Polycyclic aromatic hydrocarbons (PAHs) in Antarctic Martian meteorites, carbonaceous chondrites, and polar ice

Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level (McKay et al., 1996). The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient martian biota. We have examined PAHs in the Antarctic shergottite EETA79001, which is also considered to be from Mars, as well as several Antarctic carbonaceous chondrites. We have found that many of the same PAHs detected in the ALH84001 carbonate globules are present in Antarctic carbonaceous chondrites and in both the matrix and carbonate (druse) component of EETA79001. We also investigated PAHs in polar ice and found that carbonate is an effective scavenger of PAHs in ice meltwater. Moreover, the distribution of PAHs in the carbonate extract of Antarctic Allan Hills ice is remarkably similar to that found in both EETA79001 and ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material (McDonald and Bada, 1995) suggests that this meteorite is contaminated with terrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. Our data suggests that the PAHs observed in both ALH84001 and EETA79001 are derived from either the exogenous delivery of organics to Mars or extraterrestrial and terrestrial PAHs present in the ice meltwater or, more likely, from a mixture of these sources. It would appear that PAHs are not useful biomarkers in the search for extinct or extant life on Mars.     

The Ms = 6.2, June 15, 1995 Aigion earthquake (Greece): evidence for low angle normal faulting in the Corinth rift

We present the results of a multidisciplinary study of the M_s = 6.2, 1995, June 15, Aigion earthquake (Gulf of Corinth, Greece). In order to constrain the rupture geometry, we used all available data from seismology (local, regional and teleseismic records of the mainshock and of aftershocks), geodesy (GPS and SAR interferometry), and tectonics. Part of these data were obtained during a postseismic field study consisting of the surveying of 24 GPS points, the temporary installation of 20 digital seismometers, and a detailed field investigation for surface fault break. The Aigion fault was the only fault onland which showed detectable breaks (< 4 cm). We relocated the mainshock hypocenter at 10 km in depth, 38 ° 21.7 N, 22 ° 12.0 E, about 15 km NNE to the damaged city of Aigion. The modeling of teleseismic P and SH waves provides a seismic moment M_o = 3.4 10¹⁸ N.m, a well constrained focal mechanism (strike 277 °, dip 33 °, rake – 77°), at a centroidal depth of 7.2 km, consistent with the NEIC and the revised Harvard determinations. It thus involved almost pure normal faulting in agreement with the tectonics of the Gulf. The horizontal GPS displacements corrected for the opening of the gulf (1.5 cm/year) show a well-resolved 7 cm northward motion above the hypocenter, which eliminates the possibility of a steep, south-dipping fault plane. Fitting the S-wave polarization at SERG, 10 km from the epicenter, with a 33° northward dipping plane implies a hypocentral depth greater than 10 km. The north dipping fault plane provides a poor fit to the GPS data at the southern points when a homogeneous elastic half-space is considered: the best fit geodetic model is obtained for a fault shallower by 2 km, assuming the same dip. We show with a two-dimensional model that this depth difference is probably due to the distorting effect of the shallow, low-rigidity sediments of the gulf and of its edges. The best-fit fault model, with dimensions 9 km E–W and 15 km along dip, and a 0.87 m uniform slip, fits InSAR data covering the time of the earthquake. The fault is located about 10 km east-northeast to the Aigion fault, whose surface breaks thus appears as secondary features. The rupture lasted 4 to 5 s, propagating southward and upward on a fault probably outcropping offshore, near the southern edge of the gulf. In the shallowest 4 km, the slip – if any – has not exceeded about 30 cm. This geometry implies a large directivity effect in Aigion, in agreement with the accelerogram aig which shows a short duration (2 s) and a large amplitude (0.5 g) of the direct S acceleration. This unusual low-angle normal faulting may have been favoured by a low-friction, high pore pressure fault zone, or by a rotation of the stress directions due to the possible dip towards the south of the brittle-ductile transition zone. This fault cannot be responsible for the long term topography of the rift, which is controlled by larger normal faults with larger dip angles, implying either a seldom, or a more recently started activity of such low angle faults in the central part of the rift.     

