Mechanism of methane adsorption on groove space in organic matter surface

Organic matter plays an important role in methane adsorption in shale. Pore surface of organic matter is usually rough and uneven, which results in a large amount of groove space on the pore surface. Thus, the influence of groove space on the adsorption capacity of methane in shale cannot be neglected. Nanoscale pore structures of the organic-rich shale in the Longmaxi Formation were investigated by low-pressure nitrogen gas adsorption as a basis for constructing models. We simplified the internal groove space into triangular prisms with different angles. The grand canonical Monte Carlo simulation and molecular dynamics simulation were used to analyse the methane molecule adsorption behaviour in pores. The results showed that the pore morphology of organic-rich shale in the Longmaxi Formation was mainly slit-shaped pores. The excess adsorption isotherms showed good agreement between experiment and simulation, indicating that the model is suitable and reliable. Methane molecules can enter into the groove space with an opening size of 0.738 nm, while they fail to enter into groove spaces with an opening size less than 0.492 nm. This understanding has important significance for the study of the adsorption characteristics of organic pores which have undergone multiple evolutions in geological history.     

Palynofacies and biomarker analysis of the lowermost Permo–Carboniferous Pular Formation,a volcanic arc sequence in the Sierra de Almeida,Northern Chile

Palynofacies and molecular organic geochemical analyses indicate a probable lacustrine origin for three organic-rich black shale samples from the lowermost Pular Formation (Permo–Carboniferous) of northern Chile. The three samples examined exhibit high values for total organic carbon and hydrogen indices. Biomarkers and stable carbon isotopic compositions (−36.5 to −35.5‰) are typical for oil-prone type I organic matter associated with lacustrine source rocks and derived oils. Amorphous kerogen dominates the samples, and two distinct palynofacies can be recognized. The palynofacies can be visually distinguished by the presence/absence of petrofilaments, presence/absence of terrestrial organic material, and weak versus strong fluorescence. These organic facies can also be separated using hydrogen indices, the abundance of n-C₂₄₊ paraffins, sterane (C₂₇, C₂₈, C₂₉) patterns, and the relative amounts of perhydro-β-carotene.     

Control of stomatal aperture: A renaissance of the old guard

Stomata, functionally specialized small pores on the surfaces of leaves, regulate the flow of gases in and out of plants. The pore is opened by an increase in osmotic pressure in the guard cells, resulting in the uptake of water. The subsequent increase in cell volume inflates the guard cell and culminates with the opening of the pore. Although guard cells can be regarded as one of the most thoroughly investigated cell types, our knowledge of the signaling pathways which regulate guard cell function remains fragmented. Recent research in guard cells has led to several new hypotheses, however, it is still a matter of debate as to whether guard cells function autonomously or are subject to regulation by their neighboring mesophyll cells. This review synthesizes what is known about the mechanisms and genes critical for modulating stomatal movement. Recent progress on the regulation of guard cell function is reviewed here including the involvement of environmental signals such as light, the concentration of atmospheric CO₂ and endogenous plant hormones. In addition we re-evaluate the important role of organic acids such as malate and fumarate play in guard cell metabolism in this process.Key words: stomata movement, ions, organic acids, malate, fumarate, CO₂, ABA, light     

Arctic sediments (Svalbard): pore water and solid phase distributions of C,N, P and Si

