Source(s) and cycling of the nonhydrolyzable organic fraction of oceanic particles

A major fraction of particulate organic carbon (POC) in the deep ocean remains molecularly uncharacterized. In an effort to determine the chemical characteristics and source(s) of sinking POC, we studied a nonhydrolyzable fraction of sinking POC using ¹³C NMR (nuclear magnetic resonance) spectroscopy and analytical pyrolysis. ¹³C NMR spectra and products from analytical pyrolysis of the nonhydrolyzable fraction exhibit a strongly aliphatic character that is distinct from that of bulk POC. The aliphatic nature of this fraction is consistent with its low stable carbon isotope values. We hypothesize that the nonhydrolyzable fraction derives to a significant extent from a refractory component of organisms that selectively accumulates, resulting in its manifestation as a major part of POC sinking to the deep ocean and in underlying sediments.     

Structural analysis of sea loch sedimentary humic substances by 13C1H dipolar dephasing NMR

Nuclear magnetic resonance (NMR) techniques have been applied to the structural characterization of humic substances isolated from an organic-rich sediment in Loch Thurnaig, northwest Scotland. Both the sedimentary humic acid (SHA) and sedimentary fulvic acid (SFA) fractions from Loch Thurnaig contained substantial quantities of carboxylic and alkyl carbon with a small contribution (26 and 22% respectively) of aromatic/olefinic carbon atoms. The latter structures were shown by dipolar dephasing ¹³C NMR to be largely non-protonated. Differences in the alkyl structures of the two fractions were noted, with the SHA containing a larger amount of branched chain aliphatic material. As branched chain compounds are more resistant to microbial degradation than straight chain compounds, this may indicate that SHA is the older, more refractory fraction of the sedimentary organic matter, although it is possible that the results reflect different algal precursor material. The fraction of aromatic carbon was higher in the SHA than in the SFA as is generally found for humic and fulvic acids isolated from the same source. The low aromaticities and highly branched aliphatic structures show that the sedimentary humic substances from the loch resemble dissolved marine humic substances rather than their terrestrial counterparts.     

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.     

Exploitation of relaxation in cross-polarization nuclear magnetic resonance spectroscopy of fossil fuels

The judicious choice of dipolar dephasing times or carbon magnetization holding times has been shown to improve resolution in solid state nuclear magnetic resonance (NMR) spectra of complex materials. Signals from protonated and alkylated aromatic carbons are reduced to enhance resolution of aromatic oxygenated groups. Rapidly rotating methyl groups can be resolved from other aliphatic carbon types. These techniques were used to investigate the structure of a brown coal, xylite fractions of a brown coal, a bituminous coal, an oil shale and a solvent-refined coal. The results allow estimates of the fraction of aromatic carbon that is protonated in coal to be made, and demonstrate that methyl groups in coal rotate rapidly at room temperature.     

Characterization of soil organic carbon in drained thaw-lake basins of Arctic Alaska using NMR and FTIR photoacoustic spectroscopy

Arctic soils contain a large fraction of Earth’s stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO₂. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The ¹³C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.     

Aliphatic hydrocarbons in the bitumens of the Puertollano oil shales

The aliphatic fraction of the bitumens from 3 bands of the Puertollano oil shale field have been studied by gas chromatography and gas chromatography/mass spectrometry. Previous work published over the last years reached different conclusions about the origin of the organic matter in the Puertollano oil shales. A reappraisal of some of the biomarkers was then needed for a better understanding of the aliphatic hydrocarbons assemblage. The identified compounds, mainly n-alkanes in the medium to high boiling point region, acyclic isoprenoids and hopane-related compounds point towards a predominant algal/bacterial input. No unequivocally higher plant derived biomarkers have been detected in significant amounts, suggesting that the bulk of the organic matter derive from authocthonous organisms living in the basin. The biomarker maturity ratios indicate that the 3 Puertollano oil shales have similar maturities and are close to the onset of oil generation, assessing a slightly higher maturity than that determined by petrographic techniques.     

