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X-ray photodesorption yields of N 2 15 and CO 13 are derived as a function of the incident photon energy near the N (∼400 eV) and O K-edge (∼500 eV) for pure N 2 15 ice and mixed CO 13 : N 2 15 ices. The photodesorption spectra from the mixed ices reveal an indirect desorption mechanism for which the desorption of N 2 15 and CO 13 is triggered by the photoabsorption of CO 13 and N 2 15 , respectively. This mechanism is confirmed by the x-ray photodesorption of CO 13 from a layered CO 13 / N 2 15 ice irradiated at 401 eV on the N 1s → π* transition of N 2 15 . This latter experiment enables us to quantify the relevant depth involved in the indirect desorption process, which is found to be 30–40 monolayers in that case. This value is further related to the energy transport of Auger electrons emitted from the photoabsorbing N 2 15 molecules that scatter toward the ice surface, inducing the desorption of CO 13 . The photodesorption yields corrected from the energy that can participate in the desorption process (expressed in molecules desorbed by eV deposited) do not depend on the photon energy; hence, they depend neither on the photoabsorbing molecule nor on its state after Auger decay. This demonstrates that x-ray induced electron stimulated desorption, mediated by Auger scattering, is the dominant process explaining the desorption of N 2 15 and CO 13 from the ices studied in this work. [ABSTRACT FROM AUTHOR]

Core-excitation of water ice releases many different molecules and ions in the gas phase. Studying these desorbed species and the underlying desorption mechanisms can provide useful information on the effects of x-ray irradiation in ice. We report a detailed study of the x-ray induced desorption of a number of neutral, cationic, and anionic species from amorphous solid water. We discuss the desorption mechanisms and the relative contributions of Auger and secondary electrons (x-ray induced electron stimulated desorption) and initial excitation (direct desorption) as well as the role of photochemistry. Anions are shown to desorb not just through processes linked with secondary electrons but also through direct dissociation of the core-excited molecule. The desorption spectra of oxygen ions (O+, OH+, H2O+, O−, and OH−) give a new perspective on their previously reported very low desorption yields for most types of irradiations of water, showing that they mostly originate from the dissociation of photoproducts such as H2O2. [ABSTRACT FROM AUTHOR]

We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, is observed. In contrast, the only desorbing anions detected are O− and C−. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice. [ABSTRACT FROM AUTHOR]

Spectroscopic investigations of PAHs have been conducted for many years, commencing with solid and solution studies and more recently including gas phase characterisation of a broad range of different species. Through the development of new, efficient methods of production and more sensitive spectroscopic techniques, fresh data are becoming available for not only neutral species, but also for radicals, ions and clusters. [ABSTRACT FROM PUBLISHER]

Anion production cross sections in collisions between Cn+, Cn carbon clusters (n = 5) and helium atoms have been measured in high-velocity collisions (v = 2.25 and 2.6 au). This paper focuses on two of the three processes responsible for the Cn- production, namely double electron capture (DEC) onto Cn+ cations and single electron capture onto neutral (SECN) Cn.They were experimentally distinguished from a gaseous thickness dependence study. Dissociative and non-dissociative cross sections were measured and, in the case of DEC, all dissociative branching ratios measured; for these small systems, the C2- fragment was found magical. Data concerning electron capture in neutral-neutral collisions are extremely rare, especially at high velocity. Introduction of this measured process in the independent atom and electron (IAE) model allowed us to revisit and satisfactorily reproduce the so-far unexplained size evolution of single electron capture (SEC) cross sections in 2.6 au Cn+-He (n = 10) collisions (Chabot et al 2006 J. Phys. B: At. Mol. Opt. Phys. 39 2593-603). IAE calculations for DEC cross sections and their comparison with experiment suggest a loss of electron in anionic Cn- species after the collision, competing with fragmentation and depending on the size. [ABSTRACT FROM AUTHOR]

The infrared fluorescence decay and the dispersed emission spectrum are presented for gaseous benzene following 193 nm laser excitation. They were measured with FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), a new home-made spectrometer. Redshift and redtail in the CH stretch emission spectra (3.3 µm region) demonstrate that anharmonicity plays a key role when dealing with high internal energies, as it is the case in the interstellar medium. [ABSTRACT FROM AUTHOR]

