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1.
利用5A分子筛吸附,环己烷-正戊烷混合溶剂洗脱分离富集正构烷烃,用气相色谱法测定正构烷烃含量,气相色谱-气体同位素质谱(GC-C-IRMS)测定土壤样品中正构烷烃单体碳同位素。实验优化了5A分子筛用量和洗脱剂的比例,需要络合的正构烷烃的量与分子筛加入量呈线性关系,络合x mg的正构烷烃,需加入2.75x g分子筛,络合环己烷-正戊烷最佳比例为9∶91。探讨了络合过程中5A分子筛对不同链长正构烷烃的络合规律,短链正构烷烃被5A分子筛优先吸附,长链正构烷烃的络合相对滞后。正构烷烃的络合洗脱回收率为44%~72%,精密度(RSD,n=6)为4%~8%;正构烷烃单体碳同位素分析精度为0.04‰~0.38‰(1σ)。采用5A分子筛净化混合溶剂洗脱方法,分析加油站附近的实际土壤样品,未分峰基本消除,获得良好的净化效果,满足正构烷烃单体碳同位素分析的要求。  相似文献   

2.
通过对自配标准样品(正构烷烃)进行5à分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5à分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。  相似文献   

3.
通过对自配标准样品(正构烷烃)进行5分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。  相似文献   

4.
尿素络合法和5A分子筛法是常用的分离富集环境样品中正构烷烃的方法,但由于复杂的处理流程对于低含量正构烷烃的回收率普遍较低。本文通过优化尿素络合法分离富集正构烷烃的实验条件,建立了尿素络合法分离-气相色谱/同位素质谱分析土壤和植物中低含量正构烷烃单体碳同位素的方法。即采用正己烷-丙酮溶解样品,在4℃冰箱中与2 m L尿素-甲醇饱和溶液反应48 h;用去离子水溶解尿素络合物,加入正己烷后分离出有机相和水相,分别用正己烷、丙酮-正己烷萃取有机相和水相中的正构烷烃。中长链正构烷烃的回收率达79%~104%,高于5A分子筛法和已有尿素络合法的富集效果;单体碳同位素的分析精度为0.09‰~0.63‰(1σ)。利用改进的方法分析实际样品,大幅降低了未分峰和共流出物的干扰,提高了实际样品中ppm级中长链正构烷烃的回收率。  相似文献   

5.
应用气相色谱-气体同位素质谱(GC-C-IRMS)分析正构烷烃单体碳同位素之前,需要对饱和烃样品中正构烷烃和异构烷烃进行预分离、富集,在预分离和富集过程中正构烷烃单体碳同位素是否发生分馏是高精度分析正构烷烃单体碳同位素比值(δ~(13)C)的关键。本文以正构烷烃混合溶液为对象,利用柱色谱、5■分子筛络合、环己烷-正戊烷混合溶剂两次洗脱,GC-C-IRMS分析正构烷烃单体碳同位素,研究前处理过程中正构烷烃单体碳同位素是否发生分馏。结果表明:使用柱色谱分离前后,多数正构烷烃单体碳同位素比值相差-0.2‰~0.2‰;当5■分子筛不完全络合时,未络合的正构烷烃单体碳同位素比值偏重约0.7‰,可能发生了微弱的碳同位素分馏,但并未影响洗脱后的正构烷烃单体碳同位素比值;使用环己烷-正戊烷混合溶剂洗脱前后,碳同位素比值相差-0.2‰~0.5‰,以同样方式洗脱第二次,获得的正构烷烃单体碳同位素比值与模拟样品相差-0.3‰~0.2‰。分析不同回收率(20%)正构烷烃的单体碳同位素比值,处理前后的差值基本在0.3‰以内,可见当正构烷烃回收率低至20%左右时,其单体碳同位素仍未发生明显分馏。柱色谱分离-5■分子筛络合-混合溶剂洗脱方法适用于回收率大于20%的正构烷烃单体碳同位素分析。  相似文献   