Pore water and solid phase distributions of C, N, P and Si in sediments of the Arctic Ocean (Svalbard area) have been investigated. Concentrations of organic carbon (C_org) in the solid phase of the sediment varied from 1.3 to 2.8% (mean 1.9%), with highest concentrations found at shallow stations south/southwest of Svalbard. Relatively low concentrations were obtained at the deeper stations north/northeast of Svalbard. Atomic carbon to nitrogen ratios in the surface sediment ranged from below 8 to above 10. For some stations, high C/N ratios together with high concentrations of C_org suggest that sedimentary organic matter is mainly of terrigenous origin and not from overall biological activity in the water column. Organic matter reactivity (defined as the total sediment oxygen consumption rate normalized to the organic carbon content of the surface sediment) correlated with water depth at all investigated stations. However, the stations could be divided into two separate groups with different reactivity characteristics, representing the two most dominant hydrographic regimes: the region west of Svalbard mainly influenced by the West Spitsbergen Current, and the area east of Svalbard where Arctic polar water set the environmental conditions. Decreasing sediment reactivity with water depth was confirmed by the partitioning between organic and inorganic carbon of the surface sediment. The ratio between organic and inorganic carbon at the sediment-water interface decreased exponentially with water depth: from indefinite values at shallow stations in the central Barents Sea, to approximately 1 at deep stations north of Svalbard. At stations east of Svalbard there was an inverse linear correlation between the organic matter reactivity (as defined above) and concentration of dissolved organic carbon (DOC) in the pore water. The more reactive the sediment, the less DOC existed in the pore water and the more total carbonate (C_t or ΣCO₂) was present. This observation suggests that DOC produced in reactive sediments is easily metabolizable to CO₂. Sediment accumulation rates of opaline silica ranged from 0.35 to 5.7 μmol SiO₂ m⁻²d⁻¹ (mean 1.3 μmol SiO₂ m⁻²d⁻¹), i.e. almost 300 times lower than rates previously reported for the Ross Sea, Antarctica. Concentrations of ammonium and nitrate in the pore water at the sediment-water interface were related to organic matter input and water depth. In shallow regions with highly reactive organic matter, a pool of ammonium was present in the pore water, while nitrate conoentrations were low. In areas where less reactive organic matter was deposited at the sediment surface, the deeper zone of nitrification caused a build-up of nitrate in the pore water while ammonium was almost depleted. Nitrate penetrated from 1.8 to ≥ 5.8 cm into the investigated sediments. Significantly higher concentrations of “total” dissolved nitrogen (defined as the sum of NO₃, NO₂, NH₄ and urea) in sediment pore water were found west compared to east of Svalbard. The differences in organic matter reactivity, as well as in pore water distribution patterns of “total” dissolved nitrogen between the two areas, probably reflect hydrographic factors (such as ice coverage and production/import of particulate organic material) related to the dominant water mass (Atlantic or Arctic Polar) in each of the two areas. The data presented were collected during the European “Polarstern” Study (Arctic EPOS) sponsored by the European Science Foundation     

Bacillus agar-exedens,a new species,decomposing agar

Conclusions In stable manure, leafmold and soils (especially those with a high content of organic material) agar decomposing bacilli are relatively common. Different types of these organisms were isolated, the type described asBacillus agar-exedens being the one most frequently met. The occurrence of these bacteria in materials with a high content of organic matter suggests the presence in these materials of higher organic compounds, especially apt for their nutrition.     

Nanopore sequencing technology: nanopore preparations

For the past decade, nanometer-scale pores have been developed as a powerful technique for sensing biological macromolecules. Various potential applications using these nanopores have been reported at the proof-of-principle stage, with the eventual aim of using them as an alternative to de novo DNA sequencing. Currently, there have been two general approaches to prepare nanopores for nucleic acid analysis: organic nanopores, such as alpha-hemolysin pores, are commonly used for DNA analysis, whereas synthetic solid-state nanopores have also been developed using various conventional and non-conventional fabrication techniques. In particular, synthetic nanopores with pore sizes smaller than the alpha-hemolysin pores have been prepared, primarily by electron-beam-assisted techniques: these are more robust and have better dimensional adjustability. This review will examine current methods of nanopore preparation, ranging from organic pore preparations to recent developments in synthetic nanopore fabrications.     

Preservation of overmature,ancient, sedimentary organic matter in carbonate concretions during outcrop weathering

Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly ¹³C‐depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate‐free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ¹³C_carb) range from ?22.5 to ?3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ¹³C_org) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings indicate that concretions can promote delayed oxidative weathering of organic carbon in outcrop and therefore impact local chemical cycling.     