Carbonaceous cosmic dust is mainly observed through infrared spectroscopy either in absorption or in emission. Laboratory soot analogues of this interstellar or circumstellar dust were produced in fuel-rich, low-pressure, premixed and flat, flames. The particles were investigated by infrared absorption spectroscopy in the 2-15 µm spectral region. The details of the spectral features shed some light on the structure of the material and enable the study of its life cycle. In particular, the 8 µm band position is tentatively attributed to defects at the edge or in the polyaromatic units of the materials, revealing these structural changes in astrophysical dust. [ABSTRACT FROM AUTHOR]

Hydrogenated amorphous carbons, an important component of the interstellar carbonaceous dust, possess infrared spectral signatures (at 3.4, 6.9 and 7.3 µm) that are ubiquitous in the diffuse interstellar medium of galaxies, but not observed in dense clouds. To better understand the role played by cosmic rays in the disappearance of these absorption bands, irradiation experiments of hydrocarbon dust analogues have been performed with different swift ions. The results obtained through the in situ infrared monitoring of the samples during the irradiations allow to infer the dehydrogenation effect of the cosmic ray distribution on the interstellar hydrogenated amorphous carbons. The importance of this interstellar dust destruction by cosmic rays is discussed in comparison to other energetic processes in different interstellar environments. [ABSTRACT FROM AUTHOR]

An experiment designed for measuring the electronic spectra of PAH cations and PAH cluster cations has been set up, which is briefly described. The photodissociation spectra, reflecting the absorption spectra, of 2-methyl-naphthalene dimer cation have been recorded in the spectral ranges corresponding to the transitions from the ground state to both the excited charge resonance state and the first allowed local electronic excitation state. [ABSTRACT FROM AUTHOR]

Context. Carbonaceous cosmic dust is observed through infrared spectroscopy either in absorption or in emission. The details of the spectral features are believed to shed some light on its structure and finally enable the study of its life cycle. Aims. The goal is to combine several analytical tools in order to decipher the intimate nanostructure of some soot samples. Such materials provide interesting laboratory analogues of cosmic dust. In particular, spectroscopic and structural characteristics that help to describe the polyaromatic units embedded into the soot, including their size, morphology, and organisation are explored. Methods. Laboratory analogues of the carbonaceous interstellar and circumstellar dust were produced in fuel-rich low-pressure, premixed and flat flames. The soot particles were investigated by infrared absorption spectroscopy in the 2-15 μm spectral region. Raman spectroscopic measurements and high-resolution transmission electron microscopy were performed, which offered complementary information to better delineate the intimate structure of the analogues. Results. These laboratory analogues appeared to be mainly composed of sp2 carbon, with a low sp3 carbon content. A cross relation between the positions of the aromatic C=C bands at about 6.2 micron and the band at about 8 micron is shown to trace differences in shapes and structures of the polyaromatic units in the soot. Such effects are due to the defects of the polyaromatic structures in the form of non-hexagonal rings and/or aliphatic bridges. The role of these defects is thus observed through the 6.2 and 7.7 μm aromatic infrared band positions, and a distinction between carriers composed of curved aromatic sheets and more planar ones can be inferred. Based on these nanostructural differences, a scenario of nanograin growth and evolution is proposed. [ABSTRACT FROM AUTHOR]

Context. Carbonaceous cosmic dust is observed through infrared spectroscopy either in absorption or in emission. The details of the spectral features are believed to shed some light on its structure and finally enable the study of its life cycle. Aims. The goal is to combine several analytical tools in order to decipher the intimate nanostructure of some soot samples. Such materials provide interesting laboratory analogues of cosmic dust. In particular, spectroscopic and structural characteristics that help to describe the polyaromatic units embedded into the soot, including their size, morphology, and organisation are explored. Methods. Laboratory analogues of the carbonaceous interstellar and circumstellar dust were produced in fuel-rich low-pressure, premixed and flat flames. The soot particles were investigated by infrared absorption spectroscopy in the 2-15 μm spectral region. Raman spectroscopic measurements and high-resolution transmission electron microscopy were performed, which offered complementary information to better delineate the intimate structure of the analogues. Results. These laboratory analogues appeared to be mainly composed of sp2 carbon, with a low sp3 carbon content. A cross relation between the positions of the aromatic C=C bands at about 6.2 micron and the band at about 8 micron is shown to trace differences in shapes and structures of the polyaromatic units in the soot. Such effects are due to the defects of the polyaromatic structures in the form of non-hexagonal rings and/or aliphatic bridges. The role of these defects is thus observed through the 6.2 and 7.7 μm aromatic infrared band positions, and a distinction between carriers composed of curved aromatic sheets and more planar ones can be inferred. Based on these nanostructural differences, a scenario of nanograin growth and evolution is proposed. [ABSTRACT FROM AUTHOR]