6.
曹新星  宋之光  李艳  王丽 《地学前缘》2016,23(3):243-252
基于海洋沉积确定的始新世晚期至渐新世早期(约33.5 Ma)的气候过渡期是新生代全球性气候事件,但长期以来相关的陆相沉积记录研究则比较缺乏。本文对形成于始新世晚期至渐新世早期的茂名油柑窝组油页岩样品进行了有机质丰度、烃类组成、单体烃碳同位素组成等分析,以期研究低纬度陆相沉积有机质对古近纪始新世-渐新世气候过渡期(EOT)的响应。研究结果显示,埋藏较浅的上部层位样品正构烷烃碳同位素组成显著正偏,为-19.1‰~-25.9‰,平均值为-22.2‰;而下部层位样品正构烷烃碳同位素组成在-23.7‰~-30.2‰,平均值为-26.3‰。两个样品正构烷烃碳同位素组成之差在1.5‰~8.1‰,平均值之差为4.6‰。正构烷烃碳同位素组成的显著差异指示了EOT低纬度陆相古气候变化引起的陆相有机质响应,而这种响应与当时大气CO2浓度和海洋温度降低导致的气候和植物群落变化密切相关,即可能存在着C3植物向C4植物的转化、C4植物的迅速增加并最终导致沉积有机质碳同位素组成的变化;也可能是由于大气CO2浓度降低导致的大气CO2碳同位素组成整体正偏的结果。很显然,进一步详细的连续剖面分析将对研究古近纪EOT低纬度陆相古气候变化提供重要科学依据。  相似文献   

7.
张普  刘卫国 《岩矿测试》2010,29(3):201-206
通过对陕西洛南刘湾剖面黄土-古土壤类脂物正构烷烃组分进行超声波和加速溶剂萃取方法比较发现:在增加振荡频率(100 Hz)的条件下,对3个相同质量的同一表土样品分别超声提取1、2、3遍和采用有机溶剂浸泡过夜在较低振荡频率(60 Hz)条件下超声抽提3遍获取的正构烷烃组分分布相同,相对丰度差异较小;刘湾剖面7个古土壤样品超声波溶剂萃取获得的正构烷烃组分相对丰度较低,且随深度增加,呈现逐渐降低的趋势;超声波溶剂萃取的两个样品碳优势指数(CPI)分别为5.4和4.6,碳同位素值分别为-31.80‰和-30.52‰;加速溶剂萃取的相同样品CPI值分别为5.3和4.3,碳同位素值分别为-31.46‰和-30.56‰。两种方法萃取的土壤正构烷烃组分分布相同;但加速溶剂萃取的正构烷烃相对丰度是超声波溶剂萃取的0.9~1.5倍。结果表明超声波溶剂萃取的次数和强度不会对其抽提效率产生明显影响;对于年代较老、有机质含量较低的刘湾剖面古土壤样品,超声波溶剂萃取的效率较低;两种处理方法获得的类脂物正构烷烃组分分布和碳同位素值没有差别,但是超声波溶剂萃取的效率明显低于加速溶剂萃取的效率。因此,对于年代较老、含量较低的地质样品,采用加速溶剂萃取方法更有助于获得充分的样品量并进行可靠的气相色谱-燃烧-同位素比值分析;对于现代样品和含量较高的地质样品,采用设备相对便宜、操作简单、易于实现的超声波溶剂萃取方法即可。  相似文献   

8.
熊永强  耿安松 《地球化学》1998,27(6):532-536
生物降解原同在我国分布广泛并且在重油资源中占有一定的比例。本文通过采用单体化合物碳同位素分析技术对取自辽河油田西部凹陷的重油以及它们沥青质组分的热解产物进行单体碳同位素测定,来研究原油沥青质热解产物中正构烷烃单体碳同位素的组成及其一物降解油的指示意义。研究结果表明,沥青质热解产物中正构烷烃组分的单体碳同位素组成可用于生物降解较严重的重油样品进行油/油相比,并且与原油中的正构烷烃单体碳同位素组成的对  相似文献   

9.
对察尔汗盐湖ISL1A钻孔沉积物样品进行了有机分子地球化学分析, 检测出了丰富的类脂物, 包括正构烷烃、一元正脂肪酸、一元正脂肪醇等, 本文主要讨论正构烷烃类脂物的分布特征。正构烷烃的分布型式表明其来源于低等菌藻类生物和陆生高等植物, 正构烷烃的高碳数部分均有显著的奇偶优势, 高碳数正构烷烃全部以C31 为主峰碳。正构烷烃分布特征表明在110.1~50.1 ka B.P.期间, 察尔汗盐湖地区为草原植被景观。对C27、C29、C31 长链正构烷烃进行了单体碳同位素测定, 利用二元模式估算了C3 和 C4 植物的相对输入贡献, 结果表明, 以C3 植物为主。  相似文献   

