石油中饱合烃类的喇曼特征

本文试通过一些饱合烃类标样的喇曼分析,总结出石油中饱和烷烃组分的最大喇曼特征是在2700~2970 cm-1区域有一系列强烈的喇曼效应,有三种情况:1)直链烷烃类是以—CH3链基对称喇曼效应(约2872 cm-1)最强;2)带异构骨架链烷烃类是以—CH链基喇曼效应(约2911 cm-1)最强;3)环烷烃类是以—CH2链基对称喇曼效应(约2857 cm-1)最强。另外异构骨架在748 cm-1处有一强的喇曼效应,烷烃环基在804 cm-1处有一个强的喇曼效应。并发现不同的烃或烃混合物,若结构基团相同,喇曼谱图也相同;在混合烃组分(或烃类包裹体)的喇曼谱图中2905~2921 cm-1间喇曼峰应是—CH基团,而不能单作甲烷存在的证据。     

Distribution and Geochemical Implication of Aromatic Hydrocarbons across the Meishan Permian-Triassic Boundary

INTRODUCTIONThe Permian-Triassic ( Tr/P) boundary , datedto be (251 .4±0 .3) Ma ago ,is marked by the mostdrastic mass extinction of organisms in the Phanero-zoic .In order to explore the pattern and the cause ofthe mass extinction,extensive research has been fo-cused on biostratigraphy , isotopic chronostratigra-phy , event stratigraphy , ecostratigraphy and se-quence stratigraphy (Payne et al .,2004 ; Reichowetal .,2002 ; Yin et al .,2001 ;Jin et al .,2000 ;Zhanget al .,1996 ,1995 ;…     

傅立叶变换红外光谱联用技术在化石燃料分析中的应用

对傅立叶变换红外光谱联用技术在化石燃料分析中的应用进行了较全面的总结评述,重点介绍了气相色谱／红外光谱联机、高压液相色谱／红外光谱联机、薄层色谱／红外光谱联机、超临界流体色谱／红外光谱联机、裂解色谱／红外光谱联机、热重分析／红外光谱联机、气相色谱／红外光谱／质谱三机联用技术等在化石燃料的结构组分分析、成因机理研究及其勘探等诸方面的重要应用,尤其是在芳香族化合物和几何异构体的分离鉴定方面发挥出的突出功效。引用文献５９篇。     

现代松粉热模拟产物的碳氢同位素特征及其地质意义

对现代松粉的在热模拟过程中生成的甲烷,乙烷,丙烷及干酪根碳同位素分析表明,低温阶段（２５０℃以下）松粉热模拟生成的甲烷相对较高温阶段生成的甲烷更富集＾１３Ｃ,松粉热模拟残余干酪根松粉原样稍微富集＾１２Ｃ,反映低温阶段的热模拟产物主要来源于相对富集＾１３Ｃ的松粉原生质,高温阶段（３００℃以上）松粉热模拟生成的甲烷,乙烷,丙烷的δ＾１３Ｃ值随温度升高而富集＾１３Ｃ,松粉热模拟残余干酪根的碳同位素组成没     

A Three-year Study of Nonmethane Hydrocarbons in Surface Air over Saxony (Germany)

Measurements of the nonmethane hydrocarbon (NMHC) mixing ratio over a period of 42 months were carried out for the first time in the air of a research station situated in the former East Germany during the SANA project. Apart from four species, all other species analysed showed a statistically significant downward trend at the 95% significance level. The decrease of the hydrocarbon concentrations was superimposed by seasonal variations. A drop of about 40% of the annual mean values from 1993 to 1995 was observed. This development reflects the dramatic changes in traffic, industry, power economy, and agriculture in Saxony after the reunification of Germany. The remove of two-stroke engined cars is reflected in NMHC mixing ratio changes, as is the removal of obsolete chemical plants. Generally it was not possible to relate causes and effects of a single event, but in some cases major changes in concentrations and NMHC ratios occurred coincidentally with the disappearance of a specific emission source.     

Pelagic tar, dissolved/dispersed petroleum hydrocarbons and plastic distribution in the Cretan Sea, Greece

During the first cruise of R/V ‘Philia’ in July 1997 within the framework of the TALOS programme supported by the Greek Ministry of Physical Planning and Public Works, the sampling of floating tar, litter and sea water for dissolved/dispersed petroleum hydrocarbons (DDPH) was carried out in the Cretan Sea. Analysis of these data has allowed a first assessment of the status of floating marine pollution in the region. DDPH measurements showed a mean concentration of 0.145 μg/l of chrysene equivalents (n = 24). Tar and plastics concentrations were in the range of 1–4280 and 0–1160 μg/m², respectively. Mean pelagic tar concentration was 318 μg/m², more than two times higher than what was reported for the area in previous studies. Based on in situ hydrographic observations there is strong evidence that most of the floating tar enters the Cretan Sea through the Ionian Sea.     

