New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

The luminescent humic substances in speleothems

Calcite speleothems deposited in caves by seepage waters derived from the overlying soils of the epikarst are typically coarsely crystalline, colored various shades of brown through orange and white, and strongly luminescent. For most speleothems, the color and luminescence is due to humic substances incorporated in the calcite crystals. For a quantitative assessment of the luminescent properties of these materials, the organic content of the dissolved speleothems was separated by gel chromatography and spectra measured as a function of molecular weight. The most intense luminescence was obtained from molecular weight fractions in the range of 4000–6000 daltons, a range characteristic of fulvic acids. In addition, there was considerable variation in detail from sample to sample that would merit further investigation.     

Calculation of molecular weights of humic substances from colligative data: Application to aquatic humus and its molecular size fractions

A rigorous mathematical expression for the dependence of colligative properties on acid dissociation of water soluble humic substances is presented. New data for number average molecular weights of a river derived humic material and its gel permeation Chromatographic fractions are compared with $\text{M}\text{?}{}_{\mathrm{n}}$ values obtained by a reevaluation of previously published experimental observations on soil and water fulvic acids. The results reveal a remarkable similarity of fulvic acids from widely different sources with respect to number-average molecular weight.     

The average molecular weight and shape of the “polymeric acids” found in Black Trona Water from the Green River Basin

Macromolecular organic material, called “polymeric acids”, has been isolated from Black Trona Water by exhaustive dialysis and characterized as the sodium salt in 0.10 M sodium carbonate, pH 10, by several physico-chemical methods. Analysis by gel filtration chromatography on Sepharose-CL 6B indicates that the “polymeric acids” are polydisperse and composed of species of relatively high molecular weight ( 4 × 10⁵, using proteins as standards). With this method, the range of molecular weights appears to be rather narrow. If “polymeric acids” are transferred from sodium carbonate, pH 10, into distilled water, selfassociation occurs and all species elute in the void volume. The weight-average molecular weight determined in 0.10 M sodium carbonate, pH 10, by the light scattering method is 1.7 × 10⁵. Sedimentation velocity analysis at 20°C with the analytical ultracentrifuge gives a value for S_20,w of 5.4 and the shape of the Schlieren patterns suggest a polydisperse sample with a relatively narrow range of sizes. Analysis of the molecular weight distribution by a sedimentation equilibrium method indicates that the range of molecular weights is 8 × 10⁴ to 2.1 × 10⁵. The partial specific volume ( ) of “polymeric acids” is 0.874 ml/g. Viscosity measurements yield a value for [η] of 2.5 ml/g, which indicates that the “polymeric acids” are compact (spherical or ellipsoidal) in shape.     

Estimation of kinetic parameters of a grinding-liberation model

A method of parameter estimation is outlined for a two-component grinding-liberation model. The large number of model variables is reduced by using functional forms. The parameters for the functional forms are estimated using a modified Gauss-Newton algorithm. The technique is applied to both synthetic and real experimental data. Parameters estimated from wet grinding batch tests of Illinois No. 6 coal were used to predict mill output for a larger pilot-plant mill. The predictions were found to match the actual mill output within the limits of experimental error.     

Molecular weight of aquatic fulvic acids by vapor pressure osmometry

The molecular weights of aquatic fulvic acids extracted from five rivers were determined by vapor pressure osmometry with water and tetrahydrofuran as solvents. The values obtained ranged from 500 to 950 dallons, indicating that the molecular weights of aquatic fulvic acids are not as great as has been suggested in some other molecular weight studies. The samples were shown to be relatively monodisperse from radii of gyration measurements determined by small angle x-ray scattering. THF affords greater precision and accuracy than H₂O in VPO measurements, and was found to be a suitable solvent for the determination of molecular weight of aquatic fulvic acid because it obviates the dissociation problem. An inverse correlation was observed with these samples between the concentration of Ca⁺⁺ and Mg⁺⁺ in the river water and the radii of gyration and molecular weights of the corresponding fulvic acid samples.     

