干旱-半干旱区兰州兴隆山现代森林典型植被和土壤中类脂物分子特征及其意义

利用GC－MS对西北干旱区-半干旱区兰州兴隆山森林区典型植被与现代土壤样品中可抽提的类脂物进行了系统分析,检测出包括正构烷烃和α正构脂肪酮等一系列类脂物分子化石。在未进行族分离的情况下,检出兴隆山现代森林木本植物的正构烷烃以C₂₇或C₂₉为主峰,草本植物则以C₃₁为主峰;  土壤样品中均保留有很强的、几乎均势的C₂₇,C₂₉和C₃₁信号; α正构脂肪酮具有明显的奇碳优势,植物中以C₂₃,C₂₅或C₂₉为主峰,土壤样品以C₂₇或C₂₉为主峰;  其反映的信息是植被与微生物共同作用的结果。本研究为理解现代土壤和古土壤中类脂物所指示的植被信息、进一步探讨类脂物分子在植被(有机质)-微生物-土壤-湖泊沉积体系中存在与相互转换关系这一基础理论问题提供了科学资料。同时,为分子化石分析方法的改进和不同处理过程所得数据之间的对比和科学解释提供资料。     

洛川黄土剖面末次冰期间冰段弱古土壤 (L1 SS1)分子化石及其古植被与古环境*

利用气相色谱-质谱联用仪(GC-MS)对连续取样的洛川黄土剖面弱古土壤层(L₁ SS₁)和相邻黄土层(L₁LL₁,L₁LL₂)的分子化石进行了检测,获得正构烷烃、正烷基-2-酮和酰胺等种类众多、丰度较高的分子化石。W_草/植=nC₃₁/(nC₂₇+nC₂₉+nC₃₁),W_木/植=(nC₂₇+nC₂₉)/(nC₂₇+nC₂₉+nC₃₁)和W_木/草=(nC₂₇+nC₂₉)/nC₃₁记录了草本与植被、木本与植被、木本与草本比例变化规律的古植被信息。检测样品的CPI值为5.60~11.50,地质作用影响较小;通过磁化率、粒度和分子化石指标的相关性分析,认为磁化率、粒度记录了环境变化及主要气候事件(相关系数达-0.81);而分子化石能较好地反映古植被变化。当气候环境由干冷向温湿变化、水热配置条件改善时,植被变化响应较迅速;当环境恶化、转向干冷时,响应较弱或滞后,这种现象可能是由于植被生态系统稳定性造成的结果。整个研究剖面段样品以nC₃₁为主峰的高碳数优势,分子化石表明末次冰期间冰段洛川地区(黄土高原)发育草本植被而没有出现以森林为主的植被。     

异构比φiC4 /φnC4 和φiC5 /φnC5 的石油地质意义

同分子量的正构烷烃和异构烷烃存在着物理化学性质差异,在运移过程中受围岩的物理化学性质及其它外部因素的影响必然产生分异效应,从而使二者在空间分布上具有一定的特征和规律,异构比指标可以在一定程度上反映出这种特征和规律性。用异构比φ_iC4 /φ_nC4 和φ_iC5 /φ_nC5 指标可以判断有机质的成熟度,研究轻烃运移的途径、方向、生成环境及轻烃的生物降解。     