Chemical composition of the graphitic black carbon fraction in riverine and marine sediments at sub-micron scales using carbon X-ray spectromicroscopy

The chemical composition of the graphitic black carbon (GBC) fraction of marine organic matter was explored in several marine and freshwater sedimentary environments along the west coast of North America and the Pacific Ocean. Analysis by carbon X-ray absorption near-edge structure spectroscopy and scanning transmission X-ray microscopy shows the GBC fraction of Stillaguamish River surface sediments to be dominated by more highly ordered and impure forms of graphite, together forming about 80% of the GBC, with a smaller percent of an aliphatic carbon component. Eel River Margin surface sediments had very little highly ordered graphite, and were instead dominated by amorphous carbon and to a lesser extent, impure graphite. However, the GBC of surface sediments from the Washington State Slope and the Mexico Margin was composed almost solely of amorphous carbon. Pre-anthropogenic, highly oxidized deep-sea sediments from the open Equatorial Pacific Ocean contained over half their GBC in different forms of graphite as well as highly aliphatic carbon, low aromatic/highly acidic aliphatic carbon, low aromatic/highly aliphatic carbon, and amorphous forms of carbon. Our results clearly show the impact of graphite and amorphous C phases in the BC fraction in modern riverine sediments and nearby marine shelf deposits. The pre-anthropogenic Equatorial Pacific GBC fraction is remarkable in the existence of highly ordered graphite.     

Wetland soil organic matter composition in a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain): Insight into different carbon sequestration pathways

Wetland soils from a Mediterranean semiarid wetland (Las Tablas de Daimiel, Central Spain) were studied to characterize the organic matter (OM) and determine its origin and transformation. Cross polarization magic angle spinning (CPMAS) ¹³C nuclear magnetic resonance (NMR) spectroscopy and mathematical molecular mixing allowed analysis of the organic fraction in terms of six generic components (carbohydrate, protein, lignin, lipid, char and “carbonyl”). Las Tablas is an active carbon sink, with total organic carbon (TOC) content independent of soil OM quality; the TOC content of the upper sediment is 10.0 ± 7.8%. The inorganic carbon content is also high (5.4 ± 3.3%) and is associated mainly with OM of aliphatic character. The OM composition is variable; samples predominantly aliphatic (carbohydrate, lipid and protein) are characteristic of the northern sector, whereas predominantly aromatic samples are typical of the southern Tablas. A strong negative relationship between protein content and lignin content was found, interpreted as a consequence of different proportions of vascular vs. non-vascular (mostly charophyte) litter input. The effect of perturbation is apparent in the extended presence of char, particularly abundant in fire-prone areas. OM quantity and quality do not seem to depend on hydrology (although seasonal flooding is associated with lower TOC wetland soils) or soil characteristics. Dominant vegetation and fire are the main drivers of OM content and composition. Structural carbohydrate, protein and lipid (>60% of total organic fraction) dominate. Widespread anaerobic conditions and the recent character of the sediments could explain the preservation of different fractions of the original detritus composition (due to different vegetation and presence of microbes).     

Geochemistry,Petrography and Spectroscopy of Organic Matter of Clay‐Associated Kerogen of Ypresian Series: Gafsa‐Metlaoui Phosphatic Basin,Tunisia

This work presents geochemical characterization of isolated kerogen out of clay fraction using petrography studies, infrared absorption and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, with N‐alkane distributions of saturated hydrocarbon. Mineralogical study of clay mineral associations was carried out using X‐ray diffraction (XRD), on Ypresian phosphatic series from Gafsa‐Metlaoui basin, Tunisia. The XRD data indicate that smectite, palygorskite and sepiolite are the prevalent clay minerals in the selected samples. In this clay mineral association, the N‐alkane (m/z = 57) distribution indicates that the marine organic matter is plankton and bacterial in origin. The kerogens observed on transmitted light microscopy, however, appear to be totally amorphous organic matter, without any appearance of biological form. The orange gel‐like amorphous organic matter with distinct edges and homogenous texture is consistent with a high degree of aliphaticity. This material has relatively intense CH₂ and CH₃ infrared bands in ¹³C NMR peaks. This aliphatic character is related to bacterial origin. Brown amorphous organic matter with diffuse edges has a lower aliphatic character than the previous kerogen, deduced from relatively low CH₂ and CH₃ infrared and ¹³C NMR band intensities.     

Organic carbon and sulphur compounds in wetland soils: insights on structure and transformation processes using K-edge XANES and NMR spectroscopy