We show that an x-ray charge coupled device (CCD) may be used as a particle detector for atomic and molecular mega-electron-volt (MeV) projectiles of around a few hundred keV per atomic mass unit. For atomic species, spectroscopic properties in kinetic energy measurements (i.e., linearity and energy resolution) are found to be close to those currently obtained with implanted or surface barrier silicon particle detectors. For molecular species, in order to increase the maximum kinetic energy detection limit, we propose to put a thin foil in front of the CCD. This foil breaks up the molecules into atoms and spreads the charges over many CCD pixels and therefore avoiding saturation effects. This opens new perspectives in high velocity molecular dissociation studies with accelerator facilities. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons are a class of molecules of broad interest that has long been explored by various spectroscopic techniques. The electronic spectroscopy of these species is of particular interest since it provides a framework for the understanding of the electronic structure of large polyatomic molecules. Such studies also allow the systematic investigation of electronic relaxation mechanisms in large molecules. In this review, we focus on the gas-phase experimental work on such systems and present the latest progress. We also underline the challenges that remain to be tackled. A focus on the understanding of the electronic relaxation pathways at work in gas-phase PAHs will also be presented, as well as their possible manifestation in space. [ABSTRACT FROM AUTHOR]

Detailed 40Ar/39Ar geochronology on single grains of muscovite was performed in the Variscan Tanneron Massif (SE France) to determine the precise timing of the post-collisional exhumation processes. Thirty-two plateau ages, obtained on metamorphic and magmatic rocks sampled along an east–west transect through the massif, vary from 302 ± 2 to 321 ± 2 Ma, and reveal a heterogeneous exhumation of the lower crust that lasted about 20 Ma during late Carboniferous. In the eastern part of the massif, the closure of the K–Ar isotopic system is at 311–315 Ma, whereas in the middle part of the massif it closes earlier at 317–321 Ma. These cooling paths are likely to be the result of differential exhumation processes of distinct crustal blocks controlled by a major ductile fault, the La Moure fault that separates both domains. In the western part of the massif, the ages decrease from 318 to 303 Ma approaching the Rouet granite, which provides the youngest age at 303.6 ± 1.2 Ma. This age distribution can be explained by the occurrence of a thermal structure spatially associated to the magmatic complex. These ages argue in favour of a cooling of the magmatic body at around 15 Ma after the country rocks in the western Tanneron. The emplacement of the Rouet granite in the core of an antiform is responsible for recrystallization and post-isotopic closure disturbances of the K–Ar chronometer in the muscovite from the host rocks. These new 40Ar/39Ar ages clearly outline that at least two different processes may contribute to the exhumation of the lower crust in the later stage of collision. During the first stage between 320 and 310 Ma, the differential motion of tectonic blocks limited by ductile shear zones controls the post-collisional exhumation. This event could be related to orogen parallel shearing associated with crustal-scale strike-slip faults and regional folding. The final exhumation stages at around 300 Ma take place within the tectonic doming associated to magmatic intrusions in the core of antiformal structures. Local ductile to brittle normal faulting is coeval to Upper Carboniferous intracontinental basins opening. [ABSTRACT FROM AUTHOR]