The origin and recycling of sedimented biogenic debris in a subalphine eutrophic lake (Lake Bled, Slovenia)

The areal distribution of organic C contents, ¹³C values, total N and P and biogenic Si contents in surficial sediments were used to study the distribution, origin and diagenetic transformations of sedimented biogenic debris in the eutrophic subalpine Lake Bled (Slovenia), which for most of the yearhas an anoxic hypolimnion. The influence of an allochthonous input, restricted to the western basin, was clearly traced by higher organic C and total N and P contents, higher ¹³C values, and higher sedimentation rate in comparison to the eastern basin. The low ¹³C values of sedimentary organic matter in the major part of the lake, lower than the ¹³C values of different types of organic matter, suggest that this sedimentary organic matter is most probably the product of a microbial community and not a residue of primary production.The temporal variation of benthic diffusive fluxes of NH₄, Si and PO₄, derived from modelling the pore water profiles, was related to sedimentation of phytoplanktonic blooms, while the PO₄ fluxes were also dependent on changing redox conditions at the sediment-water interface in the period of the winter-spring overtum. The removal of PO₄ in pore waters is probably due to the adsorption of phosphate and precipitation of apatite and vivianite. The budget of C, N and P at the sediment-water interface revealed a high recycling efficiency (>70%), also confirmed by the rather uniform (or only slightly decreasing) vertical profiles of organic C, total N and P in sediment cores and C/N and C/P ratios. The percentage of biogenic Si recycling is low (<10%), suggesting its removal in sediments.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

Permeation of styryl dyes through nanometer-scale pores in membranes

Styryl dyes are widely used to study synaptic vesicle (SV) recycling in neurons; vesicles are loaded with dye during endocytosis, and dye is subsequently released via exocytosis. During putative kiss-and-run exocytosis, efflux of dye from individual SVs has been proposed to occur via two sequential steps: dissociation from the membrane followed by permeation through a small fusion pore. To improve our understanding of the kinetics of efflux of dye from vesicles during kiss-and-run events, we examined the rates of efflux of different dyes through nanometer-scale pores formed in membranes by the toxins melittin and α-hemolysin; these pores approximate the size of fusion pores measured in neuroendocrine cells. We found that the axial diameter of each dye was a crucial determinant for permeation. Moreover, the two dyes with the largest cross-sectional areas were completely unable to pass through pores formed by a mutant α-hemolysin that has a slightly smaller pore than the wild-type toxin. The overall time constant for efflux (seconds) of each dye was orders of magnitude slower than the time constant for dissociation from membranes (milliseconds). Thus, the permeation step is rate-limiting, and this observation was further supported by atomistic molecular dynamics simulations. Together, the data reported here help provide a framework for interpreting dye destaining rates from secretory vesicles.     

Photosynthetic changes and oxidative stress caused by iron ore dust deposition in the tropical CAM tree Clusia hilariana

The effect of iron solid particulate matter (SPM_Fe) deposited onto soil and leaves on photosynthesis and oxidative stress was evaluated in Clusia hilariana, a CAM tropical tree of high occurrence in Brazilian restingas. Significant increases in iron content were found in plants exposed to SPM_Fe applied onto leaf and soil surfaces. However, only the application of SPM_Fe on leaves of C. hilariana caused significant reductions in some evaluated characteristics such as photosynthetic rate, stomatal conductance, transpiration, organic acid accumulation, potential quantum yield of PSII, and changes in daily CAM photosynthesis pattern. Increase in relative membrane permeability and reduction in catalase and superoxide dismutase activities in the leaves of plants exposed to SPM_Fe also were observed; however, lipid peroxidation did not change. These responses seem to be due to the combination of physical effects such as increase of leaf temperature, reduction in light absorption, obstruction of stomatal pores, and biochemical effects triggered by oxidative stress.     

