Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.     

Organic pollutants associated with macromolecular soil organic matter: Mode of binding

A study of ether-linked moieties in macromolecular bound residues of polycyclic aromatic hydrocarbons (PAH) generated in bioremediation experiments was performed using high temperature hydrolysis degradation with subsequent analysis of the products by GC-MS. This hydrolysis reaction was specifically designed to cleave ether bonds including relatively stable diarylether structures. Among the reaction products, aromatic alcohols representing typical microbiologically derived metabolites of PAH were found in addition to natural compounds. Thus, parts of the bound residues appeared to be linked within the macromolecular material by ether bonds. Model experiments with an oxidoreductase enzyme and aromatic alcohols indicate the formation of these ether bonds to be an enzyme-catalysed process.     

Structural characterization of gilsonite bitumen by advanced nuclear magnetic resonance spectroscopy and ultrahigh resolution mass spectrometry revealing pyrrolic and aromatic rings substituted with aliphatic chains

Gilsonite, a naturally occurring asphaltite bitumen, consists of a complex mixture of organic compounds. In the present study, advanced one and two dimensional solid state and solution ¹H, ¹³C and ¹⁵N nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were employed to investigate its composition and structure. ¹³C NMR yielded a carbon aromaticity of 27%. Aromatic moieties in gilsonite were primarily single rings or small clusters of fused rings. Half of the aromatic carbons of gilsonite can be accounted for by pyrroles. ¹⁵N and ¹³C cross polarization-magic angle spinning (CP-MAS) NMR showed that most nitrogen in gilsonite was pyrrolic. The aromatic rings were heavily substituted with alkyl chains, as evidenced by ¹H¹³C correlation spectra. Advanced solid state NMR spectral editing techniques clearly identified specific functional groups such as CCH₃, CCH₂, and CCH₂ (exomethylene). ¹H¹³C wideline separation (WISE) NMR helped identify mobile and non-protonated alkyl carbons. FT-ICR-MS indicated that ∼64% of calculated formulae generated by ESI were aliphatic, while only about 0.8–2.5% of formulae contained possible aromatic rings. All of the assigned formulae contained at least one heteroatom (N, O or S), indicating that ionization by ESI was selective for the polar fraction of gilsonite and potentially less reflective of the overall chemical character of gilsonite than NMR spectroscopy. By combining the information obtained from advanced NMR and ultrahigh resolution MS we propose a structural model for gilsonite as a mixture of many pyrrolic and a few fused aromatic rings highly substituted with and connected by mobile aliphatic chains.     

C and N NMR analysis of some fungal melanins in comparison with soil organic matter

A variety of fungal melanins with natural ¹⁵N abundance are characterized by solid-state ¹³C and ¹⁵N NMR spectroscopy and are compared to solid-state ¹³C and ¹⁵N NMR spectra of organic matter from representative soils. In all solid-state ¹⁵N NMR spectra the peptide/amide region (−220 to −285 ppm) dominates with more than 70% of the total intensity. The region between −285 and −375 ppm, assigned to amino and ammonium groups, always contains more than half of the remaining intensity. The area in the region from −30 to −220 ppm, where aromatic heterocycles would show signals, makes up less than 10% of the total intensity. These findings call into question common structural models for melanins. The solid-state ¹³C NMR spectra, on the other hand, reveal large differences when the melanins are compared to each other, and to composts and soils. The concentration of the aromatic carbon varies from 5 to 40% in the melanin series. The ratio C_aro/N_tot and C_ali/N_tot were calculated, and confirm that nitrogen in these samples is bound in C_a-groups rather than in aromatic heterocyclic structures.     