10.
辽宁西部白垩系义县组三段沉积于火山活动频繁时期,是富含热河生物化石群的重要层段。本文拟对义县组三段四合屯剖面进行了系统的有机地球化学研究,包括总有机碳(TOC)丰度、饱和烃的组成与分布以及单体烃稳定碳同位素组成等分析。结果显示剖面下部(161.5 cm以下)富含化石层段的TOC含量明显高于上部,表明剖面下部生物的发育与生产力较高。饱和烃的组成分布在剖面上具有明显的阶段性变化特征,剖面底部和上部以高碳数正构烷烃占优势,中部以中等碳数正构烷烃占优势。正构烷烃碳同位素组成在–38.6‰~–26.0‰之间,自下而上逐渐呈正偏的趋势。剖面上正构烷烃主峰碳及碳同位素组成的规律性变化可能与古气候环境变化密切相关。伽马蜡烷的普遍检出以及低的姥植比(Pr/Ph0.8)表明当时沉积环境为强还原且具一定盐度分层的水体,沉积有机质得到较好保存。此外,根据高等植物叶蜡烷烃碳同位素组成重建的古大气CO_2碳同位素组成在–10‰~–3‰之间,自下而上呈逐渐正偏后又回归的特点,反映了频繁的火山喷发活动造成大气CO_2浓度变化及其碳同位素组成的偏移效应。  相似文献   

11.
The carbon isotope composition (δ13C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C3 and C4 photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ13C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C27 and C29) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C29) similar to that of terrestrial C4 plants. Thus, the use of δ13C values of sedimentary C27 and C29 n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C4 plants. For sedimentary C31, however, the contribution from submerged plants was minor, so that the δ13C values for C31 n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ13C values of sedimentary C27 and C29 n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C4 vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ13C values of sedimentary long chain n-alkanes (C27, C29 and C31) may carry different environmental signals. While the δ13C values of C31 were a reliable proxy for C4/C3 terrestrial vegetation composition, the δ13C values of C27 and C29 n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth.  相似文献   

12.
《Applied Geochemistry》2005,20(3):553-568
Seven coal and carbonaceous mudstone samples were collected from outcropping Jurassic coal beds, on the margin of the Dingxi Basin, Northwestern China. The n-alkane distributions in all of the samples are characterised by high concentrations of the C19–C29 homologues, and very much lower amounts outside of this range. C23 or C24 are usually the most abundant n-alkanes. Straight chain n-alkanes from C23 to C29 show moderate odd-to-even C number predominances (CPI range: 1.26–2.70). Long-chain acyclic n-alkan-2-ones, n-alkan-3-ones and n-alkan-4-ones ranging from C15 to C33 with moderate odd-to-even C number predominances, were detected together with one isoprenoid methyl ketone (6,10,14-trimethylpentadecan-2-one) in all of the samples. The C number distributions of the three series of alkanones show a similar distribution to that of the n-alkanes, but the correspondence is not sufficient to substantiate a product–precursor relationship. It can be concluded that the n-alkan-2-ones are a mixture of the products of microbially-mediated β-oxidation of corresponding n-alkanes in the sediments and from the microbial oxidation of higher plant-derived n-alkanes prior to incorporation in the sediments. The n-alkan-3-ones and n-alkan-4-ones were formed from microbially mediated oxidation of the corresponding n-alkanes in the γ and δ positions, respectively. Generation of the ketones from higher plant n-fatty alcohols and n-alkanoic acids could be a possible way to form some of the ketones observed, but it can only play a minor role in the samples analysed.  相似文献   

13.
The stable carbon and hydrogen isotope composition of higher plant-derived long chain n-alkanes (δ13Cn-alkanes and δDn-alkanes) from 45 surface soil samples (within well characterized vegetation zones) from eastern China (18°N–50°N) are reported. The weighted average δDn-alkanes value for n-C27, n-C29 and n-C31 in the samples and the annual average δD of meteoric water recorded at 12 weather stations proximal to the sampling sites show similar spatial variations. The δD of n-alkanes shows a gradual depletion in value with increasing latitude. The results demonstrate that, on a large spatial scale, the δD values of long chain n-alkanes derived from higher plants have the potential to record the δD of meteoric water, although many other factors can also influence the isotope values. There appears to be no apparent relationship between the δD of the n-alkanes extracted from the surface soil and the overlying vegetation type (i.e. forest/grassland or C3/C4 composition). Therefore, palaeoenvironmental studies utilizing δDn-alkanes from higher plant-derived material in geological samples have the potential to provide additional information with regard to the past hydrological cycle.  相似文献   