The annual cycle and the predictability of the tropical coupled ocean-atmosphere system

Summary Using large-scale circulation statistics from the Pacific Ocean basin, predictability of the coupled ocean-atmosphere system on interannual time scales is found both to be limited in extent and to possess a strong annual cycle. Irrespective of when lagged correlations are commenced, correlations decrease rapidly through the boreal spring, indicating an inherent predictability limitation for large scale coupled oceanicatmospheric processes such as El Niño. Long term prediction experiments using numerical coupled-models show that the models are excellent facsimiles of the real system. They, too, encounter the predictability barrier and exhibit a substantial decrease in observation-prediction correlation across the boreal spring. Thus, a predictive system based solely on the interactive physics of the Pacific Basin appears limited to a maximum of less than one year and a minimum of only one or two months.Two hypotheses are made to explain the existence of the predictability barrier. First, it is argued that the tropical coupled system is at its frailest state during the boreal spring and that the signal-to-noise ratio is weakest. In such a system, maximum random error growth may occur as the atmosphere and the ocean become temporally detached and wander onto different climate trajectories. A series of 144 preliminary Monte Carlo experiments were conducted with a coupled ocean-atmosphere model to test the hypothesis. Irrespective of when the experiments were commenced, error growth was maximized at the same time of the year. The second hypothesis suggests that the near-equatorial circulation is perturbed at the time of its weakest state by external influences such as the monsoon and that the climate wanderings are nudged deterministically. There is observational and theoretical evidence to support the hypothesis. Observations suggest that anomalous monsoons impart basin-wide coherent alterations of the wind stress field in the Pacific Ocean. Experiments with a coupled ocean-atmosphere model show that the period of an ENSO event is altered substantially by an anomalous monsoon. Given that there appear to be precursors to anomalous monsoons, it is suggested that there may be ways to avoid the predictability barrier and thus extend prediction of the entire system.Finally, noting that the two hypotheses are not mutually exclusive, they are combined to form a unified theory. As the asymmetric monsoonal and the symmetric near-equatorial heating are in approximate quadrature, it is argued that the monsoons influence the Walker circulation during the boreal spring. However, during the boreal fall and early winter the near-equatorial heating variability dominates the winter monsoon.With 18 Figures     

Biomass burning in the tropical savannas of Ivory Coast: An overview of the field experiment Fire of Savannas (FOS/DECAFE 91)

FOS/DECAFE 91 (Fire of Savannas/Dynamique et Chimie Atmosphérique en Forêt Equatoriale) was the first multidisciplinary experiment organized in Africa to determine gas and aerosol emissions by prescribed savanna fires. The humid savanna of Lamto in Ivory Coast was chosen for its ecological characteristics representative of savannas with a high biomass density (900 g m^–2 dry matter). Moreover the vegetation and the climate of Lamto have been studied for more than twenty years. The emission ratios (X/CO₂) of the carbon compounds (CO₂, CO, NMHC, CH₄, PAH, organic acids and aerosols), nitrogen compounds (NO_x, N₂O, NH₃ and soluble aerosols) and sulfur compounds (SO₂, COS and aerosols) were experimentally determined by ground and aircraft measurements. To perform this experiment, 4 small plots (100×100 m) and 2 large areas (10×10 km) were prepared and burnt in January 1991 during the period of maximum occurrence of fires in this type of savanna. The detailed ecological study shows that the carbon content of the vegetation is constant within 1% (42 g C for 100 g of vegetal dry matter), the nitrogen content (0.29 g N for 100 g of dry matter) may vary by 10% and the sulfur content (0.05 g S/100 d.m.) by 20%. These variations of the biomass chemical content do not constitute an important factor in the variation of the gas and particle emission levels. With the emission ratios characteristic of humid savanna and flaming conditions (CO/CO₂ of 6.1% at the ground and 8% for airborne measurements), we propose a set of new emission factors, taking into account the burning efficiency which is about 80%: 74.4% of the carbon content of the savanna biomass is released to the atmosphere in the form of CO₂, 4.6% as CO, 0.2% as CH₄, 0.5% as NMHC and 0.7% as aerosols. 17.2% of the nitrogen content of the biomass is released as NO_x, 3.5% as N₂O, 0.6% as NH₃ and 0.5% as soluble aerosols.     