X-ray absorption near-edge structure (XANES) and nuclear magnetic resonance (NMR) spectroscopy were used in combination to characterize organic carbon structures in a series of wetland soils in Saskatchewan, and XANES spectroscopy was also used to examine sulphur speciation in the soils. The organic C contents of most of the wetland soils are consistently higher by a factor of two to five times compared to adjacent well-drained soils. NMR analyses indicate that the organic matter in the wetland soils consists of predominantly aliphatic structures such as carbohydrates and long chain poly(methylene) units which are refractory structures found in plant waxes. The poly(methylene) structures have a significant capacity to sorb nonpolar organic molecules. The phenolic OH and carboxyl group content of the wetland soils studied is an additional significant factor in their sequestering ability for heavy metals or pesticides. Carbon XANES spectroscopy shows that the surface (∼10 nm) layer of particulate organic matter has a structure dominated by aromatic, carbohydrate and carboxylic acid-like material apparently derived from partially degraded lignin and cellulose polymers which are adsorbed onto clay minerals. The aliphatic structures remaining in this surface layer are probably recalcitrant (poly)methylene units. At a depth of ∼100 nm, the aliphatic content significantly increases suggesting the presence of more labile structures. The presence of these more labile aliphatic compounds may be due to slow decomposition rates in the wet, often cool environments present and to the protective action of the more refractory components in the surface ∼10 nm of the organic matter. Drying of the wetlands, either by draining or as a result of climate change, is likely to result in the rapid decomposition of these labile organic structures releasing carbon dioxide. Our data indicate that the preservation of the organic carbon compounds in these soils is a result of their presence as surface adsorbed layers on the soil mineral particles. The soils contain three different classes of sulphur compounds: reduced organic sulphur such as sulphides, low valent oxidized sulphur such as sulphoxides, and high valent oxidized sulphur such as sulphonate and sulphate. Of these, reduced sulphur species constitute between one-third and two-thirds of the total. Sulphonate structures comprise between a fifth and a third of the total. Sulphates exhibit a wide variation in content, and sulphoxides are either not detected or are present to a lesser extent (<5%). Drying of the wetlands would cause oxidation of sulphides to sulphates.     

Chemical characterization of microbial-dominated soil organic matter in the Garwood Valley, Antarctica

Despite its harsh environmental conditions, terrestrial Antarctica contains a relatively large microbial biomass. Natural abundance carbon and nitrogen stable isotope signatures of organic materials in the dry valleys indicate mixed provenance of the soil organic matter (SOM) with varying proportions of contributions from lichens, mosses, lake-derived algae and cyanobacteria. Here we employed two complementary analytical techniques, biomarker measurements by gas chromatography/mass spectrometry and solution-state ¹H nuclear magnetic resonance spectroscopy, to provide further information at a molecular-level about the composition and possible source of SOM in the Garwood Valley, Antarctica. The predominance of branched alkanes and short-chain lipids in the solvent extracts indicates that the primary contribution to the SOM was microbial-derived. Chemical structures in the NaOH extracts from soils were also dominated by amide, peptides, and a CH₃-dominating aliphatic region that were characteristic of microbial signatures. Furthermore, the SOM in the Garwood Valley contained compounds that were different from those in the cyanobacteria-dominated mat from a nearby lake (including monoethyl alkanes and enriched side-chain protons). This observation suggests that easily degradable carbon sources from the nearby lake did not dominate the SOM, which is consistent with a fast turnover of the mat-derived organic matter found in the valley. This study highlights the important role of native soil microbes in the carbon transformation and biogeochemistry in terrestrial Antarctica.     

Organic Composition of Sulphide Ores in the Okinawa Trough and Its Implications

A preliminary organic geochemical study shows that the sulphide ores from the hydrothermal deposit of the Okinawa Trough are generally low in the total organic carbon and extremely low in the soluble organic matter. In the aliphatic hydrocarbon fraction, the n-alkanes range from C15 to C35, with usual maxima in the middle n-C20 region and strong odd-carbon number predominance when n > C25 (CPI = 1.2). The dominant analog in the aromatic fraction is phenanthrene, a polynuclear aromatic hydrocarbon, which provides evidence for hydrothermal activity. The organic matter derived mainly from marine planktonic and terrigenous vascular plants is entrapped in a high-temperature regime such as an active chimney and cooled quickly in the sulphide ores on the seafloor. Organic matter and sulphides are definitely products of a high-temperature alteration. The biomarker compounds indicate that the ores are formed under low Eh and pH conditions-a reducing to anoxic environment, which is favourable for sulphates to be     

Analysis of the organic matter of oil shales by nuclear magnetic resonance

¹³C NMR spectroscopy was applied in the investigation of the structure of the organic matter in oil shales. By using Proton Enhanced Nuclear Induction Spectroscopy, a fair resolution of aliphatic and aromatic carbon signals was achieved. This method provided information on the relative ratio of aliphatic and aromatic carbons within a given set of samples (Aleksinac, Kimmeridge, Colorado, Australian torbanite and Estonian kukersite).     

Organic geochemical analysis of sedimentary organic matter associated with uranium

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO₂ yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO₂ contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO₂ yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO₂ corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples.     

