A TEM study of exsolution in Ca-rich pyroxenes from the Paris and Renazzo chondrites: Determination of type I chondrule cooling rates

We conducted a transmission electron microscope study of the exsolution microstructures of Ca-rich pyroxenes in type I chondrules from the Paris CM and Renazzo CR carbonaceous chondrites in order to provide better constraints on the cooling history of type I chondrules. Our study shows a high variability of composition in the augite grains at a submicrometer scale, reflecting nonequilibrium crystallization. The microstructure is closely related to the local composition and is thus variable inside augite grains. For compositions inside the pyroxene miscibility gap, with a wollastonite (Wo) content typically below 40 mole%, the augite grains contain abundant exsolution lamellae on (001). For grain areas with composition close to Wo₄₀, a modulated texture on (100) and (001) is the dominant microstructure, while areas with compositions higher than Wo₄₀ do not show any exsolution microstructure development. To estimate the cooling rate, we used the spacing of the exsolution lamellae on (001), for which the growth is diffusion controlled and thus sensitive to the cooling rate. Despite the relatively homogeneous microstructures of augite grains with Wo < 35 mole%, our study of four chondrules suggests a range of cooling rates from ~10 to ~1000 °C h⁻¹, within the temperature interval 1200–1350 °C. These cooling rates are comparable to those of type II chondrules, i.e., 1–1000 °C h⁻¹. We conclude that the formation of type I and II chondrules in the proto-solar nebula was the result of a common mechanism.     

Evaporation and Sublimation of Boric Acid: Application for Boron Purification from Organic Rich Solutions

We report in this paper a series of experiments whose purpose is to test the long held idea of boron volatility when neutral to acidic solutions containing traces of boron are evaporated. Boron recoveries have been measured precisely by isotopic dilution and boron isotopic ratios have also been determined. Most of the evaporations have been conducted at 60-65 °C. It was found that no loss of boric acid occurs when c. 1 μg of B is evaporated in water, HCl, HF and acetone solutions. At the same time, we did not observe any associated B isotopic fractionation. In contrast to previous studies on B volatilisation, it was not found necessary to use mannitol to prevent B losses during the evaporation of acidic solutions. Important losses of boron were observed from solutions of methanol, ethanol and organic-rich natural solutions. In the presence of methanol and ethanol, a volatile methyl (or ethyl) borate is likely to be formed. In contrast to these studies, we show that boron is highly volatile when the dried residues of an evaporation are heated further. The sublimation of boron that then occurs can be moderated by the use of mannitol, but a slight increase of the temperature allows B volatilisation. Despite the substantial losses of B by sublimation, no B isotopic fractionation was observed at 60-65 C. The property of boron to sublime was used to separate B from an organic matrix. A miniaturized sublimation apparatus, comprising a 5 ml Teflon beaker, and the associated microsublimation technique are described. The 100% boron recovery and the absence of B isotopic fractionation make this method suitable for extracting B from organic-rich samples.     

Contribution of long-term hydrothermal experiments for understanding the smectite-to-chlorite conversion in geological environments

The smectite-to-chlorite conversion is investigated through long-duration experiments (up to 9 years) conducted at 300 °C. The starting products were the Wyoming bentonite MX80 (79 % smectite), metallic iron and magnetite in contact with a Na–Ca chloride solution. The predominant minerals in the run products were an iron-rich chlorite (chamosite like) and interstratified clays interpreted to be chlorite/smectite and/or corrensite/smectite, accompanied by euhedral crystals of quartz, albite and zeolite. The formation of pure corrensite was not observed in the long-duration experiments. The conversion of smectite into chlorite over time appears to take place in several steps and through several successive mechanisms: a solid-state transformation, significant dissolution of the smectite and direct precipitation from the solution, which is over-saturated with respect to chlorite, allowing the formation of a chamosite-like mineral. The reaction mechanisms are confirmed by X-ray patterns and data obtained on the experimental solutions (pH, contents of Si, Mg, Na and Ca). Because of the availability of some nutrients in the solution, total dissolution of the starting smectite does not lead to 100 % crystallization of chlorite but to a mixture of two dominant clays: chamosite and interstratified chlorite/smectite and/or corrensite/smectite poor in smectite. The role of Fe/(Fe + Mg) in the experimental medium is highlighted by chemical data obtained on newly formed clay particles alongside previously published data. The newly formed iron-rich chlorite has the same composition as that predicted by the geothermometer for diagenetic to low-grade metamorphic conditions, and the quartz + Fe-chlorite + albite experimental assemblage in the 9-year experiment is close to that fixed by water–rock equilibrium.     

The dependence of albite feldspar dissolution kinetics on fluid saturation state at acid and basic pH: Progress towards a universal relation

Here we report on two separate ongoing, multi-year investigations on the dependence of the dissolution rate (R) of albite feldspar on fluid saturation state, as defined by the Gibbs free energy of reaction (ΔG_r) for dissolution. The investigations are based on dissolution at pH 9.2, 150 °C and pH 3.3, 100 °C. Both studies reveal that the R–ΔG_r relation is highly non-linear and sigmoidal. The kinetic data from the first study, being the most complete, can be fitted with a sigmoidal rate curve that is composed of two separate, parallel rate laws that represent distinct mechanisms of dissolution. The switch between one dominant mechanism and the other may be controlled by a critical free energy. The fact that in both studies the same type of sigmoidal R–ΔG_r relation exists for dissolution at different pH and temperature condition suggests that this behavior may be universal for albite and other feldspars. Moreover, the experimental data contradict the commonly used R–ΔG_r relation that is loosely based on transition state theory (TST). This has important implications with respect to the accuracy of geochemical codes that model water–rock interactions at near-equilibrium conditions.     

In-Street Wind Direction Variability in the Vicinity of a Busy Intersection in Central London

We present results from fast-response wind measurements within and above a busy intersection between two street canyons (Marylebone Road and Gloucester Place) in Westminster, London taken as part of the DAPPLE (Dispersion of Air Pollution and Penetration into the Local Environment; www.dapple.org.uk ) 2007 field campaign. The data reported here were collected using ultrasonic anemometers on the roof-top of a building adjacent to the intersection and at two heights on a pair of lamp-posts on opposite sides of the intersection. Site characteristics, data analysis and the variation of intersection flow with the above-roof wind direction (θ _ref ) are discussed. Evidence of both flow channelling and recirculation was identified within the canyon, only a few metres from the intersection for along-street and across-street roof-top winds respectively. Results also indicate that for oblique roof-top flows, the intersection flow is a complex combination of bifurcated channelled flows, recirculation and corner vortices. Asymmetries in local building geometry around the intersection and small changes in the background wind direction (changes in 15- min mean θ _ref of 5°–10°) were also observed to have profound influences on the behaviour of intersection flow patterns. Consequently, short time-scale variability in the background flow direction can lead to highly scattered in-street mean flow angles masking the true multi-modal features of the flow and thus further complicating modelling challenges.     

A TEM study of four particles extracted from the Stardust track 80

Abstract— Four particles extracted from track 80 at different penetration depths have been studied by analytical transmission electron microscopy (ATEM). Regardless of their positions within the track, the samples present a comparable microstructure made of a silica rich glassy matrix embedding a large number of small Fe‐Ni‐S inclusions and vesicles. This microstructure is typical of strongly thermally modified particles that were heated and melted during the hypervelocity impact into the aerogel. X‐ray intensity maps show that the particles were made of Mg‐rich silicates (typically 200 nm in diameter) cemented by a fine‐grained matrix enriched in iron sulfide. Bulk compositions of the four particles suggest that the captured dust particle was an aggregate of grains with various iron sulfide fraction and that no extending chemical mixing in the bulb occurred during the deceleration. The bulk S/Fe ratios of the four samples are close to CI and far from the chondritic meteorites from the asteroidal belt, suggesting that the studied particles are compatible with chondritic‐porous interplanetary dust particles or with material coming from a large heliocentric distance for escaping the S depletion.     

The influence of temperature and seawater composition on calcite crystal growth mechanisms and kinetics: Implications for Mg incorporation in calcite lattice

The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. To determine if and how temperature is kinetically responsible for the amount of Mg incorporated in calcite, we quantified the influence of temperature and specific dissolved components on the complex mechanism of calcite precipitation in seawater. A kinetic study was carried out in artificial seawater and NaCl-CaCl₂ solutions, each having a total ionic strength of 0.7 M. The constant addition technique was used to maintain [Ca²⁺] at 10.5 mmol kg⁻¹ while [] was varied to isolate the role of this variable on the precipitation rate of calcite.Our results show that the overall reaction of calcite precipitation in both seawater and NaCl-CaCl₂ solutions is dominated by the following reaction:

     

Geomorphologic evidence for Plio‐Quaternary shortening in the southern Neuquén basin (40°S,Argentina)

A morphostructural analysis of a Pliocene flood basalt formation in the southern Neuquén basin (40°S) shows evidence of contractional deformation less than 3.5 Ma ago. This formation exhibits a general dip towards the south‐east, with relict outcrops located 100 m higher than the main source volcano, which suggests a local tilting of the lava flow. This tilt has been brought about by Plio‐Quaternary reactivation of the eastern border of the Sañico Massif along two thrusts that offset the lava flow. Another long‐wavelength bulge in the southern part of the lava flow unit indicates a possible Pliocene uplift of the North Patagonian Massif. These results provide new evidence of continuing shortening in the Neuquén basin during the Plio‐Quaternary, challenging the hypothesis that an extensional regime has existed since the end of the Miocene in this basin.     

Relationship between valve activity, microalgae concentration in the water and toxin accumulation in the digestive gland of the Pacific oyster Crassostrea gigas exposed to Alexandrium minutum

The complexity of the relationships between Alexandrium minutum (A.m.) concentration in the water ([A.m.]_w), Paralytic Shellfish Poisoning contamination in the digestive gland ([PSP]_dg) and valve behavior was explored in oysters Crassostrea gigas. Two experiments were conducted, during which oysters’ valve behaviour were analyzed. Oysters, first acclimated for 10-days with the non harmful microalgae Heterocapsa triquetra (H.t.), were exposed to four microalgae mixtures at constant total concentrations of 10 × 10³ cells ml⁻¹ (experiment-1) and 5 × 10³ cells ml⁻¹ (experiment-2): 100% A.m.; 50% A.m.-50% H.t.; 25% A.m.-75% H.t.; 100% H.t. At the end of experiment-2, [PSP]_dg were measured.At 10 × 10³ cells ml⁻¹, the microalgal ingestion decreased (p < 0.05) with increasing [A.m.]_w but not at 5 × 10³ cells ml⁻¹ (p > 0.05). The frequency of microclosures specifically increased with [A.m.]_w (p < 0.05) and the opening duration with [PSP]_dg (p < 0.0001). Oysters exhibiting the maximum increase in opening duration also exhibited the highest [PSP]_dg. The results are discussed in terms of oyster physiology and origin of the behavioral response.     

Using short-lived nuclides of the U- and Th-series to probe the kinetics of colloid migration in forested soils

The recent chemical dynamics of a podzolic forest soil section (from the Strengbach watershed, France) was investigated using U- and Th-series nuclides. Analyses of (²³⁸U), (²³⁰Th), (²²⁶Ra), (²³²Th), (²²⁸Ra) and (²²⁸Th) activities in the soil particles, the seepage waters, and the mature leaves of the beech trees growing on this soil were performed by TIMS or gamma spectrometry. The simultaneous analysis of the different soil (sl) compartments allows to demonstrate that a preferential Th leaching over Ra must be assumed to explain the (²²⁶Ra/²³⁰Th), (²²⁸Ra/²³²Th) and (²²⁸Th/²²⁸Ra) disequilibria recorded in the soil particles. The overall Ra- and Th- transfer schemes are entirely consistent with the prevailing acido-complexolysis weathering mechanism in podzols. Using a continuous open-system leaching model, the (²²⁶Ra/²³⁰Th) and (²²⁸Ra/²³²Th) disequilibria measured in the different soil layers enable dating of the contemporary processes occurring in this soil. In this way, we have determined that a preferential Th-leaching from the shallow Ah horizon, due to a strong complexation with organic colloids, began fairly recently (18 years ago at most). The continual increase in pH recorded in precipitations over the last 20 years is assumed to be the cause of this enhanced organic complexation. A lower soil horizon (50-60 cm) is also affected by preferential Th leaching, though lasting over several centuries at least, with a much smaller leaching rate. The migration of Th isotopes through this soil section might hence be used as a tracer for the organic colloids migration and the induced radioactive disequilibria demonstrate to be useful for assessing the colloidal migration kinetics in a forested soil.Ra and Th isotopic ratios also appear to be valuable tracers of some mineral-water-plant interactions occurring in soil. The (²²⁸Ra/²²⁶Ra) ratio enables discrimination of the Ra flux originating from leaf degradation from that originating from mineral weathering in shallow −10 cm seepage soil waters. It appears that, at least in some cases, the Ra-isotopic ratio measured in forest-soil seepage waters may not be representative of the Ra-isotopic ratio released from mineral weathering, indicating that the different origins of the dissolved ²²⁶Ra and ²²⁸Ra must be taken into account.