Effect of N content and soil texture on the decomposition of organic matter in forest soils as revealed by solid-state CPMAS NMR spectroscopy

N has a controlling effect on litter biodegradation in the forest floor, while stabilization of organic matter in the mineral soil may be influenced by physical parameters related to soil texture. In this study, in order to understand the processes involved in soil organic matter (SOM) formation, the chemical composition of SOM was followed and evaluated with regards to N contents and soil texture. Samples were taken on sites covered with Norway spruce and displaying contrasting values of C/N ratios in the forest floor. The chemical structure of OM was characterized using solid-state CPMAS ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy, along with Proton Spin Relaxation Editing (PSRE) sequences. Four groups of sampling sites were defined based on the NMR spectra of Oh and A horizons. In each group displaying similar NMR characteristics, N content and soil texture could be highly different among sites. Some Oh horizons with similar NMR spectra had very different N contents. Highly humified OM in Oh horizons were observed mainly on sites with low N contents. Some A horizons with different soil texture displayed similar OM chemical structure. High contents of O-alkyl C in some A horizons could originate from higher fresh root material input.     

Compositional diversity in insoluble organic matter in type 1, 2 and 3 chondrites as detected by infrared spectroscopy

Insoluble organic matter (IOM) isolated from 22 carbonaceous and ordinary chondrites spanning a wide range of groups and petrologic types were analyzed using Fourier transform infrared spectroscopy (FTIR). Based on common IR spectral features, it is observed that IOM falls into 4 molecularly distinct groups (designated here as A through D). Spectral group A includes type 1 and 2 chondrites and exhibits intense aliphatic C-H and carboxyl vibrational peaks. Spectral group B includes the least metamorphosed type 3 chondrites and Tagish Lake, and exhibits weaker aliphatic and carboxyl vibrational intensity. Spectral groups C and D include metamorphosed type ?3.1 chondrites and a heated CM chondrite. The carbonyl stretching features in spectral groups C and D differ from that in spectral groups A and B and from each other. In spectral group C, the carbonyl stretching is assigned to cyclic unsaturated lactones; in spectral group D carbonyl exists predominantly in the form of unsaturated ketone moieties. Both spectral groups C and D have a relatively narrow band structure around 1210 cm⁻¹ (assigned to aromatic skeletal modes) as compared with spectral groups A and B, which is consistent with the formation of more condensed aromatics by extensive thermal metamorphism. The differences in carbonyl structures in spectral groups C and D are not the result of different effective metamorphic temperatures, rather these differences likely result from variation in the activity of water and oxygen at different stages of parent body metamorphism. Such environmental variations must be local phenomena in the parent bodies as there is no correlation between spectral grouping and chondrite class or group.     

渤中坳陷石臼陀凸起东段幔源CO2充注对储集层粘土矿物的影响

探讨了渤中坳陷石臼陀凸起东段CO2来源及CO2充注对储层粘土矿物的影响.研究表明,CO2中δ13C组成较重,R/Ra值较大,CO2为幔源成因;控盆的深大断裂是CO2的主要运移通道;CO2热流体晚期充注对砂岩储集层粘土矿物产生了明显的影响:CO2热流体侵位后形成的热波动效应加快了储集层中伊蒙混层粘土的演化,含CO2储集层中伊蒙混层中蒙脱石含量要比同深度的泥岩低15％ ～30％;CO2热流体晚期侵入加剧了长石的溶蚀作用,长石溶蚀促进了自生高岭石的大量形成;CO2热流体侵位后形成的偏酸性环境抑制伊利石生长,促进了其他粘土矿物向高岭石转化;含CO2储集层以少见的高自生高岭石、低伊利石为特征,这对储层物性改善起到了决定性的影响.     

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state C nuclear magnetic resonance spectroscopy

Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH_n selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO₂ adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO₂ saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO₂ saturation. After exposure to high pressure CO₂, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO₂ adsorption samples compared to the original lithotypes. These observations suggested chemical CO₂-coal interactions at high pressure and the selectivity of lithotypes in response to CO₂ adsorption.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.     

The nature of hydroxyl groups in aluminosilicate glasses: Quantifying Si-OH and Al-OH abundances along the SiO2-NaAlSiO4 join by H, Al-H and Si-H NMR spectroscopy

The combined results of ²⁷Al-¹H and ¹H-²⁹Si-¹H cross polarization NMR experiments for hydrous glasses (containing 0.5-2 wt% water) along the SiO₂-NaAlSiO₄ join confirm that the dissolution mechanism of water in aluminosilicate glasses is fundamentally the same as for Al-free systems, i.e. the dissolved water ruptures oxygen bridges and creates Si-OH and Al-OH groups, in addition to forming molecular water (H₂O_mol). The fraction of Al-OH increases non-linearly as the Al content increases with up to half of the OH groups as Al-OH for compositions close to NaAlSiO₄. The relative abundances of the different species are controlled by the degree of Al-avoidance and the relative tendency of hydrolysis of the different types of oxygen bridges, Si-O-Si, Si-O-Al and Al-O-Al. A set of homogeneous reactions is derived to model the measured Al-OH/Si-OH speciation, and the obtained equilibrium constants are in agreement with literature data on the degree of Al-avoidance. With these equilibrium constants, the abundance of the different oxygen species, i.e. Si-O-Si, Si-O-Al, Al-O-Al, Si-OH, Al-OH and H₂O_mol, can be predicted for the entire range of water and Al contents.