柴达木盆地原油单体正构烷烃碳同位素研究

利用GC—C—MS技术测定柴达木盆地原油单体正构烷烃碳同位素组成，研究它们的碳同位素组成特征和分布型式，以探究原油的戍因。测试结果表明：柴迭木盆地西部原油的单体正构烷烃碳同位素组成较重，分布在-23．7‰、～-28．5‰之间，分子碳同位素分布曲线呈波浪式，反映原油来自超咸水—咸水的盐湖相沉积环境。柴达木盆地北部原油的单体正构烷烃碳同位素组成为-25．3‰、～-33．4‰，分子碳同位素分布曲线呈U型和波浪式两种型式，根据单体正构烷烃的碳同位素组成和分布型式特征，认为柴迭木盆地北部原油属于煤成油和湖相偏腐泥型、混合型母质成因。     

中国几个盆地原油轻烃单体和正构烷烃系列分子碳同位素研究

本文采用最新的GC/C/MS在线碳同位素分析技术,分析研究了鄂尔多斯、四川、塔里木等盆地原油及凝析油轻烃单体和正构烷烃系列分子碳同位素特征及分布模式。探讨了不同结构烃分子及同结构不同碳数烃分子之间碳同位素分配的某些规律。研究了一些典型成因原油轻烃单体和正构烷烃系列分子碳同位素特征及分布模式,为该项新技术在油气研究与勘探中的应用奠定了基础。同时在一些原油的成因上取得了新认识。     

轮南14井原油正构烷烃和类异戊二烯单体碳同位素研究

通过对轮南14井正构烷烃和类异戊二烯烃的单体碳同位素分析,证实该井奥陶系和石炭系油藏具有相同或相似的油源,而三叠系油藏与奥陶系、石炭系油藏具有较大的碳同位素差异,反映其油源不同.在奥陶系、石炭系和三叠系油藏中,均呈现出类异戊二烯烃碳同位素值略重于同碳数正构烷烃的特征,结合前人研究成果,从生物合成途径及分子内碳同位素的分布角度出发得到合理的解释.     

东北地区五大连池湖相沉积物正构烷烃和单体碳同位素特征及其古植被意义

对中国东北地区小兴安岭与松嫩平原过渡带五大连池青石钻孔湖相沉积物进行了有机地球化学分析,检测出丰富的正构烷烃生物标志化合物.本文主要讨论了正构烷烃的分布及其单体碳同位素组成特征.正构烷烃具有前峰型和双峰型两种分布特征,表明其有机质为混合来源,包括低等菌藻类生物和陆生高等植物输入.正构烷烃的分布特征表明,自35.2ka B.P.以来,nC27/nC31和ACL指标共同记录了东北地区小兴安岭与松嫩平原过渡带的植被以草本为主.对C27、C29和C31长链正构烷烃进行了单体碳同位素测定,并利用二元模式估算了C3和C4植物相对生物量,结果表明,自35.2ka B.P.以来,研究区的植被以C3植物为主.期间在典型冷暖气候事件中,受温度变化的影响,C3/C4植物的相对生物量有明显的变化,在全新世大暖期(6.0ka B.P.),受温度升高影响,C3植物的生物量显著减少,C4植物的生物量则明显增加;而在两次典型冷气候事件(中全新世降温事件8.2ka B.P.和新仙女木事件12.9ka B.P.)时期,受温度降低影响,C3植物的生物量有增加的趋势,C4植物的生物量则相对呈减少的趋势;在末次冰盛期21.0ka B.P.时,受明显低温特征的影响,C3植物生物量高达80.0％,这可能是当时低温的气候特征抑制了C4植物的生长.研究结果对探索我国东北地区C3/C4植物分布格局,并为评估未来气候演化对该地区植被格局和农业生产的影响提供科学依据.     

察尔汗盐湖正构烷烃和单体碳同位素分布特征及其古植被意义

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。     

柱色谱分离-分子筛络合洗脱过程中正构烷烃单体碳同位素分馏研究

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（δ13C）的关键。本文以正构烷烃混合溶液为对象,利用柱色谱、5Å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5Å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-5Å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。     

