海泡石中水的红外光谱及其结构稳定性的指示作用

在仔细分析海泡石中水的约外谱图特点的基础上,本文其结构水（ＯＨ）结晶水（ＯＨ２）沸石水（Ｈ２Ｏ）吸收带进行了逐个归属,并对比分析了热液型和沉积型海泡石谱图的差异,通过分析处理海泡石样品红外谱图,发现热处理过程中谱图的变化特征与热相变过程能很好地吻合,论证了海泡石中水的红外光谱具有指示结构稳定性的作用。     

加拿大卡西碧玉宝石学性质与特征研究

对中国碧玉市场上销售的加拿大卡西碧玉样品进行了电子探针成分分析(EPMA).卡西碧玉的矿物成分主要为透闪石.碧玉的常规宝石学性质与特征与GB/T16553-2011国标数据一致.显微硬度测试其维氏硬度在813.6～605.7 N/mm²之间.利用压片法和粉末法分别测试获得了卡西碧玉的红外光谱特征,KBr压片法相比较压片法可以揭示碧玉更多的结构特征.     

干酪根的X射线衍射研究

本文讨论了干酪根X射线衍射（XRD）数据的处理方法,XRD的002峰参数t₀₀₂与化学结构参数芳碳率f_芳的关系及其计算;根据XRD谱图,研究了抚顺、茂名油页岩未成熟干酪根的化学结构。在干酪根的人工热模拟过程中,发现XRD参数t₀₀₂与芳核C轴高度L_c均随干酪根的类型和成熟度不同而变化,据此提出了不同类型干酪根的XRD(f₀₀₂-L_c)演化途经图。该图可以帮助我们判别干酪根的类型与成熟度。     

贫碱结构水类型祖母绿红外光谱特征及其控制因素探究

祖母绿红外吸收主要与其硅氧骨干、通道内结构水、相关碱性金属离子和大分子振动有关。国内外相关研究主要集中在峰位归属及谱峰特征对比方面,认为与分子振动和不同类型结构水相关,对更深层的成矿或化学控制因素的研究还较少。本文选取典型4个矿区样品,针对贫碱结构水(Ⅰ型)特征为主的祖母绿进行了近、中红外光谱测定,在此基础上初步探讨其主要控制因素。结果表明:同为Ⅰ型水主控的不同矿区祖母绿呈现一致特征,若干与结构水、碱性离子及大分子相关吸收具有稳定峰位、近似的相对峰强和峰形的特征。分析发现:祖母绿红外谱带特征直接受控于通道中结构水的占位方向和比例,进一步与祖母绿成矿元素Al~(3+)的类质同象替换相关,主要受(Mg~(2+)+Fe~(2+))离子浓度影响,当其浓度较低时,类质同象替换程度较低,祖母绿结构水占位主要表现为Ⅰ型水特征,其相关元素特征表现为高Si、Al,低Mg、Fe,总体贫碱,对应相应的典型红外特征,指示化学离子浓度与红外谱学特征之间的关系。研究过程表明红外光谱可以辅助对Ⅰ型水祖母绿产地的鉴定和成矿环境的认知。     

藻干酪根X射线衍射特征及其与油气生成的关系

通过对加水热模拟实验中藻干酪根Ｘ射线衍射特征的分析,探讨了其ＸＲＤ谱图的演化特征,结构参数间的关系及其与油气生成的关系。研究结果发现,藻干酪根的ＸＲＤ参数间的均具良好的相关性,与干酪根的Ｈ／Ｃ原子比也都具有较好的相关关系,可作为有效的热演化指标,其中以Ｆａ和Ｄ００２最好。该藻干酪根开始生油时对应的Ｆａ和Ｄ００２分别为０．３５和３．８Ａ,生油高峰时对应的Ｆａ和Ｄ００２分别为０．５０和３．６５Ａ。     

