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At least 37 records · Page 2

Carbon dioxide warming of the early Earth

Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

NASA Discipline Exobiology↗

A blast of gas in the latest Paleocene: simulating first-order effects of massive dissociation of oceanic methane hydrate

Carbonate and organic matter deposited during the latest Paleocene thermal maximum is characterized by a remarkable -2.5% excursion in delta 13C that occurred over approximately 10(4) yr and returned to near initial values in an exponential pattern over approximately 2 x 10(5) yr. It has been hypothesized that this excursion signifies transfer of 1.4 to 2.8 x 10(18) g of CH4 from oceanic hydrates to the combined ocean-atmosphere inorganic carbon reservoir. A scenario with 1.12 x 10(18) g of CH4 is numerically simulated here within the framework of the present-day global carbon cycle to test the plausibility of the hypothesis. We find that (1) the delta 13C of the deep ocean, shallow ocean, and atmosphere decreases by -2.3% over 10(4) yr and returns to initial values in an exponential pattern over approximately 2 x 10(5) yr; (2) the depth of the lysocline shoals by up to 400 m over 10(4) yr, and this rise is most pronounced in one ocean region; and (3) global surface temperature increases by approximately 2 degrees C over 10(4) yr and returns to initial values over approximately 2 x 10(6) yr. The first effect is quantitatively consistent with the geologic record; the latter two effects are qualitatively consistent with observations. Thus, significant CH4 release from oceanic hydrates is a plausible explanation for observed carbon cycle perturbations during the thermal maximum. This conclusion is of broad interest because the flux of CH4 invoked during the maximum is of similar magnitude to that released to the atmosphere from present-day anthropogenic CH4 sources.

Non-NASA Center↗

Evidence for gammacerane as an indicator of water column stratification

A new route for the formation of gammacerane from tetrahymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids. Selective cleavage of polysulphide linkages with MeLi/MeI led to formation of 3-methylthiogammacerane, indicating that the gammacerane skeleton is primarily bound via sulphur at position 3, consistent with the idea that tetrahymanol (or the corresponding ketone) is the precursor for gammacerane. Second, upon mild artificial maturation of two sediments using hydrous pyrolysis, gammacerane is released from S-rich macromolecular aggregates by cleavage of the relatively weak C-S bonds. The stable carbon isotopic compositions of gammacerane and lipids derived from primary producers and green sulphur bacteria in both the Miocene Gessoso-solfifera and Upper Jurassic Allgau Formations indicate that gammacerane is derived from bacterivorous ciliates which were partially feeding on green sulphur bacteria. This demonstrates that anaerobic ciliates living at or below the chemocline are important sources for gammacerane, consistent with the fact that ciliates only biosynthesize tetrahymanol if their diet is deprived of sterols. This leads to the conclusion that gammacerane is an indicator for water column stratification, which solves two current enigmas in gammacerane geochemistry. Firstly, it explains why gammacerane is often found in sediments deposited under hypersaline conditions but is not necessarily restricted to this type of deposits. Secondly, it explains why lacustrine deposits may contain abundant gammacerane since most lakes in the temperate climatic zones are stratified during summer.

NASA Discipline Exobiology↗

Infrared laser spectroscopy of jet-cooled carbon clusters: structure of triplet C6

We report the first structural characterization of the triplet isomer of C6. Forty-one rovibrational/fine structure transitions in the nu 4(sigma u) antisymmetric stretch fundamental of the C6 cluster have been measured by diode laser absorption spectroscopy of a supersonic carbon cluster beam. The observed spectrum is characteristic of a centrosymmetric linear triplet state with cumulene-type bonding. The measured ground state rotational constant B0 = 0.048 479 (10)cm-1 and the effective bond length r(eff) = 1.2868 (1) angstroms are in good agreement with ab initio predictions for the linear triplet (3 sigma g-) state of C6.

Non-NASA Center↗

Characterization of silicon-carbon clusters by infrared laser spectroscopy. The nu 1 band of SiC4

The nu 1 fundamental vibration of linear SiC4 has been observed by infrared diode laser spectroscopy of a supersonic cluster beam. Twenty-four rovibrational transitions were measured in the spectral region of 2094.6 to 2097.1 cm-1, the rotational temperature was 10 K. A combined least-squares fit of these transitions with previously reported microwave data yielded the following molecular constants: nu 1 = 2095.45806(37) cm-1, B" = 0.051161131(52) cm-1, and B' = 0.0509157(96) cm-1. These results are compared to vibrational spectroscopy measurements of SiC4 trapped in a solid Ar matrix and to ab initio calculations.

NASA Discipline Exobiology↗

Characterization of silicon-carbon clusters by infrared laser spectroscopy: the nu 3(sigma u) band of linear Si2C3

The nu 3(sigma u) fundamental vibration of 1 sigma g+ Si2C3 has been observed using a laser vaporization-supersonic cluster beam-diode laser spectrometer. Forty rovibrational transitions were measured in the range of 1965.8 to 1970.9 cm-1 with a rotational temperature of 10-15 K. A least-squares fit of these transitions yielded the following molecular constants: nu 3(sigma u)=1968.188 31(18) cm-1, B"=0.031 575 1(60) cm-1, and B'=0.031 437 4(57) cm-1. These results are in excellent agreement with recent Fourier transform infrared (FTIR) measurements of Si2C3 trapped in a solid Ar matrix [J. Chem. Phys. 100, 181(1994)] and with ab initio calculations [J. Chem. Phys. 100, 175 (1994)] which suggest cumulenic-like bonding for Si2C3, analogous to the isovalent C5 carbon cluster.