单甲基支链烷烃的单体碳同位素研究

轮南14井三叠系油砂中烷烃类呈双峰型分布,前峰型正构烷烃(nC₁₂～nC₂₂)单体碳同位素较轻(-33.72‰～-32.84‰);后峰型正构烷烃(nC₂₃～nC₃₂)单体碳同位素略重(-32.02‰～-30.90‰),反映两种不同生源的生烃贡献。同时,在后峰型正构烷烃之间检测到了丰富的单甲基支链烷烃系列化合物,该类化合物与后峰型正构烷烃具有相同的单体碳同位素组成(-30.52‰～-31.64‰),指示二者具有共同的母质成因。文献及实测单体碳同位素组成表明单甲基支链烷烃属细菌等微生物来源,因此,对传统的双峰型分布中后峰正构烷烃属高等植物来源的认识提出置疑。     

石油轻烃单体和正构烷烃系列分子碳同位素分析与研究

80年代后期,随着国际上GC/C/MS在线(Online)碳同位素分析技术的建立,稳定同位素地球化学开拓了新的研究领域——液态烃及其他有机化合物单分子碳同位素地球化学,从而使液态烃等的碳同位素研究进入了分子级水平。我们在完成GC—delta S气体同位素质谱仪性能和各种分析条件试验后,率先建立了原油(凝析油)和天然气中轻烃单体、原油和沥青“A”饱和烃中正烷烃系列分子等的GC/C/MS在线碳同位素分析方法。条件方法试验如在线分析与常规双进样质谱分析的对比等,以及平行分析表明,GC/C/MS在线碳同位素分析可获良好的精度和精确度,具良好分离的质谱峰(单个化合物)的平行分析误差一般小于±0.5‰。其最大特点是实现了气相色谱分     

全油正烷烃和类异戊二烯碳中同位素的变化

油样和源岩中沥青的碳同位素分析，主要是根据馏分法或全馏分法（即饱和烃、芳烃和ＮＳＯ化合物）完成的。量到最近，前人对单个碳氢化合物中碳同位素组成的研究受到了下列两个问题的限制：（１）使单个化合物分辨率平衡；（２）为获得完善的分析结果而取得足够的分析原料。前人对单个碳氢化合物中碳同位素组成变化的研究，是利用填充柱气相色谱法收集用于分析的足够量的单个化合物；或者在最近，联合利用填充柱气相色谱仪和质谱仪，     

Carbon isotope composition of long chain leaf wax n-alkanes in lake sediments: A dual indicator of paleoenvironment in the Qinghai-Tibet Plateau

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.     

南亚热带不同菌根类型树种叶凋落物化学性质

文章以南亚热带24种木本植物（丛枝菌根、外生菌根和固氮树种各8种）叶凋落物为研究对象,探讨不同菌根类型树种叶凋落物化学性质的差异性。结果表明：叶凋落物在碳相关化学性质、养分含量以及化学计量比特征方面均表现出较大程度变异。不同菌根类型树种碳相关化学性质没有显著差异（P > 0.05）,而养分含量（N、P、Mg）和化学计量特征（C/P、N/P）差异显著（P < 0.01）。固氮树种叶凋落物N含量（16.1 g · kg⁻¹）显著高于丛枝菌根树种（10.1 g · kg⁻¹）和外生菌根树种（10.7 g · kg⁻¹）,但丛枝菌根树种叶凋落物P含量（0.4 g · kg⁻¹）要显著高于固氮树种（0.1 g · kg⁻¹）和外生菌根树种（0.08 g · kg⁻¹）,而外生菌根树种Mg含量（0.51 g · kg⁻¹）则显著高于丛枝菌根树种（0.19 g · kg⁻¹）和固氮树种（0.03 g · kg⁻¹）;此外,固氮树种C/P和N/P均显著高于丛枝菌根树种。在南亚热带退化生态系统恢复过程中,应考虑不同菌根类型树种叶凋落物化学性质的差异,依据不同菌根类型树种养分利用策略的差异性选择适宜的恢复树种。     