Ozone production due to emissions from vegetation burning

Ozone has been observed in elevated concentrations by satellites over areas previously believed to be background. There is meteorological evidence, that these ozone plumes found over the Atlantic Ocean originate from vegetation fires on the African continent.In a previous study (DECAFE-88), we have investigated ozone and assumed precursor compounds over African tropical forest regions. Our measurements revealed large photosmog layers at altitudes from 1.5 to 4 km. Both chemical and meteorological evidence point to savanna fires up to several thousand km upwind as sources.Here we describe ozone mixing ratios observed over western Africa and compare ozone production ratios from different field measurement campaigns related to vegetation burning. We find that air masses containing photosmog ingredients require several days to develop their oxidation potential, similar to what is known from air polluted by emissions from fossil fuel burning. Finally, we estimate the global ozone production due to vegetation fires and conclude that this source is comparable in strength to the stratospheric input.     

Pristine vs. contaminated trends in Nb,Ta-oxide minerals of the Jihlava Pegmatite District,Czech Republic

Summary Columbite-tantalite is widespread in the lepidolite-subtype rare-element pegmatites of the Jihlava pegmatite district, western Moravia, Czechoslovakia. In most pegmatites, fractionation of columbite-tantalite shows initial enrichment in Mn followed by increasing Ta, in accordance with the usual trend from ferrocolumbite through mangano-columbite to manganotantalite, typical of the lepidolite pegmatites. Many dikes, however, show local deviations toward Fe- and Ti-rich compositions. In extreme cases, all columbite-tantalite is strongly enriched in Fe and Ti, and is associated with ixiolite and tantalian rutile. The degree of enrichment of the Nb,Ta oxide-mineral assemblage in Fe and Ti is proportional to tectonic introduction of wallrock xenoliths of mafic pyroxene-biotite syenite into the pegmatites during late stages of their consolidation. Extensive reaction of the residual pegmatite melt with the xenoliths contaminated the near-by melt, and generated Nb,Ta oxide minerals and tourmaline of non-typical chemistries. Late fersmite probably formed after thermal equilibration of the pegmatites with their syenitic country rocks, from Ca-bearing regional interstitial fluids pervading through the solidified pegmatites.

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Zusammenfassung In Selten-Element Pegmatiten (Lepidolith-Subtyp) des Jihlava Pegmatit Distriktes, West-Mähren, Tschechien, ist Columbit-Tantalit weitverbreitet. In den meisten Pegmatiten führte die Fraktionierung von Columbit-Tantalit zur einer anflinglichen Anreicherung von Mn gefolgt von einer Zunahme in Ta, vergleichbar mit dem für Lepidolith-Pegmatit bekannten Trend Ferrocolumbit-Manganocolumbit-Manganotantalit. Viele Gänge zeigen jedoch lokale Abweichungen zu Fe- und Ti-reichen Zusammensetzungen. In extremen Fällen ist Columbit-Tantalit stark an Fe und Ti angereichert und mit Ixiolith und Tantalo-Rutil vergesellschaftet. Das Ausmaß der Fe und Ti Anreicherung in (Nb,Ta)-Oxid-Assoziationen ist proportional dem tektonisch bedingten Eindringen von maischen Pyroxen-Biotit-reichen Syenit-Nebengesteinsxenolithen in die Pegmatite gegen Ende ihrer Verfestigung. Tiefgreifende Reaktion der Pegmatit-Restschmelze mit den Xenolithen kontaminierte die Schmelze und führte zur Bildung von (Nb,Ta)-Oxid-Mineralen und Turmalin ungewöhnlicher Zusammensetzung. Möglicherweise nach der thermischen Gleichgewichtseinstellung der Pegmatite mit ihren syenitischen Nebengesteinen bildete sich Fersmit unter Beteiligung von Ca-führenden regionalen Porenlösungen, welche die verfestigten Pegmatite durchdrangen.