Non-NASA Center↗

The delivery of organic matter from asteroids and comets to the early surface of Mars

Carbon delivered to the Earth by interplanetary dust particles may have been an important source of pre-biotic organic matter (Anders, 1989). Interplanetary dust is shown to deliver an order-of-magnitude higher surface concentration of carbon onto Mars than onto Earth, suggesting interplanetary dust may be an important source of carbon on Mars as well.

NASA Discipline Exobiology↗

Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

Systematic variations in the 13C contents of individual extractable n-alkanes (C16-C29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial (C16-C18, delta 13C = -37% vs PDB), phytoplanktonic (C16-C23, delta = -32%), chemoautotrophic bacterial (C20-C29, delta = -38%), phytoplanktonic or heterotrophic bacterial (C20-C29, delta = -30%), and vascular plants (C23-C29, delta = -29%). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform delta values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.

Non-NASA Center↗

Ab initio study of C + H3+ reactions

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

NASA Discipline Exobiology↗

Box models for the evolution of atmospheric oxygen: an update

A simple 3-box model of the atmosphere/ocean system is used to describe the various stages in the evolution of atmospheric oxygen. In Stage I, which probably lasted until redbeds began to form about 2.0 Ga ago, the Earth's surface environment was generally devoid of free O2, except possibly in localized regions of high productivity in the surface ocean. In Stage II, which may have lasted for less than 150 Ma, the atmosphere and surface ocean were oxidizing, while the deep ocean remained anoxic. In Stage III, which commenced with the disappearance of banded iron formations around 1.85 Ga ago and has lasted until the present, all three surface reservoirs contained appreciable amounts of free O2. Recent and not-so-recent controversies regarding the abundance of oxygen in the Archean atmosphere are identified and discussed. The rate of O2 increase during the Middle and Late Proterozoic is identified as another outstanding question.

NASA Program Exobiology↗

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.

NASA Discipline Exobiology↗

Modelling the Phanerozoic carbon cycle and climate: constraints from the 87Sr/86Sr isotopic ratio of seawater

A numerical model describing the coupled evolution of the biogeochemical cycles of carbon, sulfur, calcium, magnesium, phosphorus, and strontium has been developed to describe the long-term changes of atmospheric carbon dioxide and climate during the Phanerozoic. The emphasis is on the effects of coupling the cycles of carbon and strontium. Various interpretations of the observed Phanerozoic history of the seawater 87Sr/86Sr ratio are investigated with the model. More specifically, the abilities of continental weathering, volcanism, and surface lithology in generating that signal are tested and compared. It is suggested that the observed fluctuations are mostly due to a changing weatherability over time. It is shown that such a conclusion is very important for the modelling of the carbon cycle. Indeed, it implies that the conventional belief that the evolution of atmospheric carbon dioxide and climate on a long time scale is governed by the balance between the volcanic input of CO2 and the rate of silicate weathering is not true. Rather carbon exchanges between the mantle and the exogenic system are likely to have played a key role too. Further, the increase of the global weathering rates with increasing surface temperature and/or atmospheric CO2 pressure usually postulated in long-term carbon cycle and climate modelling is also inconsistent with the new model. Other factors appear to have modulated the weatherability of the continents through time, such as mountain building and the existence of glaciers and ice sheets. Based on these observations, a history of atmospheric carbon dioxide and climate during Phanerozoic time, consistent with the strontium isotopic data, is reconstructed with the model and is shown to be compatible with paleoclimatic indicators, such as the timing of glaciation and the estimates of Cretaceous paleotemperatures.

NASA Discipline Number 52-30↗

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Models, Chemical↗

Multiplicities of secondaries in interactions of 1.8 GeV/nucleon 56Fe nuclei with photoemulsion and the cascade evaporation model

A nuclear photographic emulsion method was used to study the charge-state, ionization, and angular characteristics of secondaries produced in inelastic interactions of 56Fe nuclei at 1.8 GeV/nucleon with H, CNO, and AgBr nuclei. The data obtained are compared with the results of calculations made in terms of the Dubna version of the cascade evaporation model (DCM). The DCM has been shown to satisfactorily describe most of the interaction characteristics for two nuclei in the studied reactions. At the same time, quantitative differences are observed in some cases.

Non-NASA Center↗

Terminal Proterozoic reorganization of biogeochemical cycles

The Proterozoic aeon (2,500-540 million years ago) saw episodic increases in atmospheric oxygen content, the evolution of multicellular life and, at its close, an enormous radiation of animal diversity. These profound biological and environmental changes must have been linked, but the underlying mechanisms have been obscure. Here we show that hydrocarbons extracted from Proterozoic sediments in several locations worldwide are derived mainly from bacteria or other heterotrophs rather than from photosynthetic organisms. Biodegradation of algal products in sedimenting matter was therefore unusually complete, indicating that organic material was extensively reworked as it sank slowly through the water column. We propose that a significant proportion of this reworking will have been mediated by sulphate-reducing bacteria, forming sulphide. The production of sulphide and consumption of oxygen near the ocean surface will have inhibited transport of O2 to the deep ocean. We find that preservation of algal-lipid skeletons improves at the beginning of the Cambrian, reflecting the increase in transport by rapidly sinking faecal pellets. We suggest that this rapid removal of organic matter will have increased oxygenation of surface waters, leading to a descent of the O2-sulphide interface to the sea floor and to marked changes in the marine environment, ultimately contributing to the Cambrian radiation.

Non-NASA Center↗