湖泊沉积物C4植物含量重建方法的讨论——以新生代柴达木盆地大红沟剖面为例

当前气候变暖是一个全球面临的重大问题,它对人类赖以生存的植被生态系统造成的影响已经在全球各地逐步显现出来。为了深入了解植物生态系统对环境和气候变化的响应机制,我们需要更好地借鉴地质历史时期气候环境和植物协同演化的重要事件。C₄植物作为陆地生产力较强的植物,在植物生态演化中占举足轻重的地位。目前研究表明C₄植物可能最晚起源于始新世-渐新世之交,但从它早期起源到随后在生态系统中的大规模扩张时间间隔长达20多个百万年。是什么因素导致了C₄植物的起源和扩张是一个悬而未决的重要问题,需要开展大量的调查研究来评估和重建C₄植物在过去生态系统中的相对生物量变化。重建C₄植物的含量目前主要的方法是建立在C₃/C₄植物碳同位素和植物内部结构形态差异基础之上。最常运用的研究材料包括(古)土壤有机质、成壤碳酸盐、陆地食草动物体组织、沉积物生物标志物、孢粉、植硅体等。这些方法在重建现代以及地质历史时期C₄植物相对生物量变化的研究中发挥了重要作用,但同时也存在很多无法避免的问题。本文介绍了C₄植物起源和扩张机制的主流观点以及不同研究材料的碳同位素所推算C₄植物生物量的基本原理,并以柴达木盆地大红沟剖面为例,针对新生代湖泊沉积物中陆生高等植物的长链正构烷烃特征和单体烃碳同位素的研究结果,详细讨论C₄植物含量重建的方法与缺点,为探讨C₄植物起源、演化及控制因素提供参考。我们通过分析前人研究的大红沟剖面长链正构烷烃及单体烃 δ¹³C_alk 值特征,推测在30~24 Ma、20~17 Ma和13~7 Ma期间δ¹³C_alk值显示相对正偏的原因,可能是干旱和C₄植物在当地生态系统中出现的双重因素叠加造成的。但这一推断还需要借助于新的研究方法,即单颗粒孢粉碳同位素的方法来提供C₄植物的确凿证据。     

东海泥质区单体正构烷烃的碳同位素组成及物源分析 *

利用气相色谱(GC)和气相色谱/同位素比值质谱(GC/IRMS)对东海近岸泥质区、济州岛西南泥质区和冲绳海槽北部表层沉积物中正构烷烃的单体碳同位素组成及分布进行了分析。结果显示东海不同泥质区典型海洋藻类源正构烷烃C₁₉同位素组成基本相似,在-27.4 ‰ ~-28.0 ‰ 之间,平均为-27.7 ‰ 。典型海洋水生植物源C₂₃同位素组成在-28.5 ‰ ~-31.6 ‰ 之间,平均为-30.5 ‰ ,碳同位素组成从近岸泥质区到冲绳海槽北部逐渐变重,表明海槽区与陆架区海洋水生植物种类有所不同。陆架区长链正构烷烃(C₂₅~C₃₁)部分随着碳数的增加,其同位素组成逐渐变轻,但海槽区这一变化不大,显示陆架区的陆源高等植物蜡具有相似的物源,而冲绳海槽北部由于黑潮主干区和黑潮分支(对马暖流)对陆架沉积物进入深海的控制性阻隔作用,其物源与陆架区区别较大。现代输入东海的陆源植物以C₃植物为显著优势,C₃植物对近岸泥质区北部、近岸泥质区南部、远端济州岛西南泥质区和冲绳海槽北部陆源植物的贡献分别为83 % ,95 ％,75 % 和70 % 。     

生物标志化合物与相关的全球变化

在各种地质体中广泛分布的生物标志化合物在全球变化研究中有着广泛应用,特别是在海洋和湖泊沉积物中,研究工作已涉及到古植被、古温度、古降水量、古大气CO₂浓度和古季风等的恢复.文章介绍利用气相色谱仪、气相色谱-质谱联用仪、气相色谱-热转换-同位素比质谱仪分析了一个长40cm泥炭岩芯(约222年)的生物标志化合物的分布及其单体氢同位素.结果显示,不管是生物标志化合物的分布,还是其单体稳定同位素特征都记载了气候(温度)的变化.正构脂肪酸的碳优势指数(CPI值)、正构烷烃C23/C31比值、正构烷烃C23的δD值与温度有很好的对应关系.     

