GPS monitoring of vertical ground motion in northern Ardenne–Eifel: five campaigns (1999–2003) of the HARD project

We present the HARD project of GPS monitoring of vertical ground motion in NE Ardenne and Eifel (western Europe). Its main purposes are to get a better insight into the present-day rates of vertical ground motion in intraplate settings and to identify the various causes of these motions. Since 1999, we have carried out yearly campaigns of simultaneous GPS measurements at 12 sites situated so as to sample the different tectonic subunits of the study area and especially to record potential displacements across the seismogenic Hockai fault zone. Five campaigns (1999–2003) have been processed currently. Key issues of the data processing with the Gamit software are discussed and first results are presented. Though temporally consistent in many cases, the obtained vertical motion rates are spatially highly variable. They are also much too high (several mm/year) to support a tectonic interpretation, and a long-term influence of groundwater level variations is proposed to account for the observed motions. This influence should be distinguished from seasonal variations and from inter-survey variations linked to the varying degree of soil and subsoil drying off during the successive spring surveys.     

Post-Collisional Transition from Subduction- to Intraplate-type Magmatism in the Westernmost Mediterranean: Evidence for Continental-Edge Delamination of Subcontinental Lithosphere

Post-collisional magmatism in the southern Iberian and northwesternAfrican continental margins contains important clues for theunderstanding of a possible causal connection between movementsin the Earth's upper mantle, the uplift of continental lithosphereand the origin of circum-Mediterranean igneous activity. Systematicgeochemical and geochronological studies (major and trace element,Sr–Nd–Pb-isotope analysis and laser ⁴⁰Ar/³⁹Ar-agedating) on igneous rocks provide constraints for understandingthe post-collisional history of the southern Iberian and northwesternAfrican continental margins. Two groups of magmatic rocks canbe distinguished: (1) an Upper Miocene to Lower Pliocene (8·2–4·8Ma), Si–K-rich group including high-K (calc-alkaline)and shoshonitic series rocks; (2) an Upper Miocene to Pleistocene(6·3–0·65 Ma), Si-poor, Na-rich group includingbasanites and alkali basalts to hawaiites and tephrites. Maficsamples from the Si–K-rich group generally show geochemicalaffinities with volcanic rocks from active subduction zones(e.g. Izu–Bonin and Aeolian island arcs), whereas maficsamples from the Si-poor, Na-rich group are geochemically similarto lavas found in intraplate volcanic settings derived fromsub-lithospheric mantle sources (e.g. Canary Islands). The transitionfrom Si-rich (subduction-related) to Si-poor (intraplate-type)magmatism between 6·3 Ma (first alkali basalt) and 4·8Ma (latest shoshonite) can be observed both on a regional scaleand in individual volcanic systems. Si–K-rich and Si-poorigneous rocks from the continental margins of southern Iberiaand northwestern Africa are, respectively, proposed to havebeen derived from metasomatized subcontinental lithosphere andsub-lithospheric mantle that was contaminated with plume material.A three-dimensional geodynamic model for the westernmost Mediterraneanis presented in which subduction of oceanic lithosphere is inferredto have caused continental-edge delamination of subcontinentallithosphere associated with upwelling of plume-contaminatedsub-lithospheric mantle and lithospheric uplift. This processmay operate worldwide in areas where subduction-related andintraplate-type magmatism are spatially and temporally associated. KEY WORDS: post-collisional magmatism; Mediterranean-style back-arc basins; subduction; delamination; uplift of marine gateways     

Origin of Exceptionally Abundant Phonolites on Ua Pou Island (Marquesas, French Polynesia): Partial Melting of Basanites Followed by Crustal Contamination

On the basis of the first systematic mapping of Ua Pou, longknown for its exceptionally abundant phonolites, we estimatethat these rocks cover 65% of the surface of the island whereasmafic lavas cover 27% and intermediate ones 8%. The silica-undersaturatedsuite was erupted in a restricted time span (2·9–2·35Myr), following the emplacement of tholeiites derived from ayoung HIMU-type source at c. 4 Ma. Primitive basanites, derivedfrom a heterogeneous mantle source with a dominant EM II + HIMUsignature, represent likely parental magmas. The series is characterizedby a Daly gap defined by a lack of phonotephrites. We considerthat the most likely model for the origin of evolved lavas ispartial melting at depth of primitive basanites, leaving anamphibole-rich residuum and producing tephriphonolitic magmas.These tephriphonolitic magmas may have evolved by closed-systemfractional crystallization towards Group A phonolites. Threeother groups of phonolites could have been derived from tephriphonoliticmagmas by open-system fractional crystallization processes,characterized respectively by seawater contamination (GroupB), assimilation of nepheline syenite-type materials (GroupC) and extreme fractionation coupled with assimilation of theunderlying oceanic crust (Group D). The prominence of evolvedlavas is a consequence of their origin from partial meltingof mafic precursors followed by crustal contamination. KEY WORDS: Marquesas; French Polynesia; phonolite; partial melting; contamination     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Accurate measurement of silver isotopic compositions in geological materials including low Pd/Ag meteorites