Molecular analysis of petroleum derived compounds that adsorb onto gas hydrate surfaces

Field observations have shown that some streams of water, gas and crude oil do not form gas hydrate plugs during petroleum production even when operating within thermodynamic conditions for hydrate formation. Also, when studied under controlled laboratory conditions, some oils are found to form hydrate dispersed systems whereas others form plugs. Oils with low tendency to form hydrate plugs are believed to contain natural hydrate plug inhibiting components (NICs) that adsorb onto the hydrate surface, making them less water-wet and preventing the particles from agglomerating into large hydrate clusters. The molecular structure of the NICs is currently unknown. In this work, hydrate adsorbing components were extracted from crude oils using freon hydrates as an extraction phase. The fractions were found to be enriched in polar material, and more polar material is associated with hydrates generated in biodegraded crude oils than in non-biodegraded oils. Various fractionation schemes and analytical techniques have been applied in the search for molecular characterisation. The average molecular weights were found to be approximately 500 g/mole. GC–MS chromatograms show a large UCM (Unresolved Complex Mixture). Thus, GC–MS has a limited potential for identification of compounds. A commercial biosurfactant was used as a model compound in the search for similar structures in the extracts. The results from analysis of the hydrate adsorbing components suggest that the type and structure are more important for hydrate morphology than the amount of material adsorbed.     

证据权模型中两种预测单元划分方式对比

证据权模型作为一种数据综合方法已被广泛应用于矿产资源定量预测与评价。在模糊证据权基础上,发展了基于地质单元思想的矢量证据图层构建和数据综合方法,并通过实例作具体阐述：它以矿点缓冲区图层作为训练图层,以各证据变量图层在空间上的叠置所形成的唯一地质单元作为评价对象,统一计算各个证据变量的证据权重,进而基于地质单元进行证据综合和后验概率成图。与基于栅格（或规则格网）的模型不同,基于矢量证据权模型以具有明确地质内涵的地质单元（而非规则网格单元）为预测单元,易于解释,并且消除了边界误差;相比基于规则格网划分所得到的成矿单元,以矿床（点）缓冲区作为训练对象,提高了已知矿点的代表性。实例表明：若预测单元大小为初始栅格大小整数倍,各缓冲等级平均面积计算误差为0.26%,否则面积平均误差达到6%;即使在预测单元大小为初始栅格大小整数倍情况下,矿点平均计算误差也达到4.78%。因此,基于地质单元思想的证据权预测单元划分方法在精度上优于基于栅格或规则格网方法。     

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.     

Studies of molecular weight distributions of fulvic and humic acids by gel permeation chromatography. Examination of the solute molecular composition using RI,UV, fluorescence and weight measurement as detection techniques

The system Sephadex LH 60/dimethylformamide/acetic acid was found to be useful for the determination of the molecular weights of humic substances. Fulvic and humic acids concentrated from natural waters, sediments and soil have number- and weight-average molecular weights less than 2000 and 4000, respectively. A theoretical model for the dependence of an experimental GPC curve on the relation between the measured property and the structure of heterogeneous polymers, is presented. The results from the examination of the molecular composition, obtained by using RI, UV, fluorescence and weight measurement as detection techniques, show that the apparent distributions of aromatic moities and fluorescent groups in the humic substances were similar to those of repeating structural subunits and end groups respectively, in synthetic polymers.     

Molecular Weight Distribution of Dissolved Organic Matter in Lake Hongfeng Determined by High Performance Size Exclusion Chromatography （HPSEC） With On-Line UV-Vis Absorbance and Fluorescence Detection

1IntroductionDissolvedorganicmatter (DOM)isamixtureoforganicsubstancesconsistingmainlyofhighmolecularweightpolymericcompounds (KenandLee,1 974) .Itplaysanimportantroleincarboncyclingandbiogeochemicalmobilizationoftracemetalsandorganiccompoundsintheaquaticenvi ronment (BeffleandLeppard ,1 995) .InrecentyearsmanyresearchershavepaidattentiontothesecomplexesbasedontheMWDofDOM ,sincethefateandtransportoftracechemicalsareinfluencedbyitsmolecularsize (Chiouetal.,1 986) .Themolecularweightorfrac…     

Geochemical significance of chemical composition and ESR properties of asphaltenes in crude oils from Alberta,Canada

