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A Vendian-Cambrian boundary succession from the northwestern margin of the Siberian Platform: stratigraphy, palaeontology, chemostratigraphy and correlation.

Siberia contains several key reference sections for studies of biological and environmental evolution across the Proterozoic-Phanerozoic transition. The Platonovskaya Formation, exposed in the Turukhansk region of western Siberia, is an uppermost Proterozoic to Cambrian succession whose trace and body fossils place broad limits on the age of deposition, but do not permit detailed correlation with boundary successions elsewhere. In contrast, a striking negative carbon isotopic excursion in the lower part of the Platonovskaya Formation permits precise chemostratigraphic correlation with upper-most Yudomian successions in Siberia, and possibly worldwide. In addition to providing a tool for correlation, the isotopic excursion preserved in the Platonovskaya and contemporaneous successions documents a major biogeochemical event, likely involving the world ocean. The excursion coincides with the palaeontological breakpoint between Ediacaran- and Cambrian-style assemblages, suggesting a role for biogeochemical change in evolutionary events near the Proterozoic Cambrian boundary.

Biological Evolution↗

Extinction from a paleontological perspective.

Extinction of widespread species is common in evolutionary time (millions of years) but rare in ecological time (hundreds or thousands of years). In the fossil record, there appears to be a smooth continuum between background and mass extinction; and the clustering of extinctions at mass extinctions cannot be explained by the chance coincidence of independent events. Although some extinction is selective, much is apparently random in that survivors have no recognizable superiority over victims. Extinction certainly plays an important role in evolution, but whether it is constructive or destructive has not yet been determined.

Adaptation, Biological↗

The biology of impact craters--a review.

Impact craters contain ecosystems that are often very different from the ecosystems that surround them. On Earth over 150 impact craters have been identified in a wide diversity of biomes. All natural events that can cause localized disruption of ecosystems have quite distinct patterns of rccovery. Impact events are unique in that they are the only extraterrestrial mechanism capable of disrupting an ecosystem locally in space and time. Thus, elucidating the chronological sequence of change at the sites of impacts is of ecological interest. In this synthetic review we use the existing literature, coupled with our own observations at the Haughton impact structure, Devon Island, Nunavut, Canada to consider the patterns of biological recovery at the site of impact craters and the ecological characteristics of impact craters. Three phases of recovery are suggested. The Phase of Thermal Biology, a phase associated with the localized, ephemeral thermal anomaly generated by an impact event. The Phase of Impact Succession and Climax, a phase marked by multiple primary and secondary succession events both in the aquatic realm (impact crater-lakes) and terrestrial realm (colonization of paleolacustrine deposits and impact-generated substrata) that are followed by periods of climax ecology. In the case of large-scale impact events (> 10(4) Mt), this latter phase may also be influenced by successional changes in the global environment. Finally, during the Phase of Ecological Assimilation, the disappearance of the surface geological expression of an impact structure results in a concomitant loss of ecological distinctiveness. In extreme cases, the impact structure is buried. Impact succession displays similarities and differences to succession following other agents of ecological disturbance, particularly volcanism.

Earth, Planet↗

A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples.

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/MS) to measure the delta18O and delta17O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degrees C, typically in 50 degrees C increments) under a flowing stream of helium carrier gas. The method has considerable advantages over others used for water analysis in that it is quick; requires only small samples, typically 1-50 mg of whole rock samples (corresponding to approximately 0.2 micromol of H2O); and the reagent is easy and safe to handle. Reproducibility in isotope ratio measurement obtained from pyrolysis of samples of a terrestrial solid standard are delta18O +/- 0.54, delta17O +/- 0.33, and delta17O +/- 0.10/1000, 1sigma in all cases. The technique was developed primarily for the analysis of meteorites, and the efficiency of the method is illustrated herein by results from water standards, solid reference materials, and a sample of the Murchison CM2 meteorite.

Meteoroids↗

The chemistry of life's origin: a carbonaceous meteorite perspective.

Carbonaceous chondrite meteorites are primitive asteroidal fragments that contain organic carbon and offer a glimpse of the abiotic chemical processes that preceded the onset of life. Their organic material displays structures as diverse as kerogen-like macromolecules and simpler soluble compounds that range from polar amino acids and polyols to nonpolar hydrocarbons. Several of these compounds have identical counterparts in terrestrial biomolecules and some of the amino acids show a unique l-asymmetry, suggesting their possible contribution to terrestrial molecular evolution and the origin of biological homochirality.

Amino Acids↗

Mass-independent isotopic compositions in terrestrial and extraterrestrial solids and their applications.

In 1983, Thiemens and Heidenreich reported the first chemically produced mass-independent isotope effect. This work has been shown to have a wide range of applications, including atmospheric chemistry, solar system evolution, and chemical physics. This work has recently been reviewed (Weston, R. E. Chem. Rev. 1999, 99, 2115-2136; Thiemens, M. H. Science 1999, 283, 341-345). In this Account, observations of mass-independent isotopic compositions in terrestrial and Martian solids are reviewed. A wide range of applications, including formation and transport of aerosols in the present atmosphere, chemistry of ancient atmospheres and oceans, history and coupling of the atmosphere-surface in the Antarctic dry valleys, origin and evolution of oxygen in the Earth's earliest environment, and the chemistry of the atmosphere and surface of Mars, are discussed.