Very precise silver (Ag) isotopic compositions have been determined for a number of terrestrial rocks, and high and low Pd/Ag meteorites by utilizing multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The meteorites include primitive chondrites, the Group IAB iron meteorites Canyon Diablo and Toluca, and the Group IIIAB iron meteorite Grant. Silver isotopic measurements are primarily of interest because ¹⁰⁷Ag was produced by decay of the short-lived radionuclide ¹⁰⁷Pd during the formation of the solar system and hence the Pd-Ag chronometer has set constraints on the timing of early planetesimal formation. A 2σ precision of ±0.05‰ can be obtained for analyses of standard solutions when Ag isotopic ratios are normalized to Pd, to correct for instrumental mass discrimination, and to bracketing standards. Caution must be exercised when making Ag isotopic measurements because isotopic artifacts can be generated in the laboratory and during mass spectrometry. The external reproducibility for geological samples based on replicate analyses of rocks is ±0.2‰ (2σ).All chondrites analyzed have similar Ag isotopic compositions that do not differ significantly (>0.3‰) from the ‘terrestrial’ value of the NIST SRM 978a Ag isotope standard. Hence, they show no evidence of excess ¹⁰⁷Ag derived from ¹⁰⁷Pd decay or, of stable Ag isotope fractionation associated with volatile element depletion within the accretion disk or from parent body metamorphism. The Group IAB iron meteorite samples analyzed show evidence of complex behavior and disturbance of Ag isotope systematics. Therefore, care must be taken when using this group of iron meteorites to obtain chronological information based on the Pd-Ag decay scheme.     

Concentration, isotopic composition, and sources of lead in Southern Ocean air during 1999/2000, measured at the Cape Grim Baseline Air Pollution Station, Tasmania

Southern Ocean aerosols were collected at the Cape Grim Baseline Air Pollution Station from onshore air under baseline conditions between February 1999 and April 2000. Thermal ionization techniques (TIMS) and isotope dilution mass spectrometry (IDMS) were used to measure the isotopic composition and concentration of lead in the air giving concentrations as low as 0.6 ± 0.1 pg · m⁻³. Air collected under baseline conditions for 12 months (May 1999-April 2000) yielded an overall lead concentration of 11.0 ± 0.2 pg · m⁻³ and isotopic composition of ²⁰⁶Pb/²⁰⁷Pb = 1.154, ²⁰⁸Pb/²⁰⁷Pb = 2.387 and ²⁰⁶Pb/²⁰⁴Pb = 17.93. The range in isotopic ratios was consistent with the mixing of lead from major population centers in the Southern Hemisphere in the mid to high latitudes, except for the presence of highly radiogenic lead in some samples. Contributions from radiogenic lead of up to ∼0.8% were observed. Three periods with the highest percentage contribution of radiogenic lead (>0.5%) were investigated in more detail, and 4-d back-trajectories and radon concentrations were used to help identify the sources. The sources are probably associated with the mining and processing of uranium rich ores in southern Africa and possibly South Australia.     

Seasonal distribution of sulfur fractions in Louisiana salt marsh soils

The profile distributions of specific sulfur forms were examined at a site in a Louisiana salt marsh over a 1-yr period. Soil samples were fractionated into acid-volatile sulfides, HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester-sulfate sulfur, carbon-bonded sulfur, and total sulfur. Inorganic sulfur constituted 16% to 36% of total sulfur, with pyrite sulfur representing <2%. Pyrite sulfur content in marsh soil was relatively high in winter. Pyrite sulfur and elemental sulfur together accounted for 4% to 24% of the inorganic sulfur fraction. Between 74% and 95% of inorganic sulfur was present as the HCl-soluble sulfur form. A significant negative correlation between acid-volatile sulfides and elemental sulfur observed in summer suggested the transformation of fulfides to elemental sulfur. Organic sulfur, in the forms of ester-sulfate sulfur and carbon-bonded sulfur, predominated in all sampling periods, comprising 64% to 84% of total sulfur. The conversion of ester-sulfate sulfur into carbon-bonded sulfur was more likely to occur in winter than in other seasons. Carbon-bonded sulfur accounted for 53% to 89% of the organic sulfur. Organic sulfur was the major contributor to the variation of total sulfur in all seasons studied. Total sulfur concentration showed a statistically significant increase with depth.     

Probing the oxidation-reduction properties of terrestrially and microbially derived dissolved organic matter

Dissolved organic matter (DOM) has been shown to be an integral component in biogeochemical electron transfer reactions due to its demonstrated ability to facilitate redox reactions. While the role of DOM as a facilitator of electron transfer processes has been demonstrated, greater knowledge would lead to better understanding of the structural components responsible for redox behavior, such as quinones and nitrogen and sulfur (N/S) functional groups. This investigation uses direct scan voltammetry (DSV) coupled with fluorescence and NMR spectroscopy as well as thermochemolysis gas chromatography mass spectrometry (GC-MS) and X-ray photoelectron spectroscopy (XPS) to elucidate the organic moieties responsible for facilitating electron transfer reactions. We contrast electrochemical properties and structural details of three organic matter isolates from diverse sources; Great Dismal Swamp DOM (terrestrially derived, highly aromatic), Pony Lake DOM (microbially derived, highly aliphatic) and Toolik Lake (terrestrially derived, photochemically and microbially altered) with juglone (a redox-active model quinone). Aromatic and phenolic constituents were detected (by ¹³C NMR) and recovered (by thermochemolysis GC-MS) from all three fulvic acid samples, highlighting the ubiquity of these compounds and suggesting that the quinone-phenol redox couple is not limited to DOM derived from lignin precursors. The range of hydroxy-benzene and benzoic acid derivatives may explain the lack of a single pair of well-defined oxidation and reduction peaks in the DSV scans. The presence of a wide-range of hydroxylated benzoic acid isomers and other redox-active aromatic residues implies that native DOM possesses overlapping redox potentials analogous to their characteristic range of pK_a values.     

星叶石族矿物红外光谱研究

在新测定的星叶石晶体结构资料的基础上,对星叶石矿物进行了详细和红外光谱研究,对比了单斜及三斜星叶石的红光谱特征,并对星叶石中工外吸收振动的归属问题进行了讨论。