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With 6 Figures     

Chemical composition of hard- and softrock groundwaters from central Norway with special consideration of fluoride and Norwegian drinking water limits

Groundwaters from crystalline and metamorphic rocks (hardrocks) and from Quaternary deposits, i.e., alluvial and glacial deposits (softrocks) from the counties of Nord-Trøndelag and Sør-Trøndelag were analyzed for major and minor elements and ions including fluoride. The median concentration of F^– in water from the hardrock aquifers is 0.28 mg/l (14.7 eq/l) in contrast to water from softrock aquifers in which it is found to be 0.05 mg/1 (2.6 eq/l). More importantly, ca. 15% of the locations where water was abstracted from hardrock wells contain 1.5 mg/l (78.9 eq/l) F^– or more. Thus, 15% of all hardrock wells returned F^– results that are at or above the maximum recommended value for drinking water. Of the softrock wells, none are above 1 mg/l. Geologists would normally expect higher F^–contents in groundwaters derived from acid rocks, e.g., in granitic or gneissic areas. When comparing the host lithology with the observed F^–contents, however, no clear relationship between F^– content and lithology is visible. The highest observed F^– values actually occur in gneissic host rocks. However, wells drilled in amphibolites/greenstones, mica schists, calcareous rocks, and sedimentary rocks all returned some analytical results above 1.5 mg/l F^–. These results suggest that all hardrock wells drilled should be tested for F^– and the users informed about the results and advised to take any necessary precautions. When applying the recently proposed Norwegian drinking water limits to our data, 51% of all softrock well waters and 56% of all hardrock well waters are unfit for consumption without prior treatment, although we analyzed only for about half of the proposed elements/parameters. This result seriously questions the concept of fixed action levels—many of them with totally unproven health implications—for so many parameters/elements for hardrock groundwaters.     

Towards an understanding of joint roughness

Summary It is argued that the currently available joint models are incapable of accurate predictions of joint shear behaviour without resorting to substantial levels of empiricism. This is because these models fail to adequately quantify joint roughness, or appreciate the importance of scale. A novel approach, which uses fractal geometry to investigate joint roughness, is described. This approach goes beyond describing the symptoms of roughness and seeks to find the cause. In the application of this approach, the concepts of fractal geometry, fractal dimension and self similarity are described and used as a framework to formulate a statistically based and practical model for the characterisation of rock joint roughness. Important relationships between the fractal dimension and the more useful statistical parameters of standard deviation of both asperity angles and asperity heights are derived. These relationships not only provide a useful, working method for quantifying joint roughness, but are also shown to provide a basis for understanding the Barton empirical JRC-JCS model. In addition, the fractal model is able to provide conceptual models for the effects of normal stress on the shear behaviour of joints and the scale-dependence of joints.     

Geochemical and structural evolution of micas in the Rožná and Dobrá Voda pegmatites,Czech Republic

Summary The chemistry, structural parameters, polytypism, optical properties and Rb-Sr isotopes were examined in 11 to 60 samples of biotite, muscovite and lepidolite from the pegmatites at Roná (the type locality of lepidolite; 323 ± 4Ma) and Dobrá Voda (306 ± 9Ma) in western Moravia. At both localities, early endocontact biotite is followed inwards by muscovite and lepidolite, which is concentrated in and around the core. At Roná, a 1M lepidolite follows after 2M₁ muscovite but all later generations of lepidolite are 2M₂, close to Tri₅₀ Ply₅₀ and in part associated with muscovite 2M₁. At Dobrá Voda, all lepidolite types are 1M and free of muscovite, and the late varieties approximate Tri₃₀ Ply₇₀. At both localities, a trend of increasing HF is indicated during the progress of mica crystallization, culminating in precipitation of topaz. Polytypism of lepidolite is not correlatable with any compositional or growth feature, or their combination. Throughout the mica crystallization, Rb/Cs decreases but K/Rb becomes reversed after an initial decrease. Boron is partitioned preferentially into muscovite (up to 1.10 wt.% B₂O₃) but Be, Zn, Mn and Sc are enhanced in lepidolite. A slight increase in Fe, Ba and Cl in the last generation of lepidolite might be possibly due to mixing of residual pegmatite fluids with metamorphic pore solutions.