More than 100 crude oils and 12 oil sands from Alberta, Canada, from stratigraphie units ranging in age from Upper Cretaceous to Middle Devonian, were processed to separate the asphaltenes which were then analysed for C, H, N, O and S and the ESR spectra run to determine g-value, spin number and line width. A factor analysis of these data, together with selected crude oil and reservoir properties, was interpreted in terms of a number of non-thermal processes which can affect the content and composition of asphaltenes during and after thermal maturation. Experiments on the effect of temperature on the signal intensity of free radicals indicate that more than half, and possibly all, the free radicals observed in asphaltenes must arise from charge transfer or closely related equilibria. An important solvent effect is demonstrated in further experiments, in which the more polar the solvent, the more the solvent dispersive forces overcome the associative forces of the asphaltene layers thus leading to lower molecular weights and a change in the charge transfer forces responsible for the ESR signal. The average molecular weight of asphaltenes from heavy, asphaltic, biodegraded crude oils and oil sands is considerably greater than the average molecular weight of asphaltenes from the more paraffinic, mature, non-biodegraded crude oils, and it seems likely that the differences in molecular weight of these asphaltenes are due to the solvent effect of the crude oils, and thus the laboratory observations have been confirmed in the Alberta basin.     

Acidic compounds in biodegraded petroleum

Twelve oil samples have been characterised by titration, FT-IR and chromatographic analysis to determine the differences between the organic acid composition of biodegraded and non-biodegraded oils. The biodegraded oils have higher total acid and total base contents, both by titration and extraction. The molecular weight ranges of the extracted acids are lowest in the biodegraded oils, and the equivalent weight calculations indicate a dominance of multi-functional molecules. Gel permeation chromatography gives a molecular weight range with most of the molecules between 300 and 500 g/mol. FT-IR shows that the extracted acids from biodegraded oils are more carboxylic and aliphatic while the non-degraded oils are more phenolic. Molecular analysis of the derivatised extracts give UCM envelopes for biodegraded oils, and no molecular identification. The results indicate that the acidic constituents in biodegraded oils are a product of the biodegradation, as the composition is very different from the non-biodegraded oils.     

Ultrafiltration of fulvic and humic acids,a comparison of stirred cell and hollow fiber techniques

The ultrafiltration of solutions of well characterized samples of fulvic and humic acids or their salts, using two different techniques, show that these materials are retained by commercial ultrafiltration membranes with molecular weight cut-off values far higher than the reported molecular weights of fulvic or humic acid. The lower molecular weight fulvic acid or its Na⁺ -salt is retained even better than the higher molecular weight Na⁺-salt of humic acid. Both stirred cell and hollow fiber techniques can be employed to concentrate or desalt solutions of these humic materials, with relatively small solute losses. Very high simple electrolyte backgrounds (above 1 M) lower the performance of a given membrane considerably, moderate concentrations of simple electrolyte do not influence the ultrafiltration efficiency.     

Behaviour of quartz suspensions in the presence of calcium ions and acrylate polymers

The effect of acrylate polymers on the behaviour of quartz-slime suspensions, in the presence or in the absence of calcium ions, is considered. Results of dispersion tests with polyacrylates of various molecular weights show that acrylates are capable of extending the pH range in which quartz is dispersed to weakly acid pH values: between 3.5 and 4.5, if calcium ions are not added to the system. On the other hand, in the presence of calcium ions, the dispersed state can be maintained only in a narrow pH range, between 4, 5 and 6 to 8.5, the latter value being reached only in the case of very low molecular weight polymer (5.400). At higher pH values, flocculation takes place, more intensively as the pH becomes more basic and the molecular weight of polymer higher.The mechanism by which dispersion or flocculation occurs is interpreted on the basis of experimental results of dispersion tests and zeta potential measurements. From these data, it is concluded that electrostatic effects and steric hindrance phenomena must not be ignored in explaining the behaviour of mineral suspensions, chiefly when a very low molecular weight is used. Adsorption of calcium ions on quartz surfaces appears also to play a fundamental part in the flocculation mechanism at basic pH values.     

