Contributions of boron isotopes to understanding the hydrogeochemistry of the coastal detritic aquifer of Castellón Plain,Spain

The Castellón Plain alluvial aquifer, Spain, is intensively exploited to meet the demand for agricultural irrigation and industrial water supply. The geochemistry of its groundwater shows complex salinization in the northern and southern parts of the aquifer, with significant pollution from human origin in the central portion. Boron content and B isotope geochemistry are useful for distinguishing between various sources of pollution and their relative importance in different parts of this aquifer. Boron concentrations in the groundwater vary between 0.01 and 0.85 mg/L. In the more saline groundwaters, found at the northern and southern ends of the study area, the presence of B is linked to inputs from seawater and water with a calcium-magnesium sulphate facies, which feed the aquifer and clearly influence the chemistry of its waters. Evidence of B adsorption processes in some samples is shown by the low B/Cl ratios and the high values of δ¹¹B. In the central portion of the aquifer, the high B/Cl ratios and the strongly negative δ¹¹B are related to pollution of human origin.     

New age constraints on emplacement of the Cévenol granitoids, South French Massif Central

During the development of the Variscan orogeny, large amounts of granitic melt were produced, giving rise to the intrusion of granitoids at different structural levels. Despite numerous studies, ages available from previous work on the Cévennes granites remain largely imprecise. In order to better constrain the age and emplacement mode of these granites, we have combined U–Pb dating on monazites and zircons and ⁴⁰Ar/³⁹Ar dating on biotites with petrological observations, major element chemical analysis and SEM zircon imaging on five samples from the Aigoual–St Guiral–Liron and Mont Lozère granitic massifs. The results revealed that granitic intrusions and cooling in Southern Cévennes occurred in a short time span at ∼306 Ma after the main episode of regional metamorphism. Petrological and chemical data suggest that they result from a mixing between mantle-derived basic magmas (lamprophyres) and lower crust acid magmas. At a regional scale the production of these melts occurred at the end of crustal thickening induced by nappe stacking, at the same time as the late anatectic events recorded further north in the Velay dome and the granulite facies metamorphism recorded in metasedimentary granulite enclaves brought up by Tertiary volcanoes of the Velay area (Bournac).     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Phase differences between irradiance and velocity low degree solar acoustic modes revisited

Since 1984, simultaneous observations of irradiance and velocity solar acoustic modes, have been carried out by several authors in order to measure the phase difference between irradiance and velocity modes. Following the earliest observations with stratospheric balloon (Frolich and van Der Raay, 1984), a two ground-based stations (Tenerife and Baja California) were established (Jimenez et al, 1990) obtaining coherence results in the frequency range from 2.5 mHz to 4.3 mHz. These phase differences between irradiance and velocity solar acoustic modes are interpreted in terms of the non-adiabatic behaviour of the solar atmosphere. In 1988 the IPHIR (Frolich et al, 1988) instrument flown on the PHOBOS-2 mission to Mars and measured the solar irradiance during 150 consecutive days. The best velocity observations obtained in Tenerife for this period were compared with IPHIR data to compute the phase differences (Schrijver et al, 1991). The final conclusion is that good agreement is attained between space quadsi-space and ground observations which yield a phase diffenrece of about -125 degrees in the frequency range 2.5 mHz to 4.2 mHz, with a slight increase suggested by the data running up to 4.6 mHz.     

On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.     

Diamondiferous eclogites from Yakutia,Siberia: evidence for a diversity of protoliths

Major-element and REE compositions of 14 diamondiferous eclogites from the Udachnaya kimberlite in Yakutia, Siberia have been determined by electron microprobe and secondary ion mass spectrometer (SIMS). Based on previous clinopyroxene classification schemes (e.g., Taylor and Neal 1989), all of these eclogite xenoliths belong to Group B/C, although some of the garnet compositions and mineral REE abundances are inconsistent with the indicated groups. This demonstrates the inadequacy of the classification scheme based on African eclogites for application to Siberian samples. Because of the coarse grain size of the Udachnaya nodules, meaningful modal abundances could not be obtained. However, reconstructed REE compositions using various garnet: clinopyroxene ratios demonstrate relative insensitivity to changes in mode for common eclogitic assemblages. Many of these reconstructed REE compositions show LREE depletions. Some depletions are consistent with an origin (either directly or through partial melting) as normal or Type-I ocean floor basalt. Others, however, require material of eclogitic or pyroxenitic affinities to undergo partial melting; this facilitates the depletion of LREE while leaving the HREE at nearly original levels. Many of the eclogites of South Africa are consistent with a protolith of anomalous or Type II ocean floor basalt. This fundamental difference between the two regions is the likely cause of the inconsistencies with the chemicallybased classification.     

Generalized Lyapunov exponents indicators in Hamiltonian dynamics: An application to a double star system

The Lyapunov characteristic numbers (LCNs) which are defined as the mean value of the distribution of the local variations of the tangent vectors to the flow (=ln _k ⁱ ) (see Froeschlé, 1984) have been found to be sensitive indicators of stochasticity. So we computed the distribution of these local variations and determined the moments of higher order for the integrable and stochastic regions in a binary star system with =0.5.     

Chemical abundance behavior of type I planetary nebulae

In this work 13 Planetary Nebulae have been classified as Type I according to Peimbert's criteria (Peimbert, 1978). These objects have been added to a previous sample (Maciel and Faúndez-Abans, 1985) and diagrams of O/H versus N/H, S/H, Ne/H and Ar/H, as well as N/H versus S/H, Ne/H and Ar/H have been drawn. All of them exhibit a tendency for linear correlation; moreover, the behavior of O and N versus Ar and S are very similar, with approximately the same slope. When the excitation class parameter was included in the diagrams, no clear tendency can be discerned, for any class.