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:

     

Kinetics of pyrite to pyrrhotite reduction by hydrogen in calcite buffered solutions between 90 and 180 °C: Implications for nuclear waste disposal

The kinetics of abiotic redox reactions induced by hydrogen are poorly documented although it represents a growing area of interest in terms of both nuclear waste storage assessment and the comprehensive study of hydrogen-rich fluid in mid-ocean ridge hydrothermal systems. We present an experimental kinetics study of pyrite reduction into pyrrhotite under significant H₂ pressure and mid-hydrothermal conditions. We describe the mechanism and kinetic behavior of this reaction by combining textural and solution