Abstract: Recent mineral separate ages obtained on the Karoo large igneous province (southern Africa) suggest that the province was built by several distinct magmatic pulses over a rather long period on the order of 5–6 Ma concerning the main erupted volume [Jourdan, F., Féraud, G., Bertrand, H., Kampunzu, A.B., Tshoso, G., Watkeys, M.K., Le Gall., B., 2005. The Karoo large igneous province: Brevity, origin, and relation with mass extinction questioned by new 40Ar/39Ar age data, Geology 33, 745–748]. Although this apparently atypical province is dated in more detail compared to many other large igneous provinces, volumetrically important areas still lack sufficient high-quality data. The timing of the Karoo province is crucial as this event is correlated with the breakup activity of the Gondwana supercontinent. The Lesotho basalts represent a major lava sequence of the province, but have not yet been precisely dated by systematic analysis of mineral separates. We analyzed plagioclase separates from five lava flows encompassing the complete 1.4-km-thick Lesotho sequence from top to bottom using the 40Ar/39Ar method. We obtained five plateau and mini-plateau ages statistically indistinguishable and ranging from 182.3±1.6 to 181.0±2.0 Ma (2σ). We derived an apparent maximum duration for this event of ∼0.8 Ma by neglecting correlated errors embedded in the age uncertainties. A critical review of previous ages obtained on the Lesotho sequence [Duncan R.A., Hooper, P.R., Rehacek, J., Marsh, J.S., Duncan, A.R., 1997. The timing and duration of the Karoo igneous event, southern Gondwana. Journal of Geophysical Research 102, 18127–18138] shows that groundmass analyses are unreliable for high-resolution geochronology, due to alteration and 39Ar recoil effects. Discrepancy between our ages and a previous plagioclase age at ∼184 Ma obtained by the later workers is tentatively attributed to the heterogeneity of the monitor used and/or cryptic excess 40Ar⁎. The current age database suggests that at least three temporally and spatially distinct brief major events (the Lesotho and southern Botswana lava piles and the Okavango dyke swarm) are so far recognized in the Karoo province. Identification of brief and volumetrically important Karoo magmatic events allows detecting the migration of the Karoo magmatism and potentially the stress regime that affected the southern African lithosphere at this time. A filtered compilation of 60 ages obtained with homogeneous intercalibrated standards suggests a shorter duration for the main pulses of the magmatism between 3 and 4.5 Ma, compared to a whole province duration of ∼10 Ma, between ∼182 and ∼172 Ma. [Copyright &y& Elsevier]

The Melilla carbonate complex (NE Morocco) is the only area of the Paleo-Mediterranean Sea where volcanic activity was present throughout most of the Messinian. 40Ar/39Ar dating of volcanic tuffs interbedded within the upper Messinian sedimentary deposits, known as the Terminal Carbonate Complex (TCC), yields accurate ages of paleoenvironmental and sea-level changes related to the Messinian Salinity Crisis. The new chronologic data (1) provide an average of 5.95–5.99 Ma for the base of the TCC, thus being synchronous with the onset of the Messinian Salinity Crisis, (2) demonstrate for the first time that the basal unconformity of the TCC does not represent a hiatus of long duration, (3) define a precise time line at 5.87±0.02 Ma (2σ) corresponding to sedimentary rocks exhibiting a lateral transition between continental and marine deposits typical of the TCC and (4) yield evidence that emersion of the Melilla platform during deposition of the TCC is partly related to tectono-magmatic activity. An erosional surface, capping the TCC deposits in the Melilla basin, is related to the major Messinian Mediterranean drawdown. The duration of the hiatus, associated with this surface, is estimated to be at most 450 kyr, but is probably shorter. [ABSTRACT FROM AUTHOR]

Abstract: Continental flood basalts consist of vast quantities of lava, sills and giant dyke swarms that are associated with continental break-up. The commonly radiating geometry of dyke swarms in these provinces is generally interpreted as the result of the stress regime that affected the lithosphere during the initial stage of continental break-up or as the result of plume impact. On the other hand, structures in the basement may also control dyke orientations, though such control has not previously been documented. In order to test the role of pre-dyke structures, we investigated four major putative Karoo-aged dyke swarms that taken together represent a giant radiating dyke swarm (the so-called “triple-junction”) ascribed to the Jurassic Karoo continental flood basalt (>3×106 km2; southern Africa). One of the best tests to discriminate between neoformed and inherited dyke orientation is to detect Precambrian dykes in the Jurassic swarms. Accordingly, we efficiently distinguished between Jurassic and Precambrian dykes using abbreviated low resolution, 40Ar/39Ar incremental heating schedules. Save-Limpopo dyke swarm samples (n =19) yield either apparent Proterozoic (728–1683 Ma) or Mesozoic (131–179 Ma) integrated ages; the Olifants River swarm (n =20) includes only Proterozoic (851–1731 Ma) and Archaean (2470–2872 Ma) dykes. The single age obtained on one N–S striking dyke (1464 Ma) suggests that the Lebombo dyke swarm includes Proterozoic dykes in the basement as well. These dates demonstrate the existence of pre-Karoo dykes in these swarms as previously hypothesized without supporting age data. In addition, aeromagnetic and air-photo interpretations indicate that: (1) dyke emplacement was largely controlled by major discontinuities such as the Zimbabwe and Kaapvaal craton boundaries, the orientation of the Limpopo mobile belt, and other pre-dyke structures including shear zones and (2) considering its polygenetic, pre-Mesozoic origin, the Olif ants River dyke swarm cannot be considered part of the Karoo magmatic event. This study, along with previous results obtained on the Okavango dyke swarm, shows that the apparent “triple junction” formed by radiating dyke swarms is not a Jurassic structure; rather, it reflects weakened lithospheric pathways that have controlled dyke orientations over hundreds of millions of years. One consequence is that the “triple-junction” geometry can no longer be unambiguously used as a mantle plume marker as previously proposed, although it does not preclude the possible existence of a mantle plume. More generally, we suggest that most Phanerozoic dyke swarms (including triple junctions) related to continental flood basalts were probably controlled in part by pre-existing lithospheric discontinuities. [Copyright &y& Elsevier]