Earth, Planet↗

Pyrolysis of p-benzosemiquinone.

In contrast to the thermolysis of p-benzoquinone, which does not decompose until the temperature is over 800 degrees C, and then primarily yields vinylacetylene, the corresponding anion radical, precipitated from liquid ammonia [Na(+)(NH(3))C(6)H(4)O(2)(*-)], decomposes at 380 degrees C and fragments primarily into phenol, hydroquinone, ammonia, methane, carbon monoxide, hydrogen, and minor amounts of other simple compounds. When the benzoquinone is replaced with perdeuteriobenzoquinone, deuterium and hydrogen are randomly scrambled into the products, and both ND(3) and CH(4) are formed. When the hot pyrolysis container is completely sealed, preventing the escape of volatile materials, p-aminophenol, as opposed to phenol, is the major liquid product.

Aminophenols↗

Cometary impact and amino acid survival--chemical kinetics and thermochemistry.

The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9 degrees above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometary delivery of amino acids to early Earth is highly unlikely.

Amino Acids↗

Functions and possible provenance of primordial proteins.

Nanobacteria or living nanovesicles are of great interest to the scientific community because of their dual nature: on the one hand, they appear as primal biosystems originating life; on the other hand, they can cause severe diseases. Their survival as well as their pathogenic potential is apparently linked to a self-synthesized protein-based slime, rich in calcium and phosphate (when available). Here, we provide challenging evidence for the occurrence of nanobacteria in the stratosphere, reflecting a possibly primordial provenance of the slime. An analysis of the slime's biological functions may lead to novel strategies suitable to block adhesion modalities in modern bacterial populations.

Apatites↗

The HNC/HCN ratio in comets.

The abundance ratio of the isomers HCN and HNC has been investigated in comet Hale-Bopp (C/1995 O1) through observations of the J = 4-3 rotational transitions of both species for heliocentric distances 0.93 < r < 3 AU, both pre- and post-perihelion. After correcting for the optical depth of the stronger HCN line, we find that the column density ratio of HNC/HCN in our telescope beam increases significantly as the comet approaches the Sun. We compare this behavior to that predicted from an ion-molecule chemical model and conclude that the HNC is produced in significant measure by chemical processes in the coma; i.e., for comet Hale-Bopp, HNC is not a parent molecule sublimating from the nucleus.

Astronomical Phenomena↗

Collisional quenching of OH radio emission from comet Hale-Bopp.

Observations of comets in the 18-cm OH transitions offer a means to probe gas production, kinematics, and OH excitation in comets. We present initial results of OH observations of comet Hale-Bopp obtained with the NRAO 43 m antenna located in Greenbank, WV. Maps of the emission provide strong constraints on the amount of quenching of the inversion of the OH ground state A-doublet in the coma. Analysis of the total radio OH flux and maps of its radial brightness distribution indicate a quenched region on the order of approximately 500,000 km during March and April 1997. This large value is generally consistent with previous observations of radio OH quenching in lower production rate comets when the high production rate of comet Hale-Bopp is considered.

Astronomy↗

HCO+ in the coma of comet Hale-Bopp.

Maps of comet C/1995 O1 (Hale-Bopp) in the millimeter-wave emission of the ion HCO+ revealed a local minimum near the nucleus position, with a maximum about 100,000 km in the antisolar direction. These observed features of the HCO+ emission require a low abundance of HCO+ due to enhanced destruction in the inner coma of the comet, within a region of low electron temperature (Te). To set constraints on the formation of HCO+ in the coma, as well as the location and magnitude of the transition to higher Te, the data are compared with the results of ion-molecule chemistry models.

Astronomical Phenomena↗

Extraterrestrial handedness: a reply.

Recent investigations of stable isotope ratios of amino acids from the Murchison meteorite have shown them to be of unambiguous extraterrestrial origin, and examinations of their enantiomeric compositions, where terrestrial contamination can be excluded, have found a consistent excess of L-enantiomers. One explanation for this observation has been the asymmetric photolysis of racemic extraterrestrial amino acids by circularly polarized light (CPL) in the synchrotron radiation from orbiting electrons around the pulsar remnants of supernovae. Mason (1997) has attempted to discredit this mechanism on the grounds that circular dichroism (CD) bands for optically active molecules alternate in sign and sum to zero over the entire spectrum, and hence enantioselective photochemical reactions cannot be induced by broad band CPL. We submit arguments disputing this conclusion and present reasons for expecting that broad band CPL synchrotron radiation would be quite capable of inducing asymmetric photolysis, particularly in aliphatic amino acids.

Amino Acids↗

Flash heating on the early Earth.