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Geochemische und strukturelle Entwicklung der Glimmer in den Pegmatiten von Roná und Dobrá Voda, Tschechische Republik

Zusammenfassung In 11 bis 60 Proben von Biotit, Muskovit und Lepidolith aus den Pegmatiten von Roná (Typlokalität des Lepidoliths; 323 ± 9 Ma) in Westmähren wurden Chemie, Struktur-parameter, Polytypie, optische Eigenschaften und Rb-Sr-Isotopie untersucht. An beiden Lokalitäten wird früher Biotit an Endokontakten nach Innen von Muskovit und Lepidolith gefolgt, letzterer ist in und um den Kern konzentriert. In Roná folgt 1M-Lepidolith auf 2M₁-Muskovit, aber alle späteren Lepidolithgenerationen sind 2M₂, nahe Tri₅₀Ply₅₀ und zum Teil mit 2M₁-Muskovit vergesellschaftet. In Dobrá Voda sind alle Lepidolithe vom Typ 1M und frei von Muskovit, die späten Varietäten kommen Tri₅₀Ply₅₀ nahe. An beiden Lokalitäten ist während des Fortschreitens der Glimmerkristallisation eine Tendenz von steigendem HF angezeigt, die in der Ausfällung von Topas ihren Höhepunkt findet. Die Polytypie des Lepidoliths kann nicht mit irgendeiner Eigenheit der Zusammensetzung oder des Wachstums korreliert worden, auch nicht mit einer Kombination von diesen. Während der ganzen Glimmerkristallisation nimmt Rb/Cs ab, aber die Tendenz von K/Rb ändert sich nach anfänglichem Abfall. Das Bor verteilt sich bevorzugt auf den Muskovit (bis zu 1.10 Gew. -% B₂O₃), aber die Be-, Zn-, Mn- und Sc-Gehalte sind im Lepidolith erhöht. Ein leichter Ansteig von Fe, Ba und Cl in der letzten Lepidolithgeneration könnte vielleicht durch eine Mischung von pegmatitischen Restlösungen mit metamorphen Porenlösungen verursacht sein.

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With 9 Figures     

Geochemistry of the Grenville Dyke Swarm: role of plume-source mantle in magma genesis

Major and trace element data of samples from the approximately 590 Ma Grenville dyke swarm, in the southeastern parts of the Canadian Shield, were used to evaluate the extent of crustal contamination of the dyke magma and to model its probable mantle source. The dyke rocks are mostly saturated, quartz tholeiites. A few samples represent transitional basalts. Their overall chemistries are similar to those of continental flood basalts. Their compositions resemble those of liquids initially produced in the garnet peridotite mantle zone and then subjected to polybaric fractionation. However, fractionation models fail to mass-balance Ti, Fe, K, and P. Geochemical and isotopic criteria indicate that crustal contamination was minimal. The incompatible elements Zr, Y, K, Rb, Nb, V, Ta, Hf, and Th show hyperbolic elemental ratio-ratio distributions indicative of mixing between two end-members. One end-member has elemental ratios similar to those of a depleted N-MORB source and the second of a P-MORB i.e. ertile or plume MORB source. The more enriched dyke compositions can be successfully reproduced by mixing models in the ratio of 6:1 between the most depleted MORB-like dyke magma and a liquid composition similar to metasomatic glass veinlets coexisting with mica peridotite mantle xenoliths, and subsequent crystal fractionation. The Grenville dykes are probably a synrift swarm that was emplaced along a rift arm related to an Iapetan rrr triple junction that is thought to have formed over a mantle plume. The chemistry of the dyke swarm is consistent with its derivation from a plume head, in that the minor enriched source can be identified with plume-source mantle and the major depleted source with entrained mantle. The magma probably originated in the upper cooler parts of the plume head.