The lower Jurassic Karoo–Ferrar magmatism represents one of the most important Phanerozoic continental flood basalt (CFB) provinces. The Karoo CFB province is dominated by tholeiitic traps and apparently radiating giant dyke swarms covering altogether ca. 3×106 km2. This study focuses on the giant N110°-trending Okavango dyke swarm (ODS) stretching over 1500 km across Botswana. This dyke swarm represents the main (failed) arm of the so-called Karoo triple junction that is generally considered as a key marker of the impingement of the Karoo starting mantle plume head. ODS dolerites yield six new plagioclase 40Ar/39Ar plateau (and miniplateau) ages ranging from 178.7±0.7 and 180.9±1.3 Ma. The distribution of the ages along a narrow Gaussian curve suggests a short period of magmatic activity centered around 179 Ma, i.e., ∼5 Ma younger than the emplacement age of Karoo mafic magmas in the southern part of the Karoo CFB province (∼184). This age difference indicates that Karoo magmatism does not represent a short-lived event as is generally the case for most CFB but lasted at least 5 Ma over the whole province. In addition, small clusters of plagioclase separated from 28 other dykes and measured by “speedy” step-heating experiments (with mostly two to three steps), gave either “Karoo” or Proterozoic ages. Integrated ages of the Proterozoic rocks range from 851±6 to 1672±7 Ma, and one plateau age (959.1±4.6 Ma) and one possibly geologically significant weighted-mean age (982.7±4.0 Ma) were obtained. Proterozoic and Karoo mafic rocks are petrographically similar, but Proterozoic dykes display clear geochemical differences (e.g., TiO2<2.1%) with the Karoo high-Ti ODS (TiO2>2.1%). Geochemical data combined with available Ar/Ar dates allow the identification of the two groups within a total set of 77 dykes investigated: ∼10% of the bulk ODS dykes are Proterozoic. Thus, the Jurassic Karoo ODS dykes were emplaced along reactivated Proterozoic structures and there is no pristine Jurassic Nuanetsi triple junction as commonly proposed. This throws into doubt the validity of the “active plume head” Karoo CFB rift models as being responsible for the observed “triple junction” dyke geometry. [Copyright &y& Elsevier]

New 40Ar/39Ar dating of hornblende and biotite, and measurement of anisotropy of magnetic susceptibility (AMS) have been performed on a 150 km section along the Oyapok river in order to better constrain the timing of cooling of the Transamazonian orogen in the south of French Guyana. From north to south, hornblende cooling ages range from 2052±4 to 1993±7 Ma, and corresponding biotite cooling ages vary from 1995±4 to 1928±4 Ma. This suggests a uniform cooling rate (3–5 °C/Ma) from 550 to below 250 °C. The South Guyana Complex (SGC) cool down later than the Southern Guyana Belt (SGB). The SGC displays high temperature metamorphism and higher magnetic anisotropy degree (P′:1.18–1.44). We interpret the high P′ values as the result of the development of a ductile fabric consecutively to transcurrent tectonic. The regular southward decrease of the cooling ages and the temperature profile determined at 1995 Ma along the studied 150 km section, indicates that no significant differential vertical movements affected the SGC. These results imply that the regional cooling was not associated with a rapid exhumation process as found in modern orogens. Instead, we propose a model of exhumation with a constant speed and later exhumation of the southern Oyapok zone belonging to a lower structural level and/or retarded by the transcurrent tectonics during the last Transamazonian magmatic event at 2100 Ma. [Copyright &y& Elsevier]