14.
Alkane hydrocarbon and n-fatty acid distributions have been examined in cores taken over a 550 ft thickness through the lower Jurassic, largely non-marine Evergreen Shale, Surat Basin, Queensland, Australia. No depth trends in compound abundances or carbon preference indices are discernible. There is no evidence for significant generation of n-alkanes from kerogen nor for cracking of long-chain n-alkanes. The present distribution patterns of the biochemicals probably reflect closely the nature of the original organic matter. The general strong dominance of long-chain (C20+) n-alkanes; the lack of evidence for diagenetic change; and the absence of correlation between abundances of n-alkanes and n-fatty acids (among both the longer- and shorter-chain compounds), lead to the conclusion that at least the long-chain n-alkanes were largely deposited as such in the sediment, having originated in land-plant material, remains of which are abundant in the samples. In the upper 170 ft. (possibly marine), n-alkanes with chain lengths below C20 become important, suggesting greater significance of aquatic life as a source of organic matter at the time of deposition, a conclusion which is in general accord with the geological history of the basin, although this history is not well known.  相似文献   

15.
Environmental parameters such as rainfall, temperature and relative humidity can affect the composition of higher plant leaf wax. The abundance and distribution of leaf wax biomarkers, such as long chain n-alkanes, in sedimentary archives have therefore been proposed as proxies reflecting climate change. However, a robust palaeoclimatic interpretation requires a thorough understanding of how environmental changes affect leaf wax n-alkane distributions in living plants. We have analysed the concentration and chain length distribution of leaf wax n-alkanes in Acacia and Eucalyptus species along a 1500 km climatic gradient in northern Australia that ranges from subtropical to arid. We show that aridity affected the concentration and distribution of n-alkanes for plants in both genera. For both Acacia and Eucalyptus n-alkane concentration increased by a factor of ten to the dry centre of Australia, reflecting the purpose of the wax in preventing water loss from the leaf. Furthermore, Acacian-alkanes decreased in average chain length (ACL) towards the arid centre of Australia, whereas Eucalyptus ACL increased under arid conditions. Our observations demonstrate that n-alkane concentration and distribution in leaf wax are sensitive to hydroclimatic conditions. These parameters could therefore potentially be employed in palaeorecords to estimate past environmental change. However, our finding of a distinct response of n-alkane ACL values to hydrological changes in different taxa also implies that the often assumed increase in ACL under drier conditions is not a robust feature for all plant species and genera and as such additional information about the prevalent vegetation are required when ACL values are used as a palaeoclimate proxy.  相似文献   

16.
To reconstruct past shifts in the upper forest line (UFL) in the Northern Ecuadorian Andes we are studying the applicability of plant-specific patterns of lipids preserved in soils as proxies for past vegetation along an altitudinal transect. Longer chain length n-alkanes, (C19–C35) were previously found to occur in plant-specific patterns in the dominant vegetation in the area as well as in preliminary soil samples, and may serve as such a proxy. In the present study, we assessed the preservation of n-alkane patterns with depth in soils from five excavations along an altitudinal transect 3500–3860 m above sea level (m.a.s.l) in the area. We used the carbon preference index (CPI) as well as chain length distributions of n-alkanes and their most likely degradation products, n-methyl (Me) ketones, n-alcohols and n-fatty acids. Clear n-alkane patterns were found in all the soils and at all depths, while a clear relationship with the observed patterns of n-Me ketones identified them as the primary degradation product of the former. Very low average n-Me ketone/n-alkane ratio values were found, ranging from 0.03 to 0.15 at the top of the mineral soil, to 0.05–0.20 at the interface with an underlying palaeosol several thousand years old. The concurrent high CPI values indicate very limited degradation of n-alkanes with depth. Except for C33, the shifts in n-Me ketone/n-alkane values were similar for all chain lengths investigated, signifying an absence of preferential degradation of individual n-alkanes. With one exception, all the soils showed a similar increase in n-Me ketone/n-alkane values with depth, indicating that the degradation rates were not influenced by altitude. This means that, even if the total concentration of n-alkanes decreases over time, the characteristic pattern remains intact, conserving their potential as a biomarker for past vegetation reconstruction in the area, as well as for investigation of degradation processes of soil organic carbon.  相似文献   

