十八烷的裂解动力学研究(I):气态烃组分及其碳同位素演化特征

本文通过对纯烃类化合物——正十八烷的动力学模拟实验,阐述了正十八烷裂解过程中气态烃组分及其同位素的演化特征,获得了产自正十八烷的甲烷生成动力学参数。运用动力学参数将模拟实验结果外推到地质条件下,表明由烷烃裂解形成的甲烷主要生成于150～200℃(Easy%Ro介于1.0%～2.0%)的范围,裂解产生的甲烷、乙烷、丙烷的碳同位素分馏效应与Easy%Ro的关系曲线受升温速率的影响,不能直接应用于地质条件。     

临沧超大型锗矿床锗赋存状态研究

采用重液分离方法研究了临沧超大型锗矿床中锗在矿化褐煤不同煤岩组份中的分配 ,结果表明锗主要富集在腐植体 (尤其是团块腐植体 )中 ( 86 .0 4%～89 1 6 % ) ,其次是轻质组份 ( 3.2 0 %～ 8.33% )和无机矿物 ( 1 .71 %～ 1 0 .2 7% ) .电子探针和质子探针分析表明 ,在矿化褐煤中没有鉴定出独立锗矿物 ,锗十分均匀地分布在整个褐煤中 .锗可能与褐煤有机质的O ,C和H等成键 .     

压力对高硫干酪根轻烃产率的影响

采用金管－高压釜体系对江汉盆地高硫干酪根进行了热解,用氘代正构烷烃作标样,色谱－质谱定量。实验结果表明,压力增加,ｎＣ６和轻烃（ｎＣ６￣ｎＣ１４）的产率明显增加;而对ｎＣ１５和沥青的产率未发现有显著影响。     

次火山热变质煤的物理测试特征

样品采自伊敏褐煤盆地中一个因次火山活动形成的烟煤区,包含了从褐煤到瘦煤的变质系列。红外光谱分析表明,煤的含氧基团在褐煤阶段已开始消失,烷基和芳环同步增加,在R°=1.10%时达最大值。顺磁共振自由基浓度和X-衍射参数La/Lc介于区域变质煤和岩浆接触热变质煤之间,芳核外官能团的热演化超前于芳核骨架及R°的演化。      

An improved method for quantitatively measuring the sequences of total organic carbon and black carbon in marine sediment cores

Understanding global carbon cycle is critical to uncover the mechanisms of global warming and remediate its adverse ef fects on human activities.Organic carbon in marine sediments is an indispensable part of the global carbon reservoir in global carbon cycling.Evaluating such a reservoir calls for quantitative studies of marine carbon burial,which closely depend on quantifying total organic carbon and black carbon in marine sediment cores and subsequently on obtaining their high-resolution temporal sequences.However,the conventional methods for detecting the contents of total organic carbon or black carbon cannot resolve the following specific difficulties,i.e.,(1)a very limited amount of each subsample versus the diverse analytical items,(2) a low and fluctuating recovery rate of total organic carbon or black carbon versus the reproducibility of carbon data,and(3)a large number of subsamples versus the rapid batch measurements.In this work,(i)adopting the customized disposable ceramic crucibles with the microporecontrolled ability,(ii)developing self-made or customized facilities for the procedures of acidification and chemothermal oxidization,and(iii)optimizing procedures and carbon-sulfur analyzer,we have built a novel Wang-Xu-Yuan method(the WXY method)for measuring the contents of total organic carbon or black carbon in marine sediment cores,which includes the procedures of pretreatment,weighing,acidification,chemothermal oxidation and quantification;and can fully meet the requirements of establishing their highresolution temporal sequences,whatever in the recovery,experimental efficiency,accuracy and reliability of the measurements,and homogeneity of samples.In particular,the usage of disposable ceramic crucibles leads to evidently simplify the experimental scenario,which further results in the very high recovery rates for total organic carbon and black carbon.This new technique may provide a significant support for revealing the mechanism of carbon burial and evaluating the capacity of marine carbon accumulation and sequestration.     