Influence of arbuscular mycorrhizal fungi on soil structure and soil water characteristics of vertisols

The influence of inoculation with arbuscular mycorrhizal fungi (AM fungi) on soil water characteristics of fast and slowly wetted vertisol samples was studied. Vertisols characteristically have a low stability to wetting, and the disruption of their larger pores when they swell leads to reduced water infiltration and thereby to runoff. The degree of aggregate breakdown determines the ability of the soil to drain. A vertisol was used in this pot experiment with four treatments: T₁: Pasteurized soil, T₃: Pasteurized soil, with plants, T₄: Inoculated, pasteurized soil, with plants, T₅: Unpasteurized soil, with plants. A treatment using inoculated, pasteurized soil (T₂) was included in a related study (Bearden and Petersen, 2000) comparing aggregate stability, and the present study follows the same numbering to aid in comparison of experiments. After fast, disruptive wetting, the soil inoculated with AM fungi (T₄) was found to have a lower soil water content than did the soils from the other treatments at matric potentials lower than –3.92 kPa. This indicates greater drainage from pores smaller than 75 m for the soil inoculated with AM fungi, and the greater drainage appears to be directly related to a characteristic pore range between 67 and 75 m. The soil without plants (T₁), when wetted fast, had a lower soil water content at matric potentials higher than –3.92 kPa than soils from the other treatments, which indicates less pore volume due to pores larger than 75 m in the treatment without plants. The pore indexes, calculated as the ratio between the slope of the fast and the slope of the slowly-wetted water characteristics, generally had the highest values for the soil inoculated with AM fungi (T₄) from matric potential 0.00 to –0.29 kPa. In this matric potential range, the pore indexes were less than one. The unpasteurized soil with naturally present AM fungi (T₅) generally had the highest pore indexes from matric potential –0.49 to –3.92 kPa, and the pore indexes in this matric potential range were above one. These results indicate the smallest loss of very large pores in the soil inoculated with AM fungi (T₄) and the largest gain of smaller sized pores in the unpasteurized soil (T₅). This suggests that the resistance to breakdown of the largest pores is related to the presence of roots, and that the gain of groups of smaller pores is related to the presence of hyphae.     

TIME SEQUENCE OF NUCLEAR PORE FORMATION IN PHYTOHEMAGGLUTININ-STIMULATED LYMPHOCYTES AND IN HELA CELLS DURING THE CELL CYCLE

The time sequence of nuclear pore frequency changes was determined for phytohemagglutinin (PHA)-stimulated human lymphocytes and for HeLa S-3 cells during the cell cycle. The number of nuclear pores/nucleus was calculated from the experimentally determined values of nuclear pores/µ² and the nuclear surface. In the lymphocyte system the number of pores/nucleus approximately doubles during the 48 hr after PHA stimulation. The increase in pore frequency is biphasic and the first increase seems to be related to an increase in the rate of protein synthesis. The second increase in pores/nucleus appears to be correlated with the onset of DNA synthesis. In the HeLa cell system, we could also observe a biphasic change in pore formation. Nuclear pores are formed at the highest rate during the first hour after mitosis. A second increase in the rate of pore formation corresponds in time with an increase in the rate of nuclear acidic protein synthesis shortly before S phase. The total number of nuclear pores in HeLa cells doubles from ~2000 in G₁ to ~4000 at the end of the cell cycle. The doubling of the nuclear volume and the number of nuclear pores might be correlated to the doubling of DNA content. Another correspondence with the nuclear pore number in S phase is found in the number of simultaneously replicating replication sites. This number may be fortuitous but leads to the rather speculative possibility that the nuclear pore might be the site of initiation and/or replication of DNA as well as the site of nucleocytoplasmic exchange. That is, the nuclear pore complex may have multiple functions.     

