Carbon isotopic fractionation in lipids from methanotrophic bacteria: relevance for interpretation of the geochemical record of biomarkers

Experiments with cultured aerobic methane oxidising bacteria confirm that their biomarker lipids will be significantly depleted in 13C compared to the substrate. The methanotrophic bacteria Methylococcus capsulatus and Methylomonas methanica, grown on methane and using the RuMP cycle for carbon assimilation, show maximum 13C fractionation of approximately 30% in the resultant biomass. In M. capsulatus, the maximum fractionation is observed in the earliest part of the exponential growth stage and decreases to approximately 16% as cells approach stationary phase. This change may be associated with a shift from the particulate form to the soluble form of the methane monooxygenase enzyme. Less than maximum fractionation is observed when cells are grown with reduced methane availability. Biomass of M. capsulatus grown on methanol was depleted by 9% compared to the substrate. Additional strong 13C fractionation takes place during polyisoprenoid biosynthesis in methanotrophs. The delta 13C values of individual hopanoid and steroid biomarkers produced by these organisms were as much as l0% more negative than total biomass. In individual cultures, squalene was 13C-enriched by as much as 14% compared to the triterpane skeleton of bacteriohopaneaminopentol. Much of the isotopic dispersion in lipid metabolites could be attributed to shifts in their relative abundances, combined with an overall reduction in fractionation during the growth cycle. In cells grown on methanol, where there was no apparent effect of growth stage on overall fractionation there were still significant isotopic differences between closely related lipids including a 5.3% difference between the hopane and 3 beta-methylhopane skeletons. Hopane and sterane polyisoprenoids were also 13C-depleted compared to fatty acids. These observations have significant implications for the interpretation of specific compound isotopic signatures now being measured for hydrocarbons and other lipids present in sediments and petroleum. In particular, biomarker lipids produced by a single organism do not necessarily have the same carbon isotopic composition.     

A photochemical model of the martian atmosphere

The factors governing the amounts of CO, O2, and O3 in the martian atmosphere are investigated using a minimally constrained, one-dimensional photochemical model. We find that the incorporation of temperature-dependent CO2 absorption cross sections leads to an enhancement in the water photolysis rate, increasing the abundance of OH radicals to the point where the model CO abundance is smaller than observed. Good agreement between models and observations of CO, O2, O3, and the escape flux of atomic hydrogen can be achieved, using only gas-phase chemistry, by varying the recommended rate constants for the reactions CO + OH and OH + HO2 within their specified uncertainties. Similar revisions have been suggested to resolve discrepancies between models and observations of the terrestrial mesosphere. The oxygen escape flux plays a key role in the oxygen budget on Mars; as inferred from the observed atomic hydrogen escape, it is much larger than recent calculations of the exospheric escape rate for oxygen. Weathering of the surface may account for the imbalance. Quantification of the escape rates of oxygen and hydrogen from Mars is a worthwhile objective for an upcoming martian upper atmospheric mission. We also consider the possibility that HOx radicals may be catalytically destroyed on dust grains suspended in the atmosphere. Good agreement with the observed CO mixing ratio can be achieved via this mechanism, but the resulting ozone column is much higher than the observed quantity. We feel that there is no need at this time to invoke heterogeneous processes to reconcile models and observations.     

Radiation-hydrodynamic waves and global solar oscillations

We investigate nonadiabatic hydrodynamic waves in a nongrey, radiating, thermally conducting, homogeneous atmosphere in LTE with a finite mean free path of photons. Avoiding the Eddington approximation the remaining simplifications in the basic equations are discussed, the generalized dispersion relation is analysed, and some wave properties in a grey model are studied. The properties of waves in a stratified atmosphere are analysed as well. In connection with the predicted properties of the nonadiabatic waves we discuss observations ofp-modes by measuring brightness fluctuations.     