A new approach for molecular characterisation of sediments with Fourier transform ion cyclotron resonance mass spectrometry: Extraction optimisation

Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) can begin to tease apart the molecular character of sedimentary organic matter (SOM). We therefore tested five different solvents (aqueous base, CHCl₃, MeOH, pyridine and water) for their ability to extract a representative fraction from two organic rich lacustrine sediments, Mangrove Lake, Bermuda (MLB) and Mud Lake, Florida (MLF). Following comparison using liquid state nuclear magnetic resonance spectroscopy (NMR) and negative ion mode electrospray ionization mass spectrometry (FTICRMS) we found that pyridine was the optimal solvent, extracting a more diverse (10–100× greater integration for carbonyl, amide and amine groups) and a larger number of peaks on average (1375–1450 vs. 380–1450). Comparison of the pyridine extracts between MLB, MLF and two organic poor sediments from the Mississippi River Delta and Bayou Grande (Pensacola, FL) showed that only 4.9% of the molecular formulae were common to all four and that unique formulae made up the highest proportion of the assignments. The use of pyridine for extracting immature (Holocene) SOM for FTICRMS analysis can therefore be widely applied to immature sediments and produce representative spectra.     

Cs and Cl NMR spectroscopy and molecular dynamics modeling of Cs and Cl complexation with natural organic matter

Interaction of dissolved aqueous species with natural organic matter (NOM) is thought to be important in sequestering some species and enhancing the transport of others, but little is known about these interactions on a molecular scale. This paper describes a combined experimental ¹³³Cs and ³⁵Cl nuclear magnetic resonance (NMR) and computational molecular dynamics (MD) modeling study of the interaction of Cs⁺ and Cl⁻ with Suwannee River NOM. The results provide a detailed picture of the molecular-scale structure and dynamics of these interactions. Individual NOM molecules are typically hundreds to thousands of Daltons in weight, and on the molecular scale their interaction with small dissolved species can be investigated in ways similar to those used to study the interaction of dissolved aqueous species with mineral surfaces. As for such surface interactions, understanding both the structural environments and the dynamics over a wide range of frequencies is essential. The NMR results show that Cs⁺ is associated with NOM at pH values from 3.4 ± 0.5 (unbuffered Suwannee River NOM solution) to 9.0 ± 0.5. The extent of interaction increases with decreasing CsCl concentration at constant pH. It also decreases with increasing pH at constant CsCl concentration due to pH-dependent negative structural charge development on the NOM caused by progressive deprotonation of carboxylic and phenolic groups. The presence of NOM has little effect on the ¹³³Cs chemical shifts, demonstrating that its local coordination environment does not change significantly due to interaction with the NOM. Narrow, solution-like line widths indicate rapid exchange of Cs⁺ between the NOM and bulk solution at frequencies of >10² Hz. The MD simulations support these results and show that Cs⁺ is associated with the NOM principally as outer sphere complexes and that this interaction does not reduce the Cs⁺ diffusion coefficient sufficiently to cause NMR line broadening. The ³⁵Cl NMR data and the MD results are consistent in demonstrating that there is no significant complexation between Cl⁻ and NOM in the pH range investigated, consistent with negative structural charge on the NOM.     

Structural changes of humic acids from sinking organic matter and surface sediments investigated by advanced solid-state NMR: Insights into sources, preservation and molecularly uncharacterized components

Knowledge of the structural changes that particulate organic matter (POM) undergoes in natural systems is essential for determining its reactivity and fate. In the present study, we used advanced solid-state NMR techniques to investigate the chemical structures of sinking particulate matter collected at different depths as well as humic acids (HAs) extracted from these samples and underlying sediments from the Saguenay Fjord and the St. Lawrence Lower Estuary (Canada). Compared to bulk POM, HAs contain more non-polar alkyls, aromatics, and aromatic C-O, but less carbohydrates (or carbohydrate-like structures). In the two locations studied, the C and N contents of the samples (POM and HAs) decreased with depth and after deposition onto sediments, leaving N-poor but O-enriched HAs and suggesting the involvement of partial oxidation reactions during POM microbial degradation. Advanced NMR techniques revealed that, compared to the water-column HAs, sedimentary HAs contained more protonated aromatics, non-protonated aromatics, aromatic C-O, carbohydrates (excluding anomerics), anomerics, OC_q, O-C_q-O, OCH, and OCH₃ groups, but less non-polar alkyls, NCH, and mobile CH₂ groups. These results are consistent with the relatively high reactivity of lipids and proteins or peptides. In contrast, carbohydrate-like structures were selectively preserved and appeared to be involved in substitution and copolymerization reactions. Some of these trends support the selective degradation (or selective preservation) theory. The results provide insights into mechanisms that likely contribute to the preservation of POM and the formation of molecules that escape characterization by traditional methods. Despite the depletion of non-polar alkyls with depth in HAs, a significant portion of their general structure survived and can be assigned to a model phospholipid. In addition, little changes in the connectivities of different functional groups were observed. Substituted and copolymerized carbohydrates and fused-ring aromatics detected in the present study likely represented an important part of molecularly uncharacterized components (MUC).     

Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: When clay minerals lead to identical molecular signature

Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.     

A molecular dynamics study of natural organic matter: 1. Lignin, kerogen and soot

Molecular dynamics (MD) simulations were performed on molecular models of a spectrum of natural organic matter (NOM) samples represented by two lignin samples (a softwood lignin and a hardwood lignin), a kerogen (Green River Shale kerogen) and a soot sample (n-hexane soot). Simulated thermodynamic properties of each model, including glass transition temperature (T_g), thermal expansion coefficient (α), density (ρ) and solubility parameter (δ) were compared against experimental data for corresponding samples. Results revealed relatively good agreement for glass transition temperature and solubility parameter for softwood lignin, Green River Shale kerogen and n-hexane soot models. An unexpectedly low solubility parameter for a hardwood lignin model suggests, however, certain model deficiencies in terms of intermolecular interactions. In addition, a lower density for a n-hexane soot model relative to the sample was attributed to the small cluster size and poor parallel stacking of aromatic clusters in the model. Discussion of the results is provided in the context of utilizing thermodynamic properties as constraints for improved structural modeling of NOM.     

一种计算岩石中矿物组成的新方法

介绍根据显微下观察,应用岩石化学全分析结果和分子量计算法计算岩石中矿物组成的新方法。所得各种矿物的组成是整块岩石在三维立体体积中各种矿物的质量分数,比目前沿用的目测一个岩石切面上各种矿物的面积百分比法更准确,比CIPW标准矿物分子法更符合岩石样品组合的实际情况,而且可用于含云母族、绿泥石族和铀矿物等蚀变矿化的花岗岩及沉积岩、变质岩的矿物组成计算。     

不同采样点数量下土壤有机质含量空间预测方法对比

运用普通克里格、泛克里格、协同克里格和回归克里格4种方法,结合由DEM获取的高程因子以及土壤全氮和阳离子交换量（CEC）,预测了黑龙江省海伦市耕地有机质含量的空间分布。不同样点数量下海伦市土壤有机质含量的空间变异结构分析表明,样点数量多并不一定能够识别土壤有机质含量的结构性连续组分,最优化的布置采样点位置可能比单纯增加...     

Changes in the compound classes of dissolved organic matter along an estuarine transect: A study using FTIR and C NMR

In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with ¹³C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.     

A new approach for stabilization of lateritic soil with Portland cement and sand: strength and durability

The presence of lateritic soils occurs in tropical and subtropical regions. The improvement of lateritic soils that are not suitable for a particular purpose through techniques that combine modification of grain size through the insertion of sand, incorporation of Portland cement and densification through compaction is seen as an alternative. In this context, a dosage method to use a local lateritic soil as construction material in a most rational way reducing the economic and environmental impacts related to this activity is still missing. Therefore, the current research aims to evaluate the performance of a lateritic soil via modification of grain size through the insertion of sand, incorporation of Portland cement and densification through compaction. For this, unconfined compression, and durability (wetting and drying) tests were carried out on specimens of compacted clayey gravel lateritic soil, whose granulometry was modified by the insertion of distinct amounts (from zero to 45%) of weathered sand, treated with distinct Portland cement contents (from 4 to 10%), molded at different dry unit weights (from 16.8 to 20.1 kN/m³) and cured for 7 and 28 days. Results of the mechanical tests have shown the significant influence exerted by cement content and dry unit weight of the blend, followed by curing time and finally sand insertion. Satisfactory correlations between the response variables (q_u and ALM) and the adjusted porosity/cement index (η/C_v) were obtained. Furthermore, an innovative approach to replacing the laborious durability test is proposed.