湘西北地区五峰-龙马溪组页岩物质组成特征与页岩气潜力分析

为了研究湘西北龙山-永顺地区上奥陶统五峰组-下志留统龙马溪组页岩气资源勘探潜力,利用野外典型露头地质剖面资料,通过对典型剖面页岩样品的系统观测、采样、利用有机地球化学和矿物组成特征研究,评价研究区目标地层页岩的成烃成藏物质基础。研究结果表明,研究区五峰-龙马溪组黑色泥页岩普遍具有有机碳含量高、残留可溶有机质氯仿沥青"A"低、生烃潜能S₁+S₂指数略低。分子生物标志化合物分析显示,正构烷烃无明显奇偶优势,受一定程度的微生物降解影响,多表现为双峰型（C₁₈/C₂₅）,∑C₂₁-/∑C₂₂₊值为0.45~1.11,显示轻烃组分缺失,重烃组分占绝对优势;Pr/Ph值范围在0.27~0.44,具有植烷优势,显示原始有机质发育于较强还原沉积环境。烃源岩样品饱和烃组成相对丰度五环三萜烷 > 三环萜烷 > 四环萜烷,三环萜烷中C₂₁、C₂₃、C₂₄呈倒V字形分布,Ts/Tm为0.39~0.66。C₂₇规则甾烷含量略大于C₂₉规则甾烷,显示沉积母质以浮游生物及海洋型自养菌为主,亦含有部分藻类为主的有机质输入。镜质组反射率Ro均在2.57%~3.01%,普遍小于3%,已经达到了过成熟阶段。全岩矿物组成成分分析显示,页岩中脆性矿物为主要组成成分,其次为黏土矿物。综合页岩有机和无机物质组成分析结果,提出研究区湘西北五峰-龙马溪组页岩具备页岩气成烃成藏的物质条件基础,有机质含量高、热演化程度适中、脆性和吸附性较好,为深入开展页岩气勘探目标区优选奠定了工作基础。     

西藏尼玛盆地古近纪湖相油页岩正构烷烃特征及其古环境与古气候意义

尼玛盆地地处青藏高原中部特殊区域,自新生代以来沉积了大套连续的湖相暗色油页岩,其富含生物分子化石,对重建青藏高原古气候和古环境具有重要意义。本文通过对尼玛盆地古近系牛堡组康嘎勒剖面正构烷烃及相关参数分布特征进行研究,结果显示,剖面油页岩正构烷烃分布从底到顶由单峰前峰型向单峰后峰型过渡,具2个旋回周期;碳优势指数相对稳定,但TAR、ACL、P_aq及nC_≤21/nC_≥25变化较大,表明湖泊沉积有机质由内源为主的低等藻类向高等水生植物和外源陆生高等植物转变,且区域气候环境由温凉湿润向炎热干旱逐步演化。综合分析认为,尼玛盆地在始新世的气候变化在很大程度上是受西风环流和季风系统的共同影响。且西风环流和季风的强度变化与全球气候存在一定的关系。即全球变暖时,西风环流势力减弱,西风环流和残余洋水汽为高原中部提供的有效降水减少,气候相对干旱;而在全球降温时,西风环流和印度季风增强,残余洋水汽的叠加又为高原中部提供了充足的有效降水,气候湿润。     

产铀矿石硅酸盐全分析中铁对五氧化二磷的干扰校正方法

应用碱熔-磷钒钼黄光度法以检测波长420nm分析产铀矿石硅酸盐中P₂O₅时,样品中共存元素铁与钒钼酸铵显色剂发生络合反应,显现与磷钒钼黄相同的黄色而同时被检测,产生正干扰使P₂O₅测定结果偏高。本文对碱熔-磷钒钼黄光度法测定产铀矿石硅酸盐P₂O₅的检测波长进行波长校正消除铁干扰。以Fe₂O₃作为硅酸盐全分析中铁的考核量,变换检测波长从400nm到480nm,考察Fe₂O₃不同添加量（0.00~0.70mg/mL）分别对0.20μg/mL、2.00μg/mL和8.00μg/mL P₂O₅吸光值的影响。实验表明：①当P₂O₅检测波长从国家标准方法420nm变换到450nm,校正了产铀矿石中铁对P₂O₅分析结果产生的正干扰。以产铀岩石国家标准物质GBW04117~GBW04122为验证样品,样品中Fe₂O₃和P₂O₅的含量均在校正范围内。②在450nm下对产铀岩石、玄武岩、泥质灰岩国家标准物质P₂O₅进行分析,其结果符合误差要求,方法精密度（RSD）在1.1%~15.7%之间。可以满足硅酸盐样品、产铀矿石等相似基体样品P₂O₅检测要求。③此波长校正方法操作简单易行,为碱熔-磷钒钼黄光度法测定产铀矿石硅酸盐P₂O₅提供了方法补充。     