A quantitative model of coherent,stimulated emission in astrophysical jets

On the basis of issues raised by observations of BL Lac objects and the qualitative jet model proposed by Bakeret al. in 1988, we have been led to consider the quantitative role of coherent, stimulated emission in jets and construct a new jet model of blazars in which a relativistic electron beam with an axial symmetric, power-law distribution is injected from the central engine into the jet plasma. We study quantitatively the synchrotron emission of the relativistic electron beams. Using the weak turbulent theory of plasma, we discuss the interaction between relativistic electron beams and jet plasma, and the roles of stimulated emission. The main results are:

1. The synchrotron emission increases sensitively with the increase of the angle between the direction of the beam and the magnetic field. When the direction of the beam is vertical to the magnetic field, the synchrotron emission reaches its maximum, i.e. the emitted waves are beamed in the direction of the jet axis. We suggest that radio selected BL Lac objects belong to this extreme classification.
2. The synchrotron emission of the relativistic beam increases rapidly with the increase of the Lorentz factor of the relativistic electron,γ, whenγ ≤ 22.5, then decreases rapidly with increase ofγ.
3. The stimulated emission also increases with increasing Lorentz factorγ of the relativistic electrons whenγ ≤ 35 and then decreases with the increasingγ. The maximum stimulated emission and the maximum synchrotron emission occur at different frequencies. Stimulated emission is probably very important and reasonable flare mechanism in blazars.
4. The rapid polarization position angle (PA) swings may arise from the interaction between the relativistic electron beam and the turbulent plasma.

     

Arctic haze: Perturbation to the radiation field

Summary A model of the polluted arctic troposphere is constructed to estimate the magnitude and seasonal variation of the climate forcing function of arctic haze. Using a pill-box bathtub model for the Arctic and envisioning it to be filled with pollution from industrial sources in Eurasia, we estimate that maximum climate perturbation from arctic contamination occurs in the spring months. The major perturbation to the radiation budget is a lowering of the albedo (heating) of the earth-atmosphere system around the vernal equinox and is due to a trace amount (about 5% by mass) of black carbon associated with the removal-resistant submicron mode of aerosols. The black carbon over the reflecting polar ice/snow introduces a heating of about 1.5 degree per day into the haze layer.With 8 Figures     

On the sampling of airborne measurements of radiative properties of cloud fields: Results from International Cirrus Experiment (ICE), 1987

Summary During the first pilot phase of the International Cirrus Experiment (ICE) in September/October 1987 radiation measurements were carried out above and below broken cloud fields over the German Bight. Analyses of the measurements of 25.9.1987 (broken cumulus cloud field) showed an unexpected high absorption of solar radiation but not those of 28.9.1987 (stratocumulus/stratus cloud field). This might be explained by a partial negligence of cloud side factor under the viewing geometry of the pyranometer and other reasons. The light guide effect (leakage) within holes can account for the depletion of cloud reflectance and the enhancement of cloud transmittance at large cloud cover, as observed during the measurements on 28.9.1987. The fluctuation of the irradiances, which can be characterized by the intermittency parameter, has been related to the corresponding cloud cover by a regression equation. On the condition of similarity, this scaling parameter derived from sample measurements could be extrapolated to that of the whole cloud field. Thus, the estimation of the irradiance spectrum for the whole cloud field may be possible, from samples taken with aircraft and imaging data.With 5 Figures     

Kinetics of peptide hydrolysis and amino acid decomposition at high temperature

Dipeptide hydrolysis and amino acid decomposition appear to follow a first-order rate law. The hydrolysis rate increases exponentially with increasing temperature in aqueous solution at both 265 atm and water steam pressures over the temperature range of 100 to 220 degrees C. Dipeptide hydrolysis has a lower apparent activation energy at 265 atm (44.1 KJ/mol) than at water steam pressure (98.9 KJ/mol). At lower temperatures (<200-220 degrees C), the rate of peptide bond hydrolysis is faster at 265 atm than at water steam pressure. At higher temperatures (>200-220 degrees C), however, peptide bond hydrolysis is slower at 265 atm than at water steam pressure. In aqueous solution, amino acid decomposition rates also increase exponentially with increasing temperature. Amino acid decomposition rates are much higher at 265 atm than at water steam pressure over the entire temperature range investigated.     