Unusual N—Alkane Distributions in Extracts from Marine Carbonate Rocks at High Levels of Maturity and Overmaturity

N-alkanes in extracts from possible carbonate source rocks of the Lower Ordovician Majiagou Formation in the central gas field of the Shanganning Basin and the Upper Sinian Dengying Formation in the Weiyuan gas field of the Sichuan Basin, are characterized by bimodal distributions with the dominant carbon numbers in the range C₁₇-C₂₁ and C₂₅-C₂₉. In most samples, the lower carbon number components are present in greater abundance than the higher carbon number ones. Most samples contain significant concentrations of waxy hydrocarbons (C₂₂₊) with C_21-/C₂₂₊ ratios between 0.50 to 3. 16, and an average value of 1. 34. The n-alkanes in extracts of outcrops and shallow core samples of Upper Proterozoic and Lower Palaeozoic carbonate rocks in the western and southern parts of the North China Basin are of unimodal distributions dominated by n-alkanes maximizing in the C₂₅-C₂₉ range. These extracts have very high concentrations of waxy hydrocarbons with C_21-/C₂₂₊ ratios all < 1. 0, ranging from 0. 14 to 0. 90 and averaging 0. 36. All of the extracts have a marked odd/even predominance in the high molecular weight n-alkane range regardless of whether they are from shallow or deep cores or out-crop samples. Simulation experiments were performed using typical sapropelic-type kerogens from the immature Sinian Lower Xiamalin Formation carbonate-rich shales collected at Jixian, Hebei Province, North China Basin, and the contemporary microplanktonic blue-green algaeSpirulina subsala. Results indicate that the unusual distribution of n-alkanes in the extracts of Upper Proterozoic and Lower Palaeozoic carbonate rocks possibly originated from algae in the source rocks at high levels of maturity and overmaturity. This research project was financially supported by the Chinese Academy of Sciences (Grant No. KZCX2-111 ).     

Pennsylvanian coalified rhizomorphs in Illinois: evidence for non-compressive coalification to bituminous coal rank

Irregular and discontinuous coalified objects, here termed rhizomorphs, occur above the Summum (No. 4) Coal Member (Carbondale Formation) at one locality in La Salle County, Illinois. These vitrinite structures, varying between 3 mm and 4 cm in diameter, occur in a blocky to structureless mottled claystone characterized by numerous carbonaceous streaks and small-scale slickensides. The rhizomorphs twist and bend in a tightly coiled and kinked pattern, and may extend laterally through the claystone for 40 cm or more before bifurcating or terminating. The rhizomorphs display little or no evidence of compressive distortion. They are composed of two types of material: structureless bright conchoidal collinite; and cellular woody structure. One or more vascular bundles occur as discrete steles within a groundmass of collinite gel; these are generally aligned longitudinally within the coal except where steles diverge laterally as offshoots. The rhizomorphs are believed to be a diagenetic derivative of rooting structures; this is based on their occurrence in an underclay-like sediment and on their irregular, kinked form, which differs from that of most vertical supportive plant stems. Non-compressive coalification of the plant material may have occurred through: (1) aerobic alteration of cell walls to non-compressive inertinite; (2) centripetal contraction and selective degradation of plant tissue; and (3) impregnation of more resistant stelar elements by organic gel derived from degradation of thin-walled tissue.     

Co-carbonization of selected American coals with commercial additives

Because of the short supply of high-quality coking coals in certain areas of the world, many methods of improving the coking characteristics of poorly coking or noncoking coals have been examined as alternatives to importing more expensive, better quality coals. Co-carbonization, or the addition of coal-derived or petroleum-derived materials to the coal charge prior to carbonization, has been used on a commercial basis in the Japanese coking industry. These additives have been used in both solid and liquid form as binders in coal briquettes or as direct additions to the coal blend.In this study three different coal lithotypes were sampled from each of three United States bituminous coal seams: (1) a marginally coking high-volatile B-rank Illinois No. 6 Seam; (2) a highly fluid, good coking quality, high-volatile A-rank Pittsburgh Seam; and (3) a strongly coking low-volatile Blue Creek Seam. Each lithotype sample was carbonized in small-scale (50 g) charges with each of three additives at 0, 2, 5, and 10% additive by weight. The additives included ASP, an asphalt pitch; KRP, a petroleum residue pitch; and SRC, a solvent-refined coal product. The different lithotypes were sampled to examine the effects of coal type as well as rank. A micro-tumbler test was used to give at least a relative coke-strength value for the cokes produced. In addition, all the cokes produced were examined microscopically to determine the effects of co-carbonization on the coke structure.The Illinois No. 6, Pittsburgh, and Blue Creek Seam coals all showed substantial strength increases when co-carbonized with 2, 5, and 10% of each of the three additives, particularly at the 5 and 10% levels. The SRC appears to be the best additive overall for the three ranks of coal, as judged by its ability to combine with the coal to make a higher strength coke. There appear to be no conclusive coke-strength differences among lithotype samples for any of the three coals, probably because of the small scale of the tests and the relatively small differences in inert maceral content among the lithotypes. Five percent by weight of additive appears to be sufficient, if properly blended with the coal charge, to produce higher strength cokes. This is also probably the maximum economically viable level, particularly in the United States coking industry. Two percent is probably the minimum additive level for adequate mixing on a commercial scale.     