17.
Various aquatic plants from Lake Qinghai, the largest inland saline lake in China, and terrestrial plants from the surrounding area were investigated for the distribution of n-alkanes and their δD values. The n-alkanes in the samples range from C15 to C33 with C preference index (CPI) values of 4.0–29.7. The n-C23 or n-C25 alkane is the dominant compound in the aquatic submerged plants. The aquatic emergent and terrestrial plants have an abundance maximum at n-C27, n-C29 or n-C31. The average chain length (ACL) values, ranging from 26.0 to 29.6, are closely related to the plant species. The n-alkanes from the aquatic plants have mean δD values of −169‰ to −121‰ and those from the terrestrial plants values of −173‰ to −109‰. The H isotopic composition (δD) and fractionation differ significantly among the plants studied. Comparison shows that additional evaporative enrichment of the lake water associated with saline lakes and humidity influence the δD values of the n-alkanes in aquatic and terrestrial plants, respectively. The mean δD values of n-alkanes in the plants decrease with increasing ACL value. The n-alkanes from the different types of plants are more depleted in D relative to environmental water and those from aquatic plants (with a mean value of −143‰) have a greater isotopic fractionation than terrestrial plants (mean value −113‰).  相似文献   

18.
Suspended particle samples from the Yellow River estuary were sorted into five grain size fractions to explore the effect of grain size distribution on organic matter content and composition. The n-alkanes and PAHs were determined for each size fraction. PAHs and n-alkanes were more abundant in the finer fractions and the loading decreases steadily with increasing of grain size. However, the total n-alkanes or PAHs normalized to organic C were lower in the smaller size fractions than those in the larger size fractions, suggesting n-alkanes or PAHs may be diluted by the addition of organic matter or gradually decreased by degradation in the smaller size fractions. The particulate n-alkanes in the Yellow River estuary consist of a mixture of compounds from terrigenous and riverine biogenic n-alkanes and more biogenic n-alkanes accumulate in finer particles. Particulate PAHs are related to combustion/pyrolysis processes of coal/wood, and the relative contribution of petrogenic PAHs increase with increasing grain size. The total particulate n-alkane and PAH discharges passing the Lijin Station are about 3.94 t d−1 and 0.52 t d−1, respectively. Fine particles (<32 μm) play a significant role in organic matter transfer.  相似文献   

19.
This study investigates the extent of post-depositional alteration of δD values of n-alkyl lipids, isoprenoids, and kerogen isolated from a continuous 450 m core that covers the transition from thermally immature to early mature sediments in the lacustrine Kissenda Formation, Lower Cretaceous, Gabon Basin. Large variations in δD values (up to 40‰ for nC17 and up to 30‰ for nC29 alkanes as well as up to 10‰ for kerogen) in closely spaced samples are evident throughout the core and remain preserved even at the bottom of the section. δD values of individual n-alkanes show a slight overall D-enrichment with depth, and a general trend of increasing δD values with increasing n-alkane chain length characterizes all samples, particularly in those below 600 m depth. Hydrogen isotopic compositions of kerogen samples overlap with those of n-alkanes throughout the section. δD values of pristane and phytane are more negative than those of nC17 alkane by as much as 120‰ at shallow depths but increase dramatically and approach δD values of nC17 alkane in the samples closest to the oil window. Integration of analytical and computational results indicates that: (1) n-alkanes and isoprenoids have the potential to preserve the original biological signal before the onset of oil generation; (2) isomeric and structural rearrangements taking place at the beginning stages of oil generation do not influence significantly the δD values of n-alkanes and kerogen. However, these processes have a major effect on the isotopic composition of isoprenoids, causing isotopic D-enrichment up to 90‰.  相似文献   

20.
To determine the degree of hydrocarbon contamination and the contribution of local petroleum industries to contaminant loadings in sediments from the Beiluohe River, China, 12 surface sediment samples were collected for geochemical analysis in 2005. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and the profiles of n-alkanes, biomarkers and polycyclic aromatic hydrocarbons (PAHs) in sediments were analyzed by gas chromatography with flame ionization detector and gas chromatography/mass spectroscopy. Concentrations of total hydrocarbons in the sediments varied from 12.1 to 3,761.5 μg g−1 dry wt, indicating that most sediments in Beiluohe River was only slightly to moderately contaminated by hydrocarbons. Concentrations of PAHs for six samples (sum of 16 isomers) varied from 17.7 to 407.7 ng g−1 dry wt and at present low levels of PAHs did not cause adverse biological effects in Beiluohe River sedimentary environment. PAH compositions, n-alkanes and biomarker profiles all suggested that there were different sources of contaminations in studied areas. n-Alkanes reflect two distinct sources: a fossil n-alkane series from crude oil at sites S40, S43, S87 and plantwax n-alkanes at sites S39 and S45. Judged by their PAH ratios, the sediments at site S15 were pyrolytic, sediments at S17 and S43 were petrogenic, and sediments at S39, S40 and S64 had a mixture source of pyrolytic and petrogenic.  相似文献   

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