高磁场固态碳13核磁共振法研究干酪根的热降解成烃机理

用高磁场(75.46MH_Z)固态碳13核磁共振(NMR)波谱仪研究了抚顺油页岩在热降解模拟试验中干酪根的化学结构变化.为了消除旋转边带的干扰,在应用交叉极化与魔角自旋(CP/MAS)技术的同时,采用了Dixon TOSS技术,从而得到高分辨的波谱图。据此测定了热降解过程中干酪根各种碳结构组成的变化,计算了芳碳率、亚甲基基团平均碳原子数、环缩合指数等一系列干酪根的结构参数,并与干酪根的相对产油潜力相关联.发现干酪根的产油潜力直接与亚甲基基团的含量有关,而芳碳以及与芳碳相连的甲基碳则贡献甚微.文中还对干酪根的热降解成烃机理作了探讨。     

Temporal variability in sources of dissolved organic carbon in the lower Mississippi river

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and ¹³C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10⁻³ Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. ¹³C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly ¹³C-depleted with respect to bulk HMW DOM indicating that C₄ grass inputs to the HMW DOM were not significant. It is speculated that C₄ organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C₃ organic matter is, because of the association of C₄ organic matter with finer sediments. The predominantly aliphatic ¹³C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.     

Solid-state (H and C) nuclear magnetic resonance spectroscopy of insoluble organic residue in the Murchison meteorite: a self-consistent quantitative analysis

Complementary, double- and single-resonance solid-state (¹H and ¹³C) nuclear magnetic resonance (NMR) experiments were performed on a solvent extracted and demineralized sample of Murchison meteorite organic macromolecule. These NMR data provide a consistent picture of a complex organic solid composed of a wide range of organic (aromatic and aliphatic) functional groups, including numerous oxygen-containing functional groups. The fraction of aromatic carbon within the Murchison organic residue (constrained by three independent experiments) lies between 0.61 and 0.66. The close similarity in cross-polarized and single-pulse spectra suggests that both methods detect the same distribution of carbon. With the exception of interstellar diamond (readily detected in slow magic angle spinning single-pulse NMR experiments), there is no evidence in the solid-state NMR data for a significant abundance of large laterally condensed aromatic molecules in the Murchison organic insoluble residue. Given the most optimistic estimation, such carbon would not exceed 10% and more likely is a fraction of this maximum estimate. The fraction of aromatic carbon directly bonded to hydrogen is low (∼30%), indicating that the aromatic molecules in the Murchison organic residue are highly substituted. The bulk hydrogen content, H/C, derived from NMR data, ranges from a low of 0.53 ± 0.06 and a high of 0.63 ± 0.06. The hydrogen content (H/C) determined via elemental analysis is 0.53. The range of oxygen-containing organic functionality in the Murchison is substantial. Depending on whether various oxygen-containing organic functional groups exist as free acids and hydroxyls or are linked as esters and ethers results in a wide range in O/C (0.22 to 0.37). The lowest values are more consistent with elemental analyses, requiring that oxygen-containing functional groups in the Murchison macromolecule are highly linked. The combined ¹H and ¹³C NMR data reveal a high proportion of methine carbon, which requires that carbon chains within the Murchison organic macromolecule are highly branched.     

Molecular level analysis of long term vegetative shifts and relationships to soil organic matter composition

Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by ¹³C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state ¹³C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.     

河北夏家沟震旦纪页岩中可提取有机质的研究

前寒武纪占了地球地质历史的八分之七,其地层中有机质的研究,是一个十分重要的领域。它主要包括两个方面的意义:一方面在于追踪地球早期历史的生物演化,企图为了解地球上生命起源和早期生命的特点提供信息;另外在于对前寒武纪、特别是晚前寒武纪地层中石油的兴趣。六十年代,G. Eglinton和M. Calvin提出了“化学化石”的概念。“化学化石”也叫做分子化石或“地球化学化石”。     

Solid state C NMR studies of selected oil shales from Queensland, Australia

Solid state ¹³C NMR techniques of cross polarization with magic-angle spinning, and interrupted decoupling have been employed to examine the nature of the organic matter in eight kerogen concentrates representing five Tertiary deposits in Queensland, Australia. The NMR results show that five of the kerogens have high proportions of aliphatic carbon in their organic matter and correspond to Type I–II algal kerogens. Three of the kerogens, derived from carbonaceous shales, have a high proportion of aromatic carbon in their organic matter and correspond to Type III kerogens. The fractions of aliphatic carbon in all the kerogens, regardless of type, are shown to correlate with the conversion characteristics of the corresponding raw shales during Fischer assay. Interrupted decoupling NMR results show the presence of more oxygen-substituted carbon in the carbonaceous shales, which may account for the greater CO₂ evolution and phenolic materials found in the pyrolysis products of the carbonaceous shales.