Fusion pore expansion is a slow, discontinuous, and Ca2+-dependent process regulating secretion from alveolar type II cells

In alveolar type II cells, the release of surfactant is considerably delayed after the formation of exocytotic fusion pores, suggesting that content dispersal may be limited by fusion pore diameter and subject to regulation at a postfusion level. To address this issue, we used confocal FRAP and N-(3-triethylammoniumpropyl)-4-(4-[dibutylamino]styryl) pyridinium dibromide (FM 1-43), a dye yielding intense localized fluorescence of surfactant when entering the vesicle lumen through the fusion pore (Haller, T., J. Ortmayr, F. Friedrich, H. Volkl, and P. Dietl. 1998. Proc. Natl. Acad. Sci. USA. 95:1579-1584). Thus, we have been able to monitor the dynamics of individual fusion pores up to hours in intact cells, and to calculate pore diameters using a diffusion model derived from Fick's law. After formation, fusion pores were arrested in a state impeding the release of vesicle contents, and expanded at irregular times thereafter. The expansion rate of initial pores and the probability of late expansions were increased by elevation of the cytoplasmic Ca2+ concentration. Consistently, content release correlated with the occurrence of Ca2+ oscillations in ATP-treated cells, and expanded fusion pores were detectable by EM. This study supports a new concept in exocytosis, implicating fusion pores in the regulation of content release for extended periods after initial formation.     

喀斯特峰丛洼地不同森林表层土壤有机质的空间变异及成因

基于动态监测样地(200 m×40 m)的网格(10 m×10 m)取样,以农作区为对照,用地统计学方法研究了喀斯特峰丛洼地人工林、次生林和原生林3类典型森林生态系统表层土壤(0—15 cm)有机质的空间变异,通过主成分分析和相关分析,探讨了其生态学过程和机制。结果表明:喀斯特峰丛洼地土壤有机质很高,沿着农作区-人工林-次生林-原生林的恢复梯度,土壤有机质显著提高,变异系数逐步增大;农作区和3类森林土壤表层有机质均具有良好的空间自相关性;农作区试验半变异函数C0/(C0+C)值为26.5%,呈中等程度的空间相关性;3类森林的C0/(C0+C)值为9.0%—22.6%,呈强烈的空间相关性;农作区和人工林土壤有机质呈单峰分布,次生林呈凹型分布,原生林呈凸型分布;不同森林的主导因子不同,农作区的主导因子为主要土壤养分,人工林为地形和物种多样性,次生林为森林结构和物种多样性,原生林为地形和物种多样性,且同一因子在不同森林与土壤表层有机质的正负作用关系和相关程度也不同。因此,农作区和3类森林应根据其土壤表层有机质的空间变异及主要影响因子制定相应的固碳措施。     

Impact of Contaminants From Oil Shale Processing on Forest Ecosystems

Oil shale mining and processing in northeast Estonia have brought about several ecological problems. The mined oil shale is used as fuel in power stations and in processing plants producing crude oil and about 40 manufactured articles. Pollutants emitted from oil shale processing and chemical plants include SO₂, CO, NO _x , oil shale fly ash, and organic compounds in which aromatic and aliphatic hydrocarbons, phenols, formaldehyde, etc., are represented. Pollution has caused changes in the condition of the forest ecosystem and the chemical character of soil and ground water. The condition of coniferous forest sites was investigated in 1995–1998. Because of the high concentration of alkaline fly ash in the air, the pH of rain water is somewhat elevated (pH = 7.0–7.1) and exceeds the level regarded as normal for rain water. The analysis of the soil samples showed that the concentrations of Ca, Mg and K, which dominate in the solid fraction of the pollutant mixture, are high, being respectively 18, 14, and 4 times as high as the control. The increases in the concentrations of K, Mg, Cu, Pb, and Ni in stemwood reflect increases in the regional oil shale fly ash deposition. Conifers influenced by high levels of air pollution emitted from the oil shale industry are characterized by retarded growth of needles and shoots and radial growth as a result of disturbances in their mineral nutrition and imbalance in their mineral composition.     