     

下古生界有机质成熟度评价新参数：笔石表皮体光学特征再研究

下古生界缺失高等植物来源的镜质组,其有机质成熟度的确定一直是油气源岩评价的难题之一。基于对含笔石页岩的反射光显微镜观察和低成熟度含笔石页岩与煤共置的热压模拟实验,研究了下古生界海相页岩笔石表皮体的光性特征及其热演化规律,探讨了笔石表皮体随机反射率作为有机质热演化参数的可行性。下古生界海相页岩非粒状笔石表皮体呈条带状顺层或者碎片状产出、颗粒较大,光学特征类似于镜质组,适合于测量反射率。非粒状笔石表皮体随机反射率■换算为等效镜质组反射率■的关系式为■。采用笔石表皮体随机反射率分析了上扬子地区东部五峰组—龙马溪组页岩的有机质成熟度分布特征,认为非粒状笔石表皮体随机反射率是一个实用的下古生界烃源岩有机质成熟度指标,为确定下古生界有机质成熟度提供了一种可信的解决方案。     

High‐resolution remote sensing and GIS techniques for geobase data supporting archaeological surveys: A case study of ancient Doliche,southeast Turkey

The detection, surveying, and analysis of ancient settlement structures using remote sensing techniques offer a unique opportunity to quickly map the locations of archaeological objects in a relatively short time. High‐resolution images contribute information to the documentation and spatial relation of these objects, especially if Geographic Information Systems (GIS) and Web‐based applications are used. The aim of this study was to assess the potential use of satellite data and aerial imagesacquired by a remote‐controlled balloon to generate geospatial data with a range of resolutions and information depths. The study area was Doliche, in the landscape of ancient Commagene (Turkey), where conventional flight campaigns are impossible or strongly restricted. Recently generated data sets (i.e., topographic maps, ortho‐images, terrain models) were combined with field observations to derive ancient and modern landscape patterns and their possible relation to an assumed “ancient procession road” between the village Doliche (Dülük) and the nearby sanctuary of theRoman divinity Iupiter Dolichenus. © 2010 Wiley Periodicals, Inc.     

潮汐沉积韵律计算新方法及其应用 ——以四川江油地区中三叠统雷口坡组藻白云岩为例

提出一种新的高精确度的方法来计算沉积旋回韵律,即以样品断面光学灰度参数作为韵律沉积变化的替代指标,利用数字图像分析软件,通过最小二乘法、一阶差分法等数据处理后,定量计算沉积旋回韵律。对采自四川江油西南部中三叠统雷口坡组的纹层藻白云岩样品进行研究,观察样品抛光面和薄片,确定藻白云石具有明显的潮汐沉积韵律纹层。应用此方法计算得出研究区样品共有217个潮汐层偶对,层偶对最大厚度为4.2mm,通过人工计数对比证明了该方法的可行性。这种技术方法与传统方法相比更省时、更高效,可推广性高,同时也可应用于其它类型频段韵律旋回中。     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Industrial strategy and rural development in Africa with special reference to Ghana: A review of current trends and suggestions for a plan of action

Africa is a late comer in the field of industrial development and, today, trails considerably behind even developing Asia and Latin America in the contribution of manufacturing to GDP. At independence, African countries inherited a structural and spatial pattern of industries incapable of contributing to rural development and nationally integrated economies. The principal weaknesses of the structural and spatial patterns of industries are the predominance of first-stage processing and consumption goods industries and the lack of basic capital goods industries, the high degree of metropolitan concentration, the low and sometimes insignificant development of intersectoral and interregional linkages, the high capital-labor ratios, the growing balance of payments' problems caused by the heavy reliance on imported materials and equipment and the monopolistic control of output and markets fostering rising domestic prices. These limitations are discussed and the main ingredients of an alternative industrial allocation pattern outlined. The sustaining thesis is that any African country seeking alternative industrial allocation patterns calibrated to stimulating rural development and the integration of the space economy must initiate critical changes in the inherited structural and spatial patterns.