煤成甲烷、乙烷碳同位素动力学研究和应用--以鄂尔多斯盆地上古生界煤成气为例

同位素动力学模型的发展和应用使天然气的研究工作进入了一个动态的研究阶段。迄今为止,大多数研究工作集中在甲烷的碳同位素动力学模拟。而少有地球化学家对乙烷及其他重烃气组分的碳同位素组成的动力学模拟加以重视。本文在甲烷碳同位素动力学模型基础上,编制了限定体系下乙烷的同位素动力学模拟软件。并在热解模拟实验的基础上对鄂尔多斯盆地上古生界煤成气甲烷、乙烷的同位素演化进行了模拟,获得长期累积甲烷、乙烷的同位素值分别为δ^1C1=-33．46‰3、δ^13C2=-23．1‰,与上古生界储层中天然气的组分特征（δ^13C1=-32．95％。、δ^13C2=-23．41‰）基本一致,与下古生界天然气的同位素组成存在着明显的差别,说明上古生界煤与上古生界天然气存在着源—气的对应关系;而对下古生界天然气来说,上古生界煤系不是主要的气源岩。     

腐殖酸与铅锌相互作用的实验地球化学

腐殖酸是沉积有机质的成分。实验证明，腐殖酸对铅锌离子具有强烈的富集能力。通过替代反应初步确定了腐殖酸与Ｐｂ，Ｚｎ之间几种结合方式及各种结合方式占数据和比例；证实富非酸和胡敏酸与Ｐｂ＾２＋，Ｚｎ＾２＋之间形成了两大类络合物：一类其稳定常数小于ＥＤＴＡ－Ｐｂ（Ｚｎ）络合物；另一类稳定常数大于ＥＤＴＡ－Ｐｂ（Ｚｎ）络合物。     

次火山热质炮的物理测试特征

样品采自伊敏褐煤盆地中一个因次火山活动形成的烟煤区，包含了从褐煤到瘦煤的变质系列。红外光谱分析表明，煤的含氧基团在褐煤阶段已开始消失，烷基和芳环同步增加，在Ｒ＾Ｏ＝１．１０％时达最大值。顺磁共振自由其浓度和Ｘ－衍射参数Ｌａ／Ｌｃ介于区域变质和岩浆接触热变质煤之间，芳核外官能团的热演化超前于芳核骨架及Ｒ＾ｏ的演化。     

Century-scale high-resolution black carbon records in sediment cores from the South Yellow Sea,China

Black carbon(BC)has received increasing attention in the last 20 years because it is not only an absorbent of toxic pollutants but also a greenhouse substance,preserving fire-history records,and more importantly,acting as an indicator of biogeochemical cycles and global changes.By adopting an improved chemothermal oxidation method(WXY),this study reconstructed the century-scale high-resolution records of BC deposition from two fine-grained sediment cores collected from the Yellow Sea Cold Water Mass in the South Yellow Sea.The BC records were divided into five stages,which exhibited specific sequences with three BC peaks at approximately 1891,1921,and 2007 AD,representing times at which the first heavy storms appeared just after the termination of long-term droughts.The significant correlation between the times of the BC peaks in the cores and heavy storms in the area of the Huanghe(Yellow)River demonstrated that BC peaks could result from markedly strengthened sedimentation due to surface runof f,which augmented the atmospheric deposition.Stable carbon isotope analysis indicated that the evident increase in carbon isotope ratios of BC in Stage 5 might have resulted from the input of weathered rock-derived graphitic carbon cardinally induced by the annual anthropogenic modulation of water-borne sediment in the Huanghe River since 2005 AD.Numerical calculations demonstrated that the input fraction of graphitic carbon was 22.97% for Stage 5,whereas no graphitic carbon entered during Stages 1 and 3.The obtained data provide new and important understanding of the source-sink history of BC in the Yellow Sea.