红外光谱在几种相似硫酸盐矿物判别中的应用

为快速、有效区分硫酸盐矿物,选取几类具代表性的硫酸盐类矿物样品,采用红外光谱法的反射法和KBr压片法收集各样品的中红外吸收光谱,并进行对比和分析。结果表明,常规矿物测试应用物理特性很难将各矿物区分,红外吸收光谱可有效区分几类相似硫酸盐矿物。对相同结构类型、分子构型、晶系及对称类型的硫酸盐矿物,[SO4]2-基团与[OH]-基团的红外活性内振动频率具随阳离子半径减小而增大、阳离子质量增大而降低的规律。对反射法和KBr压片法测试结果比对,SO4基团与OH基团内振动特征峰基本一致,偏差约0~10 cm-1,个别约40±cm-1。     

应用显微FT-IR光谱技术“原位”研究沉积岩中生油母质──干酪根

干酪根的研究，对石油地质勘探、油气资源的评价、分子有机地球化学以及油气的生成、运移、聚集等都是息息相关１.２。以往是用复杂的物理化学方法从沉积岩中分离出干酪根，然后进行各项实验研究，称“离位”。应用现代傅里叶变换红外显微光谱技术（简称显微ＦＴ-ＩＲ），可以在沉积岩中“原位”研究干酪根的形态、类型、分子结构特征以及它与周围矿物之间的关系等。这种“原位”法为石油地质的研究工作提供了新型高技术。可以预言，显微ＰＴ-ＩＲ新技术不仅推动干酪根的深入研究，而且在整个石油地质科学中将起作难于估量的作用和广阔的前景。     

煤中干酪根在热演化中结构变化的红外光谱研究

为了研究煤中干酪根的不同抽提方法对热演化过程中结构变化的影响,对新疆塔里木盆地库车坳陷阳霞侏罗纪煤中的可溶有机质采用不同的抽提方法得到部分干酪根,并对其在不同热模拟温度下的结构组成变化特征进行红外光谱测定。结果表明,干酪根的结构主要由三部分组成:脂族结构、芳香结构、含氧官能团。随热演化进行,脂族结构和含氧官能团不断脱落,芳香结构不断发生缩合。通过三个系列的比较发现,不同抽提方法导致了初始状态烃类含量的不同,因而红外光谱参数的变化趋势也有所不同。三个系列随热演化程度的进行,从Ⅲ1型干酪根转变为Ⅲ2型干酪根,生油能力降低,主要为生气型干酪根。     

一种翡翠的仿制品透辉石微晶玻璃的宝石学特征

针对市场上出现的一种外观酷似翡翠的透辉石微晶玻璃,利用常规宝石学检测仪器、X射线粉末衍射和红外光谱等测试方法,对该材料样品的宝石学特征、物相组成及谱学特征进行了初步研究。结果显示,在宝石显微镜下透辉石微晶玻璃显示特征的放射状晶花,具球晶结构;X射线粉末衍射分析表明,其主要物相为透辉石和玻璃质;红外光谱分析显示,该样品的谱学特征与翡翠的红外光谱有较大的差异。     

高岭石-多水高岭石演化系列的红外吸收光谱研究

本文用红外吸收光谱对我国所产高岭石-多水高岭石演化系列的四种不同类型的矿物及其热处理产物进行了初步研究,分析了各类矿物的吸收特征,探讨了它们之间的变化关系和脱水过程在红外光谱上的反映。 实验使用KBr压片法制备样品,在Perkin-Elmer 577型红外分光光度计记录红外光谱图。文中所用样品有江苏苏州与河北宣化的结晶完好的高岭石,广东清远清草岭与湖南谭家山的耐火粘土石,福建德化与湖南四青水库的多水高岭石以及四川叙永大树区与山西阳泉的水合多水高岭石。     

The transmittance color index of amorphous organic matter: a thermal maturity indicator for petroleum source rocks