Organic geochemical characterization of the New Albany Shale group in the Illinois Basin

Benzene extractable aliphatic hydrocarbons from the New Albany Shale in the Illinois Basin were characterized by gas chromatography and mass spectrometry, and the total organic matter of the shale was characterized by solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance. Core samples from a northwest-trending cross-section of the Illinois Basin were studied. Gas chromatography (GC) and gas chromatography-mass spectrometric analysis (GC/MS) data indicate a regional variation of the aliphatic composition of the shale extracts. A positive, linear relationship between the two ratios, pristane/n-C₁₇ and phytane/n-C₁₈, is indicated. The NMR results indicated that organic matter deposited in northwestern Illinois shale is relatively high in aliphatic hydrocarbon content while, in contrast, organic matter found in southeastern Illinois shale is relatively low in aliphatic hydrocarbon content. Our findings suggest that the organic variation of the shale is mainly due to the differences in thermal maturity of the shale organic matter and the use of pristane/n-C₁₇ ratio as a thermal parameter in the study of oil may be extended to the study of the ancient sediments.     

Environmental and tectonic influences on the formation and distribution of carbonate nodules above the Springfield coal seam, southern Illinois Basin

Carbonate nodules have been encountered for many years in the southern Illinois Basin, in parts of southern Illinois, southern Indiana, and southwestern Kentucky. The nodules occur as oblate spheroids of calcium carbonate that are isolated in the shale immediate roof of coal mines. They are common in the Springfield coal seam, known as the No. 5 seam in Illinois, and as the No. 9 seam in western Kentucky. Several different mechanisms have been proposed for the formation of various semi-spherical objects in coal measure rocks. The distribution and association with rooted horizons suggest that carbonate nodules in black fossiliferous shale observed in the roof of a studied mine in the Springfield seam represent pedogenic carbonate paleosols, which formed in a caliche-favoring environment subsequent to Springfield mire deposition. This interpretation is supported by ⁸⁷Sr/⁸⁶Sr isotope ratios of 0.710893 ± 13 to 0.711035 ± 12, which indicate a freshwater rather than seawater source.Petrographic examination of rock textures and mineral grains indicates that nodules collected from two Illinois Basin coal mines are composed of subangular grains of fine-grained, crystalline microspar. Although the carbonate is not ferroan, iron hydroxide stains interstices between microspar grains. The rounded, commonly pinched boundaries of nodules truncate commonly imbricated microspar grains. In contrast, concentric growth patterns are not observed except as defined by secondary, subhedral to euhedral pyrite crystals that form a diffuse, concentric replacement zone around the nodule's outer rind. Polished slickensides, with well-developed radial slickenlines, are developed at highly compacted margins in black shale or mudstone that commonly encases the carbonate nodules.Of the 450 carbonate nodules documented at a study mine in the southern Illinois Basin, the long axes of 36% are preferentially aligned parallel to regional structures such as anticline axes and drag folds that are interpreted to have formed in response to compression during the Late Pennsylvanian-Permian Alleghanian orogeny. Mapping also suggests that clusters of carbonate nodules are spatially associated with the trends of low-angle drag folds in the immediate roof of the Springfield seam at the study mine. The preferential elongation and distribution with respect to tectonic structures suggest that regional compression influenced the shape and distribution of carbonate nodules, and that nodule lithification may have been approximately contemporaneous with regional deformation.