Partitioning of silver,beryllium and molybdenum among chemical fractions in the sediments from the Labe (Elbe) river in Central Bohemia,Czech Rep.

Sequential extraction of the fine fraction (63 µm) of the bottom sediments of the Labe river in Central Bohemia indicates that the readily reducible sediment fraction is a major reservoir of silver for release into the aqueous phase. Molybdenum is preferentially mobilized by ion-exchange, while beryllium is accumulated in all the chemical fractions of the sediments, especially in the moderately reducible and the organic/sulphidic phases.Contamination of the aquatic system from anthropogenic sources is characterized by the formation of relatively unstable chemical forms and only a small portion of these elements remain in the stable residual fraction.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Alkaline and ultramafic carbonate lamprophyres in Central Bohemian carboniferous basins,Czech Republic

Summary Dykes of alkaline and ultramafic carbonate lamprophyres (monchiquite-ouachitite and aillikite) intrude the Carboniferous sediments of Central Bohemia. Their characteristic feature is the presence of substantial amounts of a sodalite group mineral (presumably haüyne), carbonate and barite. Isotopic compositions of ¹³C (–3.4 to –6.2) and ¹⁸O ( + 13.5 to + 15.9) indicate that the carbonate is of primary magmatic origin and that fluids were formed at temperatures of 500 to 350°C. High contents of CO₂ (3.6 to 17.6 wt.%) and incompatible elements, high LREE/HREE ratios (30.0 to 57.7), and low Rb/Sr (0.025 to 0.078) and⁸⁷Sr/⁸⁶Sr (0.7038 to 0.7042) ratios suggest the ultramafic lamprophyres are related to deep-seated carbonated magmas of mantle origin. Low degree of partial melting ( < 1%) of the mantle peridotite is envisaged, with additional transport of fluids rich in incompatible elements into the crustal chamber. Alkaline lamprophyres are fractionated derivatives which originated from the same source. Magma intrusion from different levels of a magma chamber into fracture zones under horizontal tension without a central intrusion could result in variability in lamprophyre composition (cumulates or evolved derivatives).

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Alkalische und ultramafische Karbonat-Lamprophyre der zentralen böhmischen Karbonbecken, Tschische Republik

Zusammenfassung Alkalische und ultramafische Karbonat-Lamprophyrgänge (Monchiquit-Ouachitit und Aillikit) intrudieren in karbonische Sedimente Zentralböhmens. Sie sind charakterisiert durch das Auftreten von beträchtlichen Mengen an Mineralen der Sodalith-Gruppe (v.a. Haüyn), Karbonaten und Baryt. Ihre Isotopenzusammensetzung von ¹³C (–3.4 bis –6.2) und ¹⁸O (13.5 bis 15.9) zeigt, daß die Karbonate primär magmatischen Ursprungs sind und daß assoziierte Fluide in einem Temperaturbereich von 350 bis 500°C gebildet wurden. Hohe Gehalte an CO₂ (3.6 bis 17.6 Gew. %), inkompatiblen Elementen, hohe LREE/HREE-Verhältnisse (30.0 bis 57.7), sowie niedrige Rb/Sr—(0.025 bis 0.078) und⁸⁷Sr/⁸⁶Sr-(0.7038 bis 0.7042) Verhältnisse lassen vermuten, daß die ultramafischen Lamprophyre mit karbonatischen Magmen des Mantels in Beziehung stehen. Eine niedrige Aufschmelzungsrate ( < 1%) von Mantelperidotit mit zusätzlichem Transport von, an inkompatiblen Elementen angereicherten Fluiden, in die krustale Magmenkammer wird diskutiert. Alkalische Lamprophyre sind als stärker fraktionierte Magmen, die derselben Quelle entstammen, zu verstehen. Die Intrusion der aus verschiedenen Bereichen der Magmenkammer stammenden Magmen in durch horizontale Dehnung verursachte Störungszonen könnte das Fehlen eines zentralen Intrusionskörpers und die unterschiedliche Zusammensetzung der Lamprophyre (Kumulate oder entwickelte Derivate) erklären.

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With 8 Figures