黄土高原西部地区现代植被及其表土正构烷烃分布模式研究

由于现代木本、草本植物正构烷烃主峰分布的研究结果存在一定的差异,从而导致黄土沉积中利用正构烷烃主峰分布进行古植被恢复时存在较大争议,尤其是松科植物主峰分布的不同。因此,采集黄土高原西部地区常见木本和草本植物及其表土,包括研究区常见松科植物,利用GC分析,开展现代植物及其表土正构烷烃主峰分布的研究。结果发现,黄土高原西部地区常见10种木本植物正构烷烃的主峰分布均以C27或C29为主峰,3种草本植物以C31为主峰,与分子有机地球化学研究结果一致,研究区3种常见松科植物均以C29为主峰,并无C31为主峰的分布; 研究区现代表土正构烷烃的结果显示,表土正构烷烃主峰分布与上覆植被输入量有直接关系,对于不同景观的采样点,由于其木本、草本植物输入量的差异而导致正构烷烃分布存在差异,对于有机质来源较为多元化的地区,分析要十分慎重。同一种植物腐叶与新鲜叶片正构烷烃主峰分布是一致的,说明植物叶片的腐烂过程对其正构烷烃主峰分布没有产生影响。对同一种植物不同地区的对比分析发现,木本植物正构烷烃主峰分布特征受生长环境影响较小,主峰分布不变,但是对于草本植物受生长环境影响较大,主峰分布会产生变化。因此,对于黄土沉积中利用正构烷烃主峰分布特征进行的古植被恢复在开展现代过程研究的基础上是较为可靠准确的。     

Distribution Characteristics of Alkylcyclohexanes in Lower Paleozoic Strata on the Northern Margin of the Tarim Basin,China

Organic matter from the Lower Paleozoic strata on the northern margin of the Tarim Basin of China contains abundant alkylcyclohexanes.The n-alkylcyclohexanes show the even(C16-C20) and odd (C17-C21) carbon number predominance and smooth distribution,and the methyl-n-alkylcycolhexanes the odd carbon number predominance(C17-C21) and smooth distribution,which may be related to their depositional environments and organic precursors.There are some differences in carbon number distribution between the two series of monocyclic alkanes and the n-alkanes marked by smooth distribution.The genetic relationship between the three series of compounds needs to be further studied.     

脂肪酸在古土壤层和黄土层中的分布差异及其环境指示意义

陕西洛川黄土剖面中的黄土层及古土壤层中脂肪酸存在显著差异：黄土层中的正构脂肪酸以不对称的双峰分布，前峰高于后峰，Ｃ１６：０为主峰；古土壤层中，脂肪酸以三组峰分布，Ｃ９，Ｃ１６，Ｃ２８近乎相等；古土壤层中的异构脂肪酸有ｉＣ１７，ｉＣ１９，反异构脂肪酸有ａｉＣ１４，ａｉＣ１５，ａＩＣ１７，ａｉＣ２０等，黄土层中几乎不见它们的，均含有Ｃ１６；１，Ｃ１８：１不饱和脂肪酸，其中Ｃ１８；１含量高。Ｌ２，Ｓ２的     

江苏金湖凹陷古近系奇碳优势和偶碳优势共存的正构烷烃

苏北盆地金湖凹陷古近纪阜宁组二段暗色泥岩及其生成的原油中,正构烷烃系列存在着偶碳优势、奇碳优势以及二者共存的3种分布型式。本文重点探讨正构烷烃奇碳优势和偶碳优势共存的形成原因。在这类暗色泥岩与原油中,正构烷烃通常低碳数部分呈nC15、nC17优势,中碳数具有nC20、nC22优势,高碳数为nC25、nC27、nC29、nC31优势;并且具有强烈的植烷优势、较高的伽玛蜡烷指数、含有一定量β胡萝卜烷和C24四环萜烷。分析认为沉积水体环境和有机质来源的变化决定了正构烷烃的分布形式,该类正构烷烃形成于湖盆水体盐度分层的沉积环境,主要来源于湖盆内藻类和湖盆外高等植物蜡。      