Accumulation of petroleum hydrocarbons and heavy metals in clams （Ruditapes philippinarum） in Jiaozhou Bay, China

Accumulation and distributions of aliphatic and polyaromatic hydrocarbons (PAHs) and heavy metals were measured in tissues of the clam Ruditapes philippinarum collected from 5 sites in Jiaozhou Bay, Qingdao, China. The concentrations of total aliphatic hydrocarbon and PAHs ranged from 570 to 2 574 ng/gdw (gram dry weight) and from 276 to 939 ng/gdw, in the most and least polluted sites, respectively. The bio-accumulation of hydrocarbons and PAHs in the clams appeared to be selective. Aliphatic hydrocarbons were predominantly represented by short chain (<nC₂₃) n-alkanes, suggesting that petroleum hydrocarbons were likely the major contamination source. The selective uptake of 3 and 4 ring PAHs, such as naphthalene, fluorene, phenanthrene, fluoranthene and pyrene, by the clams was probably related to the physiological and bio-kinetic processes that were energetically favorable for uptake of compounds with fewer rings. Accumulation of the metals Cd, Cu, Zn, Pb, Cr, Hg, and As in the clam tissues also showed high variability, ranging from 0.043 to 87 μg/gdw. Among the 7 detected metals, Zn, Cd, Cu, and As had a particularly high potential of accumulation in R. philippinarum. In general, a positive correlation was found between the tissue concentrations and sediment concentrations of hydrocarbons and of some metals. Our study suggests that moderate contamination with polyaromatic hydrocarbons, and low to moderate contamination with metals, currently exists for clam R. philippinarum in Jiaozhou Bay, in comparison with other regional studies. A long-term monitoring program is certainly needed for assessment of the potential ecological influence and toxicity of these contaminants of R. philippinarum in Jiaozhou Bay.     

Measurements of stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean: A useful indicator of atmospheric transport process

Stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean between 31°N and 26°S was investigated from February through March 2004. The isotopic composition of ethane ranged from −28 to −18‰ and showed a gradual increase from north to south. Conversely, that of propane was between −31 and −24‰; it showed no systematic latitudinal variation. Investigation of the ethane/propane ratio indicates that ethane and propane that originated from northern mid-latitude countries in the eastern part of Eurasia were both transported into the western North Pacific region. However, the results of the isotopic analyses indicate the contribution of oceanic emission to the atmospheric propane during transport, although that contribution can not be discerned for ethane. A ship based stationary observation conducted in the western equatorial North Pacific showed that the isotopic composition of ethane varied from −25 to −19‰ and showed clear systematic diurnal variation: propane ranged between −32 to −26‰ and no such isotopic diurnal signal was observed. The diurnal variation for ethane is explained by entrainment of free tropospheric air, whereas the variation for propane was influenced by oceanic emissions as well as the entrainment. The contribution of oceanic emissions to the atmospheric propane inventory was considered from our isotopic observation. Isotopic composition of dissolved propane is estimated to be less than −38‰, and the contribution up to 79% was calculated when the isotopic composition of dissolved propane is assumed to be −40‰. Our study demonstrates that isotopic analysis can be more useful than ratio-based analysis to improve our present understanding of transport processes, especially for impact of the oceanic emissions on the atmospheric distribution of low level C₂–C₅ non-methane hydrocarbons such as propane in the remote marine atmosphere.     

气相色谱-质谱法同时测定河流沉积物中多环芳烃和有机氯农药

建立了用加速溶剂萃取,气相色谱-质谱法同时测定河流沉积物中16种多环芳烃和19种有机氯农药的分析方法,优化了萃取溶剂、萃取温度和时间、凝胶渗透色谱收集时间、固相萃取洗脱溶剂和洗脱体积等条件。16种多环芳烃的方法检出限在0.15~0.59 ng/g,加标回收率为82%~102%,相对标准偏差(RSD,n=5)为1.1%~4.5%。19种有机氯农药的方法检出限在0.14~2.23 ng/g,加标回收率为71%~108%,相对标准偏差(RSD,n=5)为1.0%~4.5%。实际样品的测定结果表明,该方法分离效果较好,能够满足沉积物样品中多环芳烃和有机氯农药的分析要求。     

样品前处理过程中多环芳烃的稳定碳同位素分馏

利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。