有放线菌、G-细菌和真菌，其中以G-细菌为主，同时，也检测到有真菌的参与；污染土壤中的降解菌群较清洁土壤丰富。研究还发现，芘在土壤中的降解可能存在不经过菲为中间产物的代谢途径。采用不同的吸附性载体所富集的优势细菌显著不同。从不同的吸附性载体上最终得到8株芘的降解菌，其中鉴定出的三株菌中Sp-A56，Sp-A21为多食鞘氨醇杆菌（Sphingobacterium multivorum）；Sp-B05氨基杆菌属的一个亚种（Aminobacter sp.），未见有关该菌株芘降解能力的报道，可能是一株新的芘降解菌。

千金子和暖地大叶藓的化学成分研究

本论文由三部分共4 章组成。第一部分阐述了大戟科大戟属传统中药千金子（Euphorbia lathyris L.）化学成分、生物学活性以及千金子化学成分的HPLC、UPLC-MS、GC-MS 分析成果。第二部分介绍了民族药材暖地大叶藓（Rhodobryum giganteum (Schwaegr.) Par.）的化学成分研究和结构鉴定。第三部分概述了大戟属 植物中大环二萜酯的研究进展。 第一章包括1－3 节。在第1, 2 节中报道了千金子（Euphorbia lathyris L.）95% 乙醇提取物的化学成分分离鉴定。我们采用正、反相硅胶柱层析、重结晶等各种分离方法，凭借MS、IR、NMR、X-ray 等现代仪器手段,从中共分离鉴定22 个化合物。其中8 个是高活性化合物前体-续随子烷型大环二萜及3 个巨大戟烷型二萜，还有香豆素、生物碱、甾体等类型，其中完成对5 个大环二萜酯构型的确认，对2 个二萜酯构型进行了修正。第3 节中介绍对千金子化学成分的细胞毒性、α-葡萄糖苷酶抑制活性、P-gp 表达抑制活性的模型筛选结果。 第二章包括3 节，第1 节报道不同产地千金子高效液相色谱定量分析结果。第2 节介绍了各大环二萜酯的HPLC-MS/MS 的分析结果，并且对其质谱裂解规律、UPLC-MS 快速鉴定方法做了进一步讨论。第3 节介绍了千金子挥发油成分分析。采用传统水蒸气蒸馏方法提取千金子中的挥发油，并经气相色谱－质谱联用（GC-MS）技术共分离鉴定出 49 个化合物，占挥发油总量的90.48％。 第三章包括1, 2 两节，第1 节报道了暖地大叶藓化学成分。采用正、反相硅胶，凝胶柱层析等各种分离方法和MS、IR、NMR 等解析手段，共分离鉴定10个化合物，其中一个环肽化合物为新化合物。第2 节介绍了暖地大叶藓挥发油成分分析，共分离鉴定出 52 个化合物，占其挥发油总量的85.67％。 第四章概述了大戟科大戟属植物中大环二萜酯的研究进展。 This dissertation consists of three parts. In the first part, it is elaborated that the phytochemical investigation from the traditional Chinese medicine: seeds of Euphorbia lathyris L.. Biological activity and constituents analysis by HPLC、UPLC-MS、GC-MS were reported. In the second part, it is discussed that the chemical constituents were isolated and identificated from minority nationalitical herb－Rhodobryum giganteum (Schwaegr.) Par.. The third part is a review about the progress of studies on macrocyclic diterpenes from Euphorbia. The first part is composed of 1－3 sections. The section 1and 2 is focused on the isolation and identification of chemical constituents from seeds of E. lathyris. 22 compounds were isolated from the seeds of E. lathyris. by isolation methods of column chromatography (silica gel, including reversed phase) and recrystallisation on the basis of spectroscopic methods including IR, MS, NMR and X-ray. In 8 macrocyclic and 3 ingenane diterpenes, the relative configuration of 5 macrocyclic diterpenes were confirmed, in which 2 were amended. In the third section, cell cytotoxic activity, restraining activity of α-Glucosidase and multidrug resistance (MDR) reversing activity about P-gp were tested. 5 potential revsering reagents were found. The second part is composed of 1－3 sections. In first section it is described that the quality of the chemical constituents of E. lathyris from 5 sources , which were analyzed by high-performance liquid chromatography. In addition, the fractionation rules of some macrocyclic diterpenes were discussed and Ultra Performance Liquid Chromatography/ electrospray ionization mass spectrometry (UPLC-MS) was applied for quick determination of compounds in the second section. In the third section, chemical analysis of the essential oil from seeds of E. lathyris by GC-MS were reported. The essential oil from the seeds of E. lathyris L. in Sichuan was extracted by steam distillation and 49 compounds were isolated and identified from the essential oil by gas chromatography-mass spectrometer (GC-MS). These compounds are accounted for 90.46% of the total essential oil. The second part, including section 4 and 5, is about the phytochemical investigation of R. giganteum. In the former section, ten compounds were isolated and identified. Among them, a new peptide was characterized by spectroscopic analysis including IR, MS and NMR. In the other section, 52 compounds were isolated and identified from the essential oil by gas chromatography-mass spectrometer (GC-MS). These compounds are accounted for 85.67% of the total essential oil. The third part is a review about the progress of studies on macrocyclic diterpenes from Euphorbia.