Alteration of the structural attributes of a compact clay loam soil by growth of a perennial grass crop

Soil aggregate stability, organic matter content, pH, bulk density, strength, and macropore attributes were assessed in order to evaluate the influence of grass root growth in a field sward. The amount of grass grown was varied by varying the quantity of applied nitrogen fertilizer: following one year with a uniform application rate, nitrogen fertilizer was applied over the subsequent three years to a compact soil at zero (N0), moderate (N1) and high (N2) rates. Differences in herbage production were evident in the three years of the contrasting nitrogen treatments. An index of soil aggregate stability increased in response to the increased grass growth promoted by heavier applications of nitrogen, but both bulk density and vane shear strength were unchanged. Binary images of the soil solid and pore space showed that for each treatment the largest volume of macropores occurred close to the surface, particularly in N0 where there was more pore space than in either N1 or N2. Analysis of the pore structure attributes of the binary images revealed further differences between treatments, in particular, at 40–80 mm depth, the soil in treatment N0 had fewer and smaller pores, and greater distance between pores, than the soil in the N1 and N2 treatments. The larger macropore volume in N1 and N2 constituted a major portion of the air-filled porosity when the soil was relatively wet. It was concluded that the root growth in the intensively cropped grassland was conducive to maintenance of a relatively stable and porous soil structure. An attendant increase in soil acidity close to the soil surface was a disadvantage of the larger nitrogen inputs.     

Nanoscale petrographic and geochemical insights on the origin of the Palaeoproterozoic stromatolitic phosphorites from Aravalli Supergroup,India

Stromatolites composed of apatite occur in post‐Lomagundi–Jatuli successions (late Palaeoproterozoic) and suggest the emergence of novel types of biomineralization at that time. The microscopic and nanoscopic petrology of organic matter in stromatolitic phosphorites might provide insights into the suite of diagenetic processes that formed these types of stromatolites. Correlated geochemical micro‐analyses of the organic matter could also yield molecular, elemental and isotopic compositions and thus insights into the role of specific micro‐organisms among these communities. Here, we report on the occurrence of nanoscopic disseminated organic matter in the Palaeoproterozoic stromatolitic phosphorite from the Aravalli Supergroup of north‐west India. Organic petrography by micro‐Raman and Transmission Electron Microscopy demonstrates syngeneity of the organic matter. Total organic carbon contents of these stromatolitic phosphorite columns are between 0.05 and 3.0 wt% and have a large range of δ¹³C_org values with an average of ?18.5‰ (1σ = 4.5‰). δ¹⁵N values of decarbonated rock powders are between ?1.2 and +2.7‰. These isotopic compositions point to the important role of biological N₂‐fixation and CO₂‐fixation by the pentose phosphate pathway consistent with a population of cyanobacteria. Microscopic spheroidal grains of apatite (MSGA) occur in association with calcite microspar in microbial mats from stromatolite columns and with chert in the core of diagenetic apatite rosettes. Organic matter extracted from the stromatolitic phosphorites contains a range of molecular functional group (e.g. carboxylic acid, alcohol, and aliphatic hydrocarbons) as well as nitrile and nitro groups as determined from C‐ and N‐XANES spectra. The presence of organic nitrogen was independently confirmed by a CN^? peak detected by ToF‐SIMS. Nanoscale petrography and geochemistry allow for a refinement of the formation model for the accretion and phototrophic growth of stromatolites. The original microbial biomass is inferred to have been dominated by cyanobacteria, which might be an important contributor of organic matter in shallow‐marine phosphorites.     

Editorial

Abstract

Grand canonical molecular dynamics (GCMD) simulations are used to study the adsorption and desorption of Lennard-Jones nitrogen in three slit pore junction models of microporous graphite. These networks consist of two narrow pores separated by a wider (cavity) pore. We report results for cases where the narrow pore has a width of only two or three molecular diameters. Using the GCMD technique, a novel freezing transition is observed which results in pore blocking in the narrow pores of the network, which are less than 1 nm wide. This freezing results from the adsorption energy barrier at the junction between the narrow and wider pores. This type of pore blocking could account for the apparent increase in pore volume with increasing temperature that has been experimentally observed in microporous graphite systems. For networks in which the narrower pores are somewhat larger, with a width of 1.28 nm, this pore blocking effect is much reduced, and adsorbate molecules enter and fill the central cavity. In such cases, however, desorption is incomplete, some residual adsorbate remaining in the central cavity even at the lowest pressures.