It has been suggested that very large impact events (approximately 500 km diameter impactors) sterilized the surface of the young Earth by producing enough rock vapor to boil the oceans. Here, we consider surface heating due to smaller impactors, and demonstrate that surface temperatures conductive to organic synthesis resulted. In particular, we focus on the synthesis of thermal peptides. Previously, laboratory experiments have demonstrated that dry heating a mixture of amino acids containing excess Asp, Glu, or Lys to temperatures approximately 170 degrees C for approximately 2 hours yields polypeptides. It has been argued that such temperature conditions would not have been available on the early Earth. Here we demonstrate, by analogy with the K/T impact, that the requisite temperatures are achieved on sand surfaces during the atmospheric reentry of fine ejecta particles produced by impacts of bolides approximately 10-20 km in diameter, assuming approximately 1-100 PAL CO2. Impactors of this size struck the Earth with a frequency of approximately 1 per 10(4)-10(5) y at 4.2 Ga. Smaller bolides produced negligible global surface heating, whereas bolides > 30 km in diameter yielded solid surface temperatures > 1000 K, high enough to pyrolyze amino acids and other organic compounds. Thus, peptide formation would have occurred globally for a relatively narrow range of bolide sizes.

Amino Acids↗

Primary sources of phosphorus and phosphates in chemical evolution.

In this work we consider the role of phosphorus in chemical evolution from an interdisciplinary approach. First we briefly review the presence of this element in different cosmic sites, such as massive stellar cores, circumstellar and interstellar clouds, meteorites, lunar and Martian samples, interplanetary dust particles, cometary dust and planetary atmospheres. Thus we illustrate the fact that phosphorus seems to be, at the same time, scarce and ubiquitous in the solar system. Afterwards, by comparing the phosphorus content of our planet's main reservoirs with the amount of cometary and meteoritic matter captured by the primitive Earth, we conclude that comets may have provided a primary source for phosphorus compounds of prebiotic interest. Finally, we make a number of proposals aimed to gain observational supporting evidence to the above conclusion and other suggestions made in the article.

Cosmic Dust↗

Prebiotic phosphorus chemistry reconsidered.

The available evidence indicates that the origin of life on Earth certainly occurred earlier than 3.5 billion years ago and perhaps substantially earlier. The time available for the chemical evolution which must have preceded this event is more difficult to estimate. Both endogenic and exogenic contributions to chemical evolution have been considered; i.e., from chemical reactions in a primitive atmosphere, or by introduction in the interiors of comets and/or meteorites. It is argued, however, that the phosphorus chemistry of Earth's earliest hydrosphere, whether primarily exogenic or endogenic in origin, was most likely dominated by compounds less oxidized than phosphoric acid and its esters. A scenario is presented for the early production of a suite of reactive phosphonic acid derivatives, the properties of which may have foreshadowed the later appearance of biophosphates.

Atmosphere↗

Molecular distribution of monocarboxylic acids in Asuka carbonaceous chondrites from Antarctica.

Molecular distribution of low-molecular-weight monocarboxylic acids was studied in three CM2 Asuka carbonaceous chondrites (A-881280, A-881334 and A-881458), which were recovered from Antarctica by the 29th Japanese Antarctic Research Expedition in 1988. GC and GC/MS analyses identified more than 30 monocarboxylic acids in A-881458, including aliphatic and aromatic acids with various structural isomers. Isomeric phenolic compounds were also identified. The aliphatic carboxylic acids have straight-chain structures having 2 to 12 carbon atoms (C2 to C12), and branched-chain structures (C4 to C9). The quantities of straight-chain acids decrease logarithmically with increasing carbon number. At the same carbon number, a straight-chain isomer is always predominant compared to branched-chain isomers. All of the 14 possible C4, C5 and C6 aliphatic monocarboxylic acids (not including optical isomers) have been identified, although all the isomers were not reported in Murchison and Y-791198 meteorites. Of the 17 possible isomeric C7 acids, at least 14 isomers were tentatively identified by mass spectra (EI and CI mode). At C8 or above, peaks of branched-chain isomers become obscure, probably due to the large number of isomers and small concentrations. Branched-chain monocarboxylic acids over C6 have never been reported in Muchison. Although occurrence of aliphatic acids are similar between A-881458 and Murchison at C4, C5 and C6 acids, a major difference is that A-881458 as well as Y-791198 have straight-chain predominance among isomers in contrast to Murchison being branched-chain predominant. In the case of isomeric aromatic compounds such as toluic acids and cresols, m-toluic acid and p-cresol are more abundant among their isomers, respectively. The molecular distribution may not reflect thermodynamic equilibrium but rather a kinetically controlled process for their formation mechanism. The other two CM2 chondrites (A-881280 and A-881334) were depleted in carboxylic acids in spite of similar carbon contents. The depletion is not due to weathering on ice, because the degrees of weathering are small and similar among the three chondrites. Probably those latter two chondrites may have been subjected to aqueous alteration or metamorphism on their meteorite parent bodies.

Antarctic Regions↗