若尔盖高原花湖湖滨湿地甲烷排放研究

若尔盖高原湿地位于青藏高原东北部地区，平均海拔3,400-3,600m，是长江和黄河的自然分水区，区内发育了大面积的草本沼泽以及高寒沼泽化草甸、高寒湖泊。由于它所处的位置海拔高、气候波动较大，并处于我国三大自然区的交错过渡带，因而被认为是我国最为典型的脆弱湿地生态系统之一。由于地处偏远、自然环境条件恶劣等多方面的原因，针对若尔盖湿地的科学研究资料一直以来还非常缺乏。本文对国内外近年来在湿地生态系统甲烷排放过程、研究方法，以及关于湿地生态系统甲烷排放的影响因素进行了综述，并采用静态箱－气相色谱法，从湿地环境格局、湿地甲烷排放等方面，对若尔盖高原典型高寒湖泊湖滨不同类型湿地甲烷排放特征进行了研究，并进一步探讨了影响若尔盖高原高寒湖泊湖滨带甲烷排放的因素。得到如下结果：1．若尔盖高原花湖湖滨湿地在植物生长季（6 至8 月），甲烷排放平均速率为0.315 mg·m-2·h-1；不同月份间甲烷排放速率存在差异，分别为：-0.054、0.471、0.493 mg·m-2·h-1。不同类型湿地甲烷排放速率亦表现出差异，两栖蓼（Polygonum amphibium）湿地、滩涂和藏嵩草（Kobresia tibetica）草甸甲烷排放速率分别为：0.464、0.477、0.005mg·m-2·h-1。2．若尔盖高原花湖湖滨湿地甲烷排放速率与土壤10cm 温度显著相关。土壤温度是影响若尔盖高原花湖湖滨不同类型湿地甲烷排放的重要因素之一。随着土壤温度的升高，土壤微生物活性增强，使土壤中的氧消耗加快，氧化还原电位下降，有利于产甲烷菌的生长，从而增加土壤的甲烷产生量。3．地表水位与若尔盖高原花湖湖滨湿地甲烷排放速率相关性不显著。地表水覆盖，使得湿地土壤缺氧状况得到加强，增强了土壤中产甲烷菌的活性，促进甲烷形成，再通过植物、气泡或扩散的形式释放出土壤。但水层的加深，也使土壤中已产生的甲烷在通过气泡或扩散形式穿越水层时，被氧化的量增加，从而减少了甲烷向大气中的排放。4．植被高度以及植被地上生物量与若尔盖高原花湖湖滨带甲烷排放速率的相关性不显著。植物主要通过凋落物以及根系分泌物的输入为产甲烷菌提供基质，并作为土壤与大气之间的甲烷气体交换的传输途径；与其他环境因素共同影响湿地生态系统甲烷排放。The Zoige wetland on the eastern fringe of Qinghai-Tibetan Plateau, with averagealtitude between 3,400 and 3,600m, is the watershed of Yangtze River and YellowRiver. There are large area of peatland, subalpine meadow and lakes in this region.Due to its high elevation, transitional topology and high fluctuation of climate, theZoige wetlands represent one of the most fragile wetland ecosystems in China. And asa result of remote location and harsh environment conditions, the researches on theZoige wetland are relatively rare, especially the researches on the methane emissionfrom littoral zone of alpine lakes. Variations of methane emission rates as measuredby the method of static chamber – gas chromatography (GC) were detected fromlittoral zone of alpine lake on the Zoige Plateau. Relationships between methaneemission rates and environmental factors were analyzed. It is concluded that:1．The average methane emission rate in the littoral zone of Huahu Lake, ZoigePlateau is 0.315 mg·m-2·h-1, with evident spatial and temporal variations. The littoralzone has different methane effluxes with -0.054, 0.471, and 0.493 mg·CH4·m-2·h-1in June, July and August respectively. Different types of wetland have differentmethane emission rates, with value of 0.464, 0.477, and 0.005 mg·CH4·m-2·h-1 forPolygonum amphibium wetland ( PA ), Shoal ( S ) and Kobresi tibetica meadow ( KT ), respectively.2． The soil temperature at 10cm is significantly correlated with the methane effluxesin littoral zone of Huahu Lake, Zoige Plateau, and which is one of the most important factors influencing the methane emission from this region. The activities of soilmicroorganisms rise under higher soil temperature and increases oxygen consumptionand decreases Eh, which is in favor of the methanogensis, and enhances theproduction of methane in soil.3． The correlation between the standing water and methane effluxes from littoralzone of Huahu Lake is not significant. Because of the standing water, the anaerobicconditions of wetland soil have been enhanced, and are favor to the decomposition oforganic matter. And the anaerobic conditions strengthen the methanogensis’ activities,thus the methane production, which release to the atmosphere by diffusion, ebullitionand aerenchymal plants. With the water level’s increase, more methane produced insoil which is transferred by ebullitions or diffusion are oxidated, thus reduce themethane release to the atmosphere.4． The height and aboveground biomass of vegetation are not significant related tothe methane effluxes from littoral zone of Huahu Lake, Zoige Plateau. The vegetationprovides substrates for methanogensis by litter and root exudates; act as thetransportation way of methane between soil and atmosphere; influence the methaneemission of wetland ecosystems with other environment factors.