镜质体反射率热演化规律研究

镜质体反射率的演化并不是人们传统意义上认为的随着温度（深度）的增加成指数增加,而是分阶段演化的。通过对有机质热模拟实验数据和自然演化数据进行分析后发现镜质体反射率的演化可以分为明显的3段：1）缓慢变化阶段,随着温度的增加镜质体反射率缓慢地变化,2）中等快速阶段,随着温度的增加镜质体反射率相比较前一阶段增加速率有明显的加大,3）快速增加阶段,随着温度的增加镜质体反射率呈指数快速增加。这种分阶段的演化是由镜质体本身的化学组成和化学结构所决定的。镜质体反射率演化阶段的划分对于热历史的恢复以及认识镜质体的热演化机制和规律具有重要的意义。     

Physical and chemical environments of abnormal vitrinite reflectance evolution in the sedimentary basins

Based on the tested data of pressure and vitrinite reflectance of some wells in sedimentary basins, abnormal high pressure is regarded as not the only factor to retard the increase of vitrinite reflectance (R _o). Apart from the types of the organic matter, the physical environment (temperature and pressure) and chemical environment (fluid composition and inorganic elements) will result in the abnormal vitrinite reflectance values in the sedimentary basins. This paper tested trace elements and vitrinite reflectance data from the the abnormal high pressure and normal pressure strata profiles, respectively, and found that the acidic and lower salinity starta are favorable for the increase of R _o. By discussing the corresponding relationship between the contents of some trace elements in the mudstone and the vitrinite reflectance values, the typical trace elements were found to suppress and/or catalyze the vitrinite reflectance of organic matter, while the elements of Ca, Mn, Sr, B, Ba and P may result in the retardation of R _o. However, elements of Fe, Co, Zn, Ni and Rb may catalyze the organic matter maturation. This study is conductive to the organic maturation correction, oil and gas assessment and thermal history reconstruction by the paleothermometry. Translated from Acta Geologica Sinica, 2006, 80(11): 1760–1769 [译自: 地质学报]     

Chemical structural models for coalified wood (vitrinite) in low rank coal

Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state ¹³C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.     

镜质体反射率测定结果的影响因素

简要回顾了镜质体反射率测定的发展过程,概括了镜质体反射率在石油地质中的应用及存在的问题,重点探讨影响镜质体反射率测定的因素。这些因素既有地质的,也有人为的,包括:镜质体本身的局限,烃源岩有机质类型、岩性,样品采集与处理过程以及测定环节4个方面。镜质体反射率测定结果正是这些因素相互作用的体现。针对上述影响因素,提出几点建议,供有关研究人员参考。     

煤镜质体反射率测定条件与测定值分析

针对部分应用单位在煤镜质体反射率测定中存在的对测定条件把握不准、对影响测定值准确性的因素理解不深等问题,提出了煤镜质体反射率测定必须遵守的仪器状态一致性与组分定位一致性原则,据此确立了仪器校正、样品测定和结果检验的方法与要求;分析了仪器线性度、稳定性、工作曲线、单色光、温度校正、视频窗口、油浸物镜与浸油、准焦程度和测定样品磨抛质量等对测定值准确性的影响与测定误差控制措施。在此基础上,提出了测定值精密度分级的改进建议,以及用煤镜质体反射率测定结果指导企业生产可简化的仪器条件与测定过程,即：使用50倍干物镜;勿需546 nm滤光片;用有固定反射率值的镀膜玻璃替代宝石标准片;建立工作曲线数据库等。     

四川盆地东部构造-热演化:来自镜质体反射率和磷灰石裂变径迹的约束

利用镜质体反射率(Ro)和磷灰石裂变径迹(AFT)数据,对四川盆地东部不同地区的古地温梯度、古热流、剥蚀量进行了研究。AFT模拟结果表明,四川盆地东部在晚白垩世早期(100~80 Ma)开始抬升,抬升剥蚀过程具有一定的阶段性且不同地区存在差异:以约30 Ma为界,重庆北碚地区表现为两期冷却,先期冷却缓慢,后期冷却迅速;川东北持续的冷却过程虽有波动但冷却速率差别较小。依据重建的最高古地温剖面恢复了侏罗系顶部不整合面的剥蚀量,川东北普光地区剥蚀量在2.45~2.85km,鄂西渝东地区齐岳山复背斜北部剥蚀量较大,达3.65km,齐岳山复背斜南部剥蚀量2.67km,川东南地区剥蚀量2.05km。研究区的构造热演化表现为既存在抬升剥蚀又存在盆地冷却效应的双重作用:由三叠纪至今,研究区地温梯度和热流持续降低,地温梯度由30~38℃/km降低至20~23℃/km;热流由70~85mW/m2降低至50~55mW/m2。     

Statistical analysis of vitrinite reflectance data—a new approach

The reflectance of vitrinite (collotelinite) particles is a widely used parameter as a geothermometer for the estimation of the thermal maturity of organic matter enclosed in rocks. However, several problems have occurred during the last decades, which can be traced back to basically three causes: human mistakes, technical problems, and problems associated with the structural and compositional inhomogeneity of organic matter. Whilst in most cases the first two types of uncertainties can be handled by standardization, the third can cause significant problems during interpretation due to its generally inestimable character. The suppression of vitrinite reflectance and statistical problems originated from small sample size, and outliers belong to this latter type.International standards, such as the ASTM and the ISO, define the vitrinite reflectance parameter as a statistical average of measured data, disregarding the fact that the average is an unresisting and unrobust statistical parameter. In other words, the average is very sensitive to outliers and distribution.The aim of this research was to find and test a better, more resistant, and robust statistical parameter used by traditional parametric and nonparametric statistics, which can be applied in practice instead of the average. Three categories of statistical problems were studied on coal and disperse organic matter (DOM) samples: the distribution of measured values, the effect of data number, and the effect of outliers on statistical parameters. The statistical experiments carried out on numerous original and generated sample sets show that the median (med) and the most frequent value (Mn), a special weighted average, are better parameters to estimate the thermal maturity of organic matter especially above 1% reflectance value.     

利用新近系煤的镜质组反射率计算滇西高原的隆升幅度

为了定量地计算滇西高原的隆升幅度,在滇西中甸、保山、景东、景谷四地分别取新近纪煤岩样,在野外实测煤层上覆地层残留厚度和测得样品的镜质组反射率并确定有效作用时间后,根据三者关系曲线图计算出成煤时的最大古地温和最大埋深,进而计算出滇西高原上新世时期自北而南的隆升幅度在1500~1700m之间。该时期隆升表现出总体均匀抬升的特征。     

利用镜质体反射率恢复地层剥蚀厚度的新方法

Dow在1977年提出的利用上下构造层镜质体反射率 (Ro) 差值来估算不整合面地层剥蚀厚度的方法,在国内仍有广泛的应用。但国内有些学者已认识到了该方法的不合理性并提出了一些改进方法,其中最高古地温法因其思想合理而具有代表性。为了能更合理和更简便地利用Ro数据来估算不整合面地层剥蚀厚度,对最高古地温法作了改进,得到了一种利用Ro数据恢复剥蚀厚度的新方法。新方法不仅继承了最高古地温法的合理思想,而且大大简化了具体操作过程。对某一构造层恢复其顶面剥蚀厚度时,在使用Ro数据恢复剥蚀厚度的前提条件得到满足的情况下,直接将该构造层的ln (Ro)－H线性回归关系外推至ln (0.2) 处而得到近似的古地表位置,古地表位置和不整合面位置的差值即为剥蚀厚度。用最高古地温法和新方法对Dow (1977) 的实例数据进行了重新计算,分别得到2 735 m和2 537 m的剥蚀厚度,相近的结果说明了新方法的实际可行性,并且相比之下新方法操作起来更加简便。但与Dow (1977) 得出的500m剥蚀厚度相差甚远。从多个方面讨论了Dow (1977) 结果和原理的不合理性。新方法将广泛应用于多个地质分支学科中。     

利用新近系煤的镜质组反射率计算滇西高原的隆升幅度

为了定量地计算滇西高原的隆升幅度,在滇西中甸、保山、景东、景谷四地分别取新近纪煤岩样,在野外实测煤层上覆地层残留厚度和测得样品的镜质组反射率并确定有效作用时间后,根据三者关系曲线图计算出成煤时的最大古地温和最大埋深,进而计算出滇西高原上新世时期自北而南的隆升幅度在1500~1700m之间。该时期隆升表现出总体均匀抬升的特征。     

利用新近系煤的镜质组反射率计算滇西高原 的隆升幅度

为了定量地计算滇西高原的隆升幅度,在滇西中甸、保山、景东、景谷四地分别取新近纪煤岩样,在野外实测煤层上覆地层残留厚度和测得样品的镜质组反射率并确定有效作用时间后,根据三者关系曲线图计算出成煤时的最大古地温和最大埋深,进而计算出滇西高原上新世时期自北而南的隆升幅度在1500~1700m之间。该时期隆升表现出总体均匀抬升的特征。     

Influence of oxidability of carboniferous coals from the Dobrudja foredeep on vitrinite reflectance

Importance of the study of the influence of coal oxidability on vitrinite reflectance (VR) as a criterion of the quality of coals and indicator of paleogeothermal regime is shown. Overview of relevant concepts demonstrates that this issue remains debatable. Carboniferous coals of the Dobrudja foredeep, which belong to the class of helitolites in terms of their microcomponent composition, were studied. They were subjected to oxidation during storage outdoors. Consequently, the VR value of high volatile bituminous (long-flame and gas ranks, according to the Russian classification) coals decreased, but this parameter remained virtually unaltered for medium volatile bituminous (fat) coals. Bulgarian researchers obtained similar results for Carboniferous coals of the Dobrudja basin represented by helitolites and mixtohumolites. In our opinion, the VR decrease in the course of coal oxidation is caused by decrease in the condensation and density of aromatic structures and increase in the share of nonaromatic carbon atoms.     

湖相烃源岩Ro异常与无机元素相关性初探

对东营凹陷牛38井主力烃源岩段沙河街三段 Ro值与对应的无机元素含量进行了相关性分析,结果表明 ,牛38井沙河街组烃源岩中, K、Na、Zn、Ni、Mg、Li、Ba、Co、Rb等无机元素含量与 Ro值分布总体呈正相关性,其中 K、Na、Rb等强碱金属元素含量与 Ro值正相关性相对较强;Ca、Sr、Mn等金属元素含量与 Ro值总体呈负相关性;Fe、B含量与 Ro值相关性差.     

海相镜质体反射率用作早古生代烃源岩成熟度指标研究

中国早古生代烃源岩由于缺乏镜质组,加之成熟度较高,常现成熟度指标较难应用,长期以来,对这套烃源岩成熟度评价一直存在问题。塔里木盆地是中国最大的以早古生代地层为主的含油气盆地,在寒武系和奥陶系生油岩中发育有海相镜质体。应用有机岩石学方法主要对塔里木盆地四口深井岩芯样品进行了研究,发现海相镜质体反射率与孔深呈正相关,且其相关性优于沥青反射率,人工热模拟实验结果进一步表明,海相镜质体成熟作用轨迹不同于镜质组。在R＜1．5％时,其反射率比镜质组低;在R＞1．5％时,其反射率比镜质组高。结合天然剖面与热模拟系列样品研究成果,发现R与Ro的相关性可划分为三个阶段,可分别近似用三个直线方程表示：根据海相镜质体反射率实测结果,应用这些方程计算出等价Ro,可较客观地评价早古生代烃源岩成熟度。     

Using reflectance crossplots and rotational polarization for determining first-cycle vitrinite for maturation studies

Vitrinite reflectance on dispersed sedimentary organic matter is traditionally determined from histograms of vitrinite and inertinite reflectance measured on either whole rock samples or kerogen concentrates, or from particles usually in whole rock preparations chosen by morphology and relative reflectance to be first-cycle vitrinite. This paper discusses an alternative method: discrimination of first-cycle vitrinite using apparent maximum and minimum reflectance data plotted on reflectance crossplots. The use of crossplots increases the confidence that the macerals identified as first-cycle vitrinite are optically similar. The maximum–minimum data, in this study, were collected on a quantitative reflectance microscope outfitted with rotational polarization, a technique that eliminates the usual difficulty in collecting such data on very small macerals by stage rotation.     

Laboratory organic matter maturation at high pressures: heat-up effect on vitrinite reflectance

A laboratory study was conducted to assess the effect of heat-up to high diagenetic to low metamorphic temperatures on vitrinite reflectance (VR) at high pressures using the same heat-up processes, apparatus and starting material as those employed in prior experimental studies on huminite/vitrinite maturation. ??Heat-up?? is the isobaric increase in temperature of an organic matter maturation experiment from room temperature to the desired run temperature T ^ehu (T ^ehu ?=?temperature at the end of heat-up). The experiments were performed on xylite of swamp cypress and used a heating rate of 50?°C/min. These confined system maturation experiments were carried out at 10?kbar and involved temperatures T ^ehu ranging from 175 to 450?°C. Additional experiments were conducted at pressures of 5, 20 and 25?kbar to evaluate the influence of pressure on the effect of heat-up on VR. At 10?kbar, results of this study show that heat-up does not influence VR for T ^ehu ?< ~270?°C. This absence of maturation is viewed as the result of an activation time delaying vitrinite maturation at these diagenetic to very low metamorphic temperatures. For T ^ehu ?> ~270?°C, heat-up has a significant effect on VR at 10?kbar: VR greatly increases with T ^ehu during the short heat-up event. This effect of heat-up on VR points out the rapid kinetics of the initial VR increase. Increasing pressure reduces VR increase gained during heat-up. Obviously, pressure retards the initial VR increase and thus controls organic matter maturation. In addition to temperature, the formulation of VR evolution rate equation must consider pressure, activation time and VR gained during heat-up.     

豫西煤田构造煤反射率及其与古构造应力场的关系

为研究构造应力对煤反射率的影响,以豫西煤田不同构造区的构造煤和原生结构煤为对象,采用定向标本及反射率测定的方法作对比研究,发现构造煤的反射率比原生结构煤的反射率普遍偏高。根据反射率与构造应力的关系,求得各构造区的古构造应力场,通过与聚煤期后多次构造运动的主应力方向进行对比,可推知:影响嵩箕区二1煤变形和镜煤反射率的主要构造,是在前期断裂基础上喜山早期掀斜运动诱发的重力滑动构造,而影响崤熊区的则为燕山晚期的逆冲推覆作用。     

The use of automated coal petrography in determining maceral group composition and the reflectance of vitrinite

Using photometric and image analysis methods, a reasonable technique and procedure have been developed for the determination of maceral group composition and the reflectance of vitrinite. This procedure is introduced by an optimum method for seeking the interval values of each maceral group, i.e., from the “fingerprint” reflectance histogram, it seeks reasonable interval values and distribution values for vitrinite and other maceral groups. After checking and correction, these values can be put into a program and computerized. This method had advantages such as increased speed of analysis and reproducibility of the results.     

Estimation of relative depth of burial using vitrinite reflectance: Implications for a sedimentary basin formation by basement tilting

The kinetics of coalification are still debatable; the role of time has not been conclusively assigned. If accepting the importance of time, we have not reached consensus in formulation of the kinetics.Here we show that estimation of burial depth is possible under some conditions using vitrinite reflectance neither with computation of a specific kinetic equation of organic metamorphism nor with postulating plausible geothermal gradients of the past. The present technique is based only on empirical linear relations between vitrinite reflectance and burial depth, and is demonstrated to be effective for investigation of syn-depositional tectonics. The authors applied the technique to Miocene coals of the Chichibu Basin, Central Japan, and this study indicates that the sedimentary basin was formed by tilting of the basement rocks.     

Influence of particle and surface quality on the vitrinite reflectance of dispersed organic matter: Comparative exercise using data from the qualifying system for reflectance analysis working group of ICCP

The development of a qualifying system for reflectance analysis has been the scope of a working group within the International Committee for Coal and Organic Petrology (ICCP) since 1999, when J. Koch presented a system to qualify vitrinite particles according to their size, proximity to bright components and homogeneity of the surface. After some years of work aimed at improving the classification system using photomicrographs, it was decided to run a round robin exercise on microscopy samples. The classification system tested consists of three qualifiers ranging from excellent to low quality vitrinites with an additional option for unsuitable vitrinites. This paper reports on the results obtained by 22 analysts who were asked to measure random reflectance readings on vitrinite particles assigning to each reading a qualifier. Four samples containing different organic matter types and a variety of vitrinite occurrences have been analysed. Results indicated that the reflectance of particles classified as excellent, good or poor compared to the total average reflectance did not show trends to be systematically lower or higher for the four samples analysed. The differences in reflectance between the qualifiers for any given sample were lower than the scatter of vitrinite reflectance among participants. Overall, satisfactory results were obtained in determining the reflectance of vitrinite in the four samples analysed. This was so for samples having abundant and easy to identify vitrinites (higher plant-derived organic matter) as well as for samples with scarce and difficult to identify particles (samples with dominant marine-derived organic matter). The highest discrepancies were found for the organic-rich oil shales where the selection of the vitrinite population to measure proved to be particularly difficult. Special instructions should be provided for the analysis of this sort of samples. The certainty of identification of the vitrinite associated with the vitrinite reflectance values reported has been assessed through a reliability index which takes into account the number of readings and the coefficient of variation. The same statistical approach as that followed in the ICCP vitrinite reflectance accreditation program for single seam coals has been used for data evaluation. The results indicated low to medium dispersion for 17 out of 22 participants. This, combined with data from other sets of comparative analyses over a long period, is considered an encouraging result for the establishment of an accreditation program on vitrinite reflectance measurements in dispersed organic matter.