Textural evolution of polyhedral olivine experiencing rapid cooling rates

Dynamic crystallization experiments in the CaO–MgO–Al₂O₃–SiO₂ (CMAS) system have been used to investigate the change in crystal shape when pre-existing polyhedral olivine crystals are cooled rapidly (1,639–2,182°C/h). Polyhedral olivines are crystallized initially in a first step using a slow cooling rate (2°C/h), then skeletal and dendritic overgrowths develop on the polyhedral crystals during a subsequent fast cooling event. During this second episode small dendritic olivines also nucleate within the liquid phase. Observation of the experimental sample by optical microscopy shows that the polyhedral olivine shape progressively changes to a skeletal and then to a dendritic morphology in the following sequence: polyhedral ⇒ hopper polyhedral ⇒ dendritic polyhedral. This evolutional sequence is discussed in terms of changes in the crystal growth conditions during cooling and a general relation between these olivine dynamic crystallization experiments and the integrated model of crystal growth by Sunagawa (Bull Minér 104:81–87, 1981, Morphology of crystals, Terra Scientific Publishing Company, 1987) is proposed.     

Fatty acid transfer in the food web of a coastal Mediterranean lagoon: Evidence for high arachidonic acid retention in fish

The transfer of fatty acids (FAs) in the food web of a Mediterranean lagoon was studied using FA compositional patterns across several trophic levels. The structure of the food web was inferred from C and N stable isotopes values and an isotope mixing model was used in order to estimate the relative contribution of the different potential food sources to the biomass of consumers. Bidimensional plots of FA composition of food web components against their δ¹⁵N values indicated a general trend of increasing proportions of highly unsaturated fatty acids (HUFAs) with increasing trophic levels while the proportions of saturated fatty acids (SAFAs) and 18-carbon polyunsaturated fatty acids (PUFAs) decreased. Using the relative contributions of food sources to consumers and their FA compositions, a model was built in order to estimate the PUFA composition of consumer mixed diets which was compared to consumer PUFA profiles. The latter allowed the identification of the PUFAs which were mostly enriched/retained in consumer lipids. There was a surprisingly high retention of arachidonic acid (ARA), a trend which challenges the idea of low ARA needs in marine fish and suggests the important physiological role of this essential FA for fish in estuarine environments.     

Hydrological conditions over the western Mediterranean basin during the deposition of the cold Sapropel 6 (ca. 175 kyr BP)

A new oxygen isotope record is reported from a stalagmite collected in the Argentarola Cave located on the Tyrrhenian coast of Italy. As shown from observations and numerical modeling of δ¹⁸O in modern precipitation, the recorded δ¹⁸O variability for this zone is dominated by the amount of precipitation (so-called ‘amount effect’). The δ¹⁸O profile measured in the stalagmite is characterized by a prominent negative excursion (ca. 2-3‰) between 180 and 170 kyr BP. This paleoclimatic feature is interpreted as being due to a relatively wet period which occurred during the penultimate glacial period, more precisely, during Marine Isotope Stage 6.5. This pluvial phase is shown to correspond chronologically to the deposition of the sapropel event 6 (S6). Although this particular sapropel event occurred during a cold phase, the δ¹⁸O excursion is similar to those corresponding to other sapropels (S4, S3 and S2). The evidence for humid conditions during S6 in the western Mediterranean basin agrees with previous studies based on deep-sea sediment cores. Taken collectively, the data suggest that during sapropel events dilution of ocean surface waters was not restricted to the output of the river Nile but was rather widespread over the entire Mediterranean Sea due to increased rainfall.     

Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO₄·2H₂O), ferric arsenates, arseniosiderite (Ca₂Fe₃(AsO₄)₃O₂·3H₂O), Ca-Fe arsenates, pharmacosiderite (KFe₄(AsO₄)₃(OH)₄·6-7H₂O), jarosite (K₂Fe₆(SO₄)₄(OH)₁₂) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As⁵⁺in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.     

Spatial Variability of Trends in the Rainfall-Runoff Relationship: A Mesoscale Study in the Mosel Basin

The spatial variability of observed trends in rainfall structure over the last 5 decades and its effects on the spatial variability of maximum daily water levels in the Grand-Duchy of Luxembourg (Europe) were investigated in 9 sub-basins of the Mosel river. Over the past 25 years, an increase in westerly atmospheric circulation types during winter months has caused an increase in winter rainfall totals, duration and intensity. More specifically, the spatial variability of trends having affected winter rainfall totals, duration and intensity have led to spatially varying positive trends in maximum daily water levels. Observed trends in rainfall characteristics and maximum daily water levels during winter show closely linked spatial patterns that are strongly related to the topography of the study area.     

Ptolemaic Transformation in Keplerian Problem

We propose the Ptolemaic transformation: a canonical change of variables reducing the Keplerian motion to the form of a perturbed Hamiltonian problem. As a solution of the unperturbed case, the Ptolemaic variables define an intermediary orbit, accurate up to the first power of eccentricity, like in the kinematic model of Claudius Ptolemy. In order to normalize the perturbed Hamiltonian we modify the recurrent Lie series algorithm of HoriuuMersman. The modified algorithm accounts for the loss of a term's order during the evaluation of a Poisson bracket, and thus can be also applied in resonance problems. The normalized Hamiltonian consists of a single Keplerian term; the mean Ptolemaic variables occur to be trivial, linear functions of the Delaunay actions and angles. The generator of the transformation may serve to expand various functions in Poisson series of eccentricity and mean anomaly.     

Fundamental processes controlling the first stage of alteration of a basalt glass by seawater: an experimental study between 200° and 320°C

The first stage of alteration of a basalt glass by seawater has been studied experimentally between 200° and 320°C under vapor pressure, following both the chemical evolution of the reacting solutions during the experiments and the chemical and mineralogical transformations of the altered glass surface via microprobe, scanning transmission electron microscope and resonant nuclear reactions.The alteration is controlled by diffusion of dissolved species through an altered layer and not by surface chemical reaction. Selective removal of cations with respect to SiO₂ leads to the formation of a thick, porous protonated surface layer enriched in SiO₂. Aqueous diffusion of dissolved species from the reacting glass and from solution through the pores of this layer results in the formation of an amorphous silicate gel which is the precursor of normal crystalline clays (saponites) appearing in a later stage.Computer simulations of the alteration generated with the EQ3/6 computer software package account for the chemical composition of the rim and the sequence of secondary minerals found in the experiments.     

Keplerian expansions in terms of Henrard's practical variables

Formulae for the Keplerian expansions in terms of Henrard's practical variables are given. Two different methods were applied: one using the Bessel functions and one based on the Lie transforms. The former involves less series products, but the latter is more flexible and universal.     

Determination of the petrologic type of CV3 chondrites by Raman spectroscopy of included organic matter

This paper reports the first reliable quantitative determination of the thermal metamorphism grade of a series of nine CV3 chondrites: Allende, Axtell, Bali, Mokoia, Grosnaja, Efremovka, Vigarano, Leoville, and Kaba. The maturity of the organic matter in matrix, determined by Raman spectroscopy, has been used as a powerful metamorphic tracer, independent of the mineralogical context and extent of aqueous alteration. This tracer has been used along with other metamorphic tracers such as Fe zoning in type-I chondrules of olivine phenocrysts, presolar grain abundance and noble gas abundance (bulk and P3 component). The study shows that the petrologic types determined earlier by Induced ThermoLuminescence were underestimated and suggests the following values: PT (Allende-Axtell) >3.6; PT (Bali-Mokoia-Grosnaja) ∼3.6; PT (Efremovka-Leoville-Vigarano) = 3.1-3.4; PT (Kaba) ∼3.1. The most commonly studied CV3, Allende, is also the most metamorphosed. Bali is a breccia containing clasts of different petrologic types. The attribution suggested by this study is that of clasts of the highest petrologic types, as pointed out by IOM maturity and noble gas bulk abundance. CV3 chondrites have complex asteroidal backgrounds, with various degrees of aqueous alteration and/or thermal metamorphism leading to complex mineralogical and petrologic patterns. (Fe,Mg) chemical zoning in olivine phenocrysts, on the borders of type I chondrules of porphyritic olivine- and pyroxene-rich textural types, has been found to correlate with the metamorphism grade. This suggests that chemical zoning in some chondrules, often interpreted as exchanges between chondrules and nebular gas, may well have an asteroidal origin. Furthermore, the compositional range of olivine matrix is controlled both by thermal metamorphism and aqueous alteration. This does not support evidence of a nebular origin and does not necessarily mirror the metamorphism grade through (Fe,Mg) equilibration. On the other hand, it may provide clues on the degree of aqueous alteration vs. thermal metamorphism and on the timing of both processes. In particular, Mokoia experienced significant aqueous alteration after the metamorphism peak, whereas Grosnaja, which has similar metamorphism grade, did not.