南黄海柱状沉积物中烃类化合物的地球化学特征及其对沉积环境的指示

重点探讨了南黄海柱状沉积物中烃类化合物的分子组成特征及其对沉积环境的指示意义,结果显示,沉积柱中总有机碳（TOC）和总氮（TN）具有较好的正相关性,无机氮的影响较弱,这可能跟本区受径流输入的陆源物质的影响较弱有关。上层样品（0～10 cm）中长链正构烷烃占优势,奇偶优势显著,反映了陆源高等植物贡献;藿烷、甾烷的组成则显示该段样品中有机质具有较高的热成熟度;且姥鲛烷（Pr）/植烷（Ph）比值大于1.0,指示沉积环境以氧化为主,这相对不利于海洋源有机质的保存,从而凸显了陆源有机质的贡献。在10～20 cm之间,沉积环境由相对偏氧化向偏还原过渡;20 cm以下表现为强还原性的沉积环境,有机质成熟度较低。中、下层样品中正构烷烃多呈现双峰分布,短链烷烃具有一定的偶奇优势,这可能主要跟海洋浮游生物、藻类及微生物的贡献有关。与渤海烃类化合物的沉积记录进行对比,发现渤海沉积柱中烃类化合物主要跟历史时期不同来源物质的输入及人类活动的影响有关,而南黄海沉积柱中烃类化合物的特征则主要反映了沉积环境和微生物作用对有机质的埋藏保存有重要影响。     

Lipid Distribution in Marine Sediments from the Northern South China Sea and Association with Gas Hydrate

The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18(or C19) and n-C27 –n-C31 as well as at C29(or C31). The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters(n-FAMEs) that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2(400–420 cm depth) and ZS5-2(241–291 cm depth).     

Even-carbon predominance of Monomethyl branched alkanes in Humic coal from Junggar Basin,NW China

A series of Monomethyl branched alkanes compounds were detected between nC₁₄–nC₃₆, in immature and low maturity Jurassic humic coal, Junggar basin. 2-methyl alkanes and 3-methyl alkanes accounted for the vast majority of the compounds. It is worth noting that the 2-methyl alkanes in the humic coal samples show an obvious distribution of even carbon predominances rarely reported in the literature. The results show that with the increase of Pr/Ph (pristane/phytane), the even carbon dominance of 2-methyl alkanes is more obvious, while the odd carbon number distribution of 3-methyl alkanes is weakened. As Pr/Ph increases in the humic coal, the relative content of the hopanes increased, while the relative content of 2-methyl alkanes and 3-methyl alkanes increases first and then decreases.

     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin,NE Tibetan Plateau: Implications for climate change

This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13–4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C₁₆–n-C₂₀ with maximum values at n-C₁₈ and n-C₂₇–n-C₃₁ as well as at n-C₂₉. The first mode shows a strong even C-number predominance (OEP_16–20 0.34–0.66). In contrast, the second mode has a strong odd C-number predominance (OEP_27–31 1.20–2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic–anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.     

The occurrence and geochemistry of Di - and trimethyl - 2- (4,8,12 trimethyltridecyl) chromans and benzohopanes in Fushun cannel coal,Northeast China

The distribution of methyl-2-methyl-2-(4,8,12-trimethyltridecyl)chromans (M - MTTC) is related to sedimentary environments. 5,7,8 - tri-Me-MTTC, 5,8 -di - Me-MTTC and 7,8 - di - Me - MTTC have been found in coal for the first time, implying that M-MTTC is widely spread in sediments.The distribution of M - MTTC. the presence of C₃₂—C₃₅ benzohopanes, high Pr/Ph ratio, obvious even - odd predominance in C₂₄—C₃₄ alkanes and odd-even predominance in normal alkanes provide strong evidence of a near - shore lacustrine environment.     

Docosane in rock extracts: A possible contaminative source

A large predominance of docosane, a wide range of n-alkanes otherwise possessing an odd/even ratio and a complex mixture of branched/cyclic hydrocarbons has been isolated from polythene vial closures. One of two types of polythene feedstock granules of a type used in the manufacture of laboratory plastic ware gave similar results with the exception that the n-alkane homology possessed a slight even/odd predominance; the other type produced a small amount of alkanes in which the normals had a more pronounced even/odd predominance. These findings are noteworthy on two counts. Firstly, docosane has been reported to be a predominant member of the homologous n-alkanes isolated from a series of sediments and indeed its predominance has been suggested as a measure of the maturity of these sediments. Secondly, odd/even alkane homologies are usually regarded, in geochemical analyses, as being biological environmental indicators.