微生物磷脂脂肪酸单体碳同位素示踪碳循环过程

碳循环对于维持地球生命和调控气候变化具有重要意义。微生物是碳循环的关键驱动者之一,微生物群落结构和碳代谢活动的变化,能够影响温室气体的释放和碳储量,并进一步对气候变化产生反馈作用。在当前全球变化和人类活动加剧的背景下,需要进一步了解不同环境中的微生物群落组成和碳代谢活动的特征和响应。磷脂脂肪酸（PLFA）因其快速的周转速率和多样的分子结构,已经被广泛用于原位识别不同环境中活体微生物的生物量和群落结构。在此基础上,PLFA的单体碳同位素组成进一步指示了微生物利用哪些碳源,以及通过何种方式同化这些碳源,从而揭示微生物介导的碳流通和碳循环过程。本文综述了PLFA单体稳定碳同位素组成（δ¹³C）和放射性碳同位素组成（Δ¹⁴C）在示踪微生物碳循环过程中的应用。对比了农田、草地、森林、湿地以及海洋沉积物中活体微生物的碳源利用和碳同化途径的差异,这些差异可能与不同微生物对碳源的偏好以及不同环境中底物碳的可用性有关。对比了岩石、地下水、表层和深层土壤环境中微生物对化石碳源和年轻碳源的差异利用,化石碳是岩石和地下水环境中活体微生物碳源的重要组成部分,表明现代活体微生物可以直接利用部分老碳;相反,表层和深层土壤微生物倾向于利用现代碳源,这些碳源可能来自根系分泌物和从表面垂直输送的溶解有机碳。随着加速器质谱和单个化合物制备技术的进一步发展,预计PLFA单体放射性碳同位素将在微生物碳循环过程中发挥更重要的作用,值得在不同环境中进一步探索。

     

Hydrogen isotope ratios of leaf wax n-alkanes in grasses are insensitive to transpiration

We analyzed hydrogen isotope ratios of high-molecular weight n-alkanes (δD_l) and oxygen isotope ratios of α-cellulose (δ¹⁸O_C) for C₃ and C₄ grasses grown in the field and in controlled-environment growth chambers. The relatively firm understanding of ¹⁸O-enrichment in leaf water and α-cellulose was used to elucidate fractionation patterns of δD_l signatures. In the different relative humidity environments of the growth chambers, we observed clear and predictable effects of leaf-water enrichment on δ¹⁸O_C values. Using a Craig-Gordon model, we demonstrate that leaf water in the growth chamber grasses should have experienced significant D-enriched due to transpiration. Nonetheless, we found no effect of transpirational D-enrichment on the δD_l values. In field samples, we saw clear evidence of enrichment (correlating with relative humidity of the field sites) in both δ¹⁸O_C and δD_l. These seemingly contrasting results could be explained if leaf waxes are synthesized in an environment that is isotopically similar to water entering plant roots due to either temporal or spatial isolation from evaporatively enriched leaf waters. For grasses in the controlled environment, there was no enrichment of source water, whereas enrichment of grass source water via evaporation from soils and/or stems was likely for grass samples grown in the field.Based on these results, evaporation from soils and/or stems appears to affect δD_l, but transpiration from leaves does not. Further evidence for this conclusion is found in modeling expected net evapotranspirational enrichment. A Craig-Gordon model applied to each of the field sites yields leaf water oxygen isotope ratios that can be used to accurately predict the observed δ¹⁸O_C values. In contrast, the calculated leaf water hydrogen isotope ratios are more enriched than what is required to predict observed δD_l values. These calculations lend support to the conclusion that while δ¹⁸O_C reflects both soil evaporation and transpiration, δD_l appears to only record evaporation from soils and/or stems. Therefore, the δD of n-alkanes can likely be used to reconstruct the δD of water entering a leaf, supporting the soil-enrichment model of Smith and Freeman (2006). In both the field and controlled studies, we found significant photosynthetic pathway effects on n-alkane δD suggesting that biochemical pathways or plant phylogeny have a greater effect on leaf wax δD than leaf-water enrichment in grasses.     

Seasonal variations of phosphorus species in sediment from the middle Adriatic Sea

Phosphorus (P) species concentrations in 0–2 cm surface sediment layer were investigated monthly from November 2001 to December 2002 at the bay, channel and open sea stations in the middle Adriatic. Modified SEDEX method was used for inorganic phosphorus species determination [P in biogenic (P-FD), authigenic (P-AUT), detrital apatite (P-DET) and P adsorbed on to iron oxides and hydroxides (P–Fe)], and organic phosphorus (P-ORG). P-FD, P-AUT and P-DET concentration ranges (1.5–5.4, 0–2.7 and 0.4–3.4 μmol g⁻¹, respectively) were similar at all stations, and showed no obvious common trend of seasonal changes. P–Fe ranged from 1.9 to 11.9 μmol g⁻¹ with the highest values at bay station and higher seasonal oscillations than other inorganic P forms. P-ORG ranged from 0.3 to 18.7 μmol g⁻¹ with higher concentrations at stations of fine-sized sediments and showed increased concentrations in warm part of the year at all stations. Correlation between concentrations of P–Fe in the surface sediment layer and orthophosphate sediment-water interface concentration gradients at bay and channel stations indicated to P–Fe importance in the orthophosphate benthic flux. For the bay station, linkage between sediment P-ORG and chlorophyll a concentrations, primary production and microzooplankton abundance was established, indicating a 1 month delay of sediment response to production fluctuations in the water column.     

Using stable isotope analyses to assess carbon dynamics in a shallow subtropical estuary

The sources of carbon, which fuel water column respiration, remain unresolved for most estuaries; our objective was to examine carbon dynamics in a shallow subtropical estuary. We sampled the Sabine-Neches estuary, Texas, during low (November 1999) and high (May 2000) freshwater inflow and measured stable carbon isotope ratios of the dissolved inorganic and orgnaic carbon (δ¹³C-DIC, δ¹³C-DOC), as well as quantifying accessory parameters (salinity, nutrients, total suspended solids, and photosynthetic pigments). Pigment analysis indicated that diatoms were the predominant phytoplankton. Data from the May 2000 sampling event exhibited conservative mixing, indicating that the system was acting as a conduit between the watershed and the Gulf of Mexico. During November, mixing was generally nonconservative indicating extensive recycling of allochthonous and autochthonous carbon sources. Our data imply that both carbon sources had similar isotope, ratios that made it impossible to unambiguously determine the dominant source supporting respiration. The nonconservative DIC concentration data indicating an autotrophic sink as well as the strong relationship between δ¹³C-DOC and chlorophylla, suggest that in situ production was an important component of the DOC pool. We hypothesize that uncharacteristically calm wind conditions during sampling may have promoted phytoplankton settling, removing autotrophs, from the water column, but leaving behind a dissolved biogeochemical signature. Interpretation of carbon dynamics may be confounded by spatial and temporal decoupling of producers and consumers from biogeochemical indicators.     

Abundance and distribution of leaf wax n-alkanes in leaves of Acacia and Eucalyptus trees along a strong humidity gradient in northern Australia

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.     

Global significance of oxygen and carbon isotope compositions of pedogenic carbonates since the Cretaceous

Few global syntheses of oxygen and carbon isotope composition of pedogenic carbonates have been attempted,unlike marine carbonates.Pedogenic carbonates represent in-situ indicators of the climate conditions prevailing on land.The δ~(18)O and δ~(13)C values of pedogenic carbonates are controlled by local and global factors,many of them not affecting the marine carbonates largely used to probe global climate changes.We compile pedogenic oxygen and carbon isotopic data(N= 12,167) from Cretaceous to Quaternary-aged paleosols to identify potential trends through time and tie them to possible controlling factors.While discrete events such as the PaleoceneEocene Thermal Maximum are clearly evidenced,our analysis reveals an increasing complexity in the distribution of the δ~(18)O vs δ~(13)C values through the Cenozoic.As could be expected,the rise of C_4 plants induces a shift towards higher δ~(13)C values during the Neogene and Quaternary.We also show that the increase in global hypsometry during the Neogene plays a major role in controlling the δ~(18)O and δ~(13)C values of pedogenic carbonates by increasing aridity downwind of orographic barriers.Finally,during the Quaternary,an increase of 3‰ inδ~(18)O values is recorded both by the pedogenic carbonates and the marine foraminifera suggesting that both indicators may be used to track global climate signal.     

Helium and carbon isotope variations in Liaodong Peninsula,NE China

Chemical and C–He isotopic compositions have been measured for N₂-rich hydrothermal gases from the Liaodong (abbreviation of East Liaoning Province) Peninsula from which the oldest crustal rocks in China with ⩾3.8 Ga outcrop. With the exception of one sample containing tritogenic ³He and atmospheric ⁴He in Liaoyang, the observed ³He/⁴He ratios from 0.1 Ra to 0.7 Ra indicate 1–8% helium from mantle, 92–98% from crust and 0.1–0.8% from atmosphere. Despite the lack of Quaternary volcanism, such ³He/⁴He ratios suggest, together with geophysical evidences, the existence of intrusive magmas that contain mantle helium and heat within the Liaodong middle-lower crust. The ³He/⁴He ratios are high along the NE-trending Jinzhou faults and gradually decrease with the increase of distance from the faults. Such a spatial distribution suggests that the mantle helium exsolves from magmatic reservoir in the middle-lower crust, becomes focused into the root zones of Jinzhou faults, and subsequently traverses the crust via permeable fault zones. When transversely migrated by groundwater circulation in near surface, mantle helium with high ³He/⁴He ratio may have been further diluted to the observed values by addition of radiogenic helium produced in the crust. This pattern shows strong evidence that the major faults played an important role on mantle-derived components transport from mantle upwards.