Since the mid-1980s, Texaco has used the transmittance color index (TCI) of amorphous kerogen as an indicator of kerogen thermal maturation. The technique simply involves the direct measurement of a white-light spectrum as it is transmitted through a particle of amorphous organic matter (AOM). In brief, TCI values are obtained by the analysis of white light originating from a 100-W 6-V tungsten lamp attached to a photometric microscope. The assignment of particular TCI values is based on the increasing curvature of spectra with increasing maturity. TCI curves shift from an average wavelength around 580 nm for samples of immature, amorphous kerogen (i.e., material with a mean, random vitrinite reflectance of about 0.20%) to about 660 nm for samples containing very dark brown to some black particulate material (i.e., kerogen with a mean, random vitrinite reflectance of about 2.15%). The range of TCI values covers all zones of petroleum generation and preservation. In our opinion, TCI can provide as accurate a basis for maturation interpretations as is available from vitrinite reflectance (or from the mean random reflectance of some zooclasts, such as graptolites and chitinozoans), or the widely used visual estimate the thermal alteration index (TAI) or the similarly determined conodont color index (CAI). TCI is probably most useful, however, in those situations where the rocks to be examined have not yet reached the semianthricite coalification stage (≈2.0% vitrinite reflectance).     

Stable carbon isotopic analysis of sedimentary organic matter by stepped combustion

A stepped combustion technique, incremental heating in oxygen, has been used to study the carbon isotopic composition of carbonaceous sediments. This technique can afford data on the organic matter of the sediment and can give information on the structure, namely the variations in the isotopic composition of different portions, of the kerogen. Green River shale has been used as a model material and results indicate that it contains two distinct carbonaceous components, a carbonate and kerogen. Isotopic compositions for the kerogen measured by stepped combustion closely match those obtained by normal methods following preconcentration of the kerogen by mineral removal and solvent extraction.The variation in isotopic composition with combustion temperature has been used to investigate relationships with maturity and to look at its use as a possible correlation tool.     

Kerogen based characterization of major gas shales: Effects of kerogen fractionation

Research into the origin and the mode of entrapment and expulsion of natural gas from unconventional plays requires the isolation and separation of kerogen in its purest and most intact form from the rock matrix. This study expands on the comparative analysis of the effects that isolation methods, conservative closed system versus conventional open system, have on kerogen’s elemental, isotopic and physical properties. Four major gas shales, including the Barnett, the Marcellus, the Haynesville and a Polish gas shale, were chosen. In addition, the Monterey shale, though not strictly a gas shale, was included to address the effects on sulfur rich, Type II-S kerogen.Results indicate that the kerogen residues from the conventional open system method showed lower recovery and higher mineral content than those from the conservative closed system method. Differences were manifested in the elemental analysis data, where kerogens isolated using the open system method showed a significant deficit in the organic C, H, O, S and N material balance. Furthermore, the recovered residues show different sulfur content and δ³⁴S composition, most likely attributable to differences in pyrite content. Nevertheless, the relative abundances of the various macerals in the kerogen residues from the same parent shale are not very different; neither was the bulk δ¹³C composition of the recovered residues. This is not particularly surprising, considering that in all the five cases examined in this study, the organic matter was fairly homogeneous.     

Improvement of kerogen structural interpretations based on oxidation products isolated from aqueous solutions

A detailed investigation of kerogen oxidation products remaining in aqueous solutions after the usual isolation of degradation products by extraction with ether or precipitation, was carried out for the first time in kerogen structural studies. Three shale samples were investigated: Green River shale (type I kerogen), Toarcian shale, Paris Basin (type II), and Mannville shale, Canada (type III). The yields of acids from aqueous solutions were noticeable: 12.98, 15.32 and 22.32%, respectively, based on initial kerogens. Qualitative and quantitative capillary GC/MS analysis showed that the ratios of different kinds of identified acids depended much on the type of precursor kerogen. Some of the acids identified in aqueous solutions have not been found earlier among the degradation products of the same kerogen samples, or were obtained in different ranges and yields. Consequently, slight modifications were suggested of the image on the nature of various types of kerogens based on examination of ether-soluble acids only. Namely, slightly higher proportions of aromatic and alkane-polycarboxylic acids in the total oxidation products of both type I and type II kerogens indicated larger participation of aromatic and alicyclic and/or heterocyclic structures in these two kerogens. On the other hand, for type III Mannville shale kerogen, a somewhat larger share of aliphatic type structures was demonstrated.     

Modeling the attenuated total reflectance infrared (ATR-FTIR) spectrum of apatite

Attenuated total reflectance (ATR) infrared spectra were measured on a synthetic and a natural fluorapatite sample. A modeling approach based on the computation of the Fresnel reflection coefficient between the ATR crystal and the powder sample was used to analyze the line shape of the spectra. The dielectric properties of the samples were related to those of pure fluorapatite using an effective medium approach, based on Maxwell–Garnett and Bruggeman models. The Bruggeman effective medium model leads to a very good agreement with the experimental data recorded on the synthetic fluorapatite sample. The poorer agreement observed on the natural sample suggests a more significant heterogeneity of the sample at a characteristic length scale larger than the mid-infrared characteristic wavelength, i.e., about 10 micrometers. The results demonstrate the prominent role of macroscopic electrostatic effects over fine details of the microscopic structure in determining the line shape of strong ATR bands.     

Study of petroleum generation by pyrolysis—I. Pyrolysis experiments by Rock-Eval and assumption of molecular structural change of kerogen using13C-NMR

Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%R_o) measurement, maceral observation, infrared spectroscopy (IR) and¹³C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when R_o does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by¹³C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.     

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm⁻¹) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.     

Mössbauer spectroscopic studies of iron in organic material from natural sedimentary environments

⁵⁷Fe Mössbauer spectra have been obtained from samples of humic acid, fulvic acid and kerogen and from the organic material extracted from bituminous chalk with benzene-methanol. The spectra indicate that iron occurs in a trivalent form in the silicate residue of the humic acid fraction, as hydrated ferrous ions associated with the fulvic acid fraction, as pyrite in kerogen and in a form not detectable by Mössbauer spectroscopy in the benzene-methanol extract.     

Prognostication of hydrocarbon generative potential in the onshore and offshore Niger Delta,Nigeria using TOC content and rock-eval pyrolysis techniques

This article prognosticates the hydrocarbon generation potential of core samples from fields A, B, C and D in Niger delta, Nigeria. The objectives of this study are to characterize the quality of these core samples by organic geochemical analyses. A total of ten core samples collected from fields A, B, C and D in Niger delta were analyzed using total organic carbon （TOC） content analysis, rock-eval pyrolysis technique. The analytical results of the stud- ied core samples reveal that they have generally high total organic carbon contents （TOC）, suggesting that conditions in the Niger delta favour organic matter production and preservation. There is a variation in the kerogen types and this may be attributed to the relative stratigraphic positions of the core samples within the Niger delta. The rock-eval results indicate that the samples from fields C and D contain predominantly Type II kerogen with a capacity to gen- erate oil and gas and hence have good generative potential. The samples from fields A and B contain mainly Type III kerogen and are gas-prone with moderate generative potential.     

Determination of hydrocarbon generation potential of a non-isothermal pyrolysis of Faraghun and Sarchahan Formations in Coastal Fars and the Persian Gulf,Iran

Source rock assessment is a key step in any petroleum exploration activity. The results of Rock-Eval analysis showed that Sarchahan Formation was in the late oil window, while the Faraghun and Zakeen Formations were just in the early stages of the oil window. Furthermore, Sarchahan, Zakeen and Faraghun Formations exhibited different kerogen types (types-Ⅱ, types-Ⅲ and type-Ⅲ, respectively). Refining the kinetic parameters using the OPTKIN software, the error function returned error values below 0.1, indicating accurate optimization of the kinetic parameters. Based on the obtained values of activation energy, it was clear that Sarchahan Formation contained type-Ⅱ kerogen with an activation energy of 48–52 kcal/mol, while Zakeen and Faraghun Formations contained type-III kerogen with activation energies of 70–80 kcal/mol and 44–56 kcal/mol, respectively. The geographical distribution of the samples studied in this work, it was found that the organic matter (OM) quantity and quality increased as one moved toward the Coastal Fars in Sarchahan Formation. The same trend was observed as one moved from the southern coasts of Iran toward the shaly and coaly portions of Faraghun Formation in the center of the Persian Gulf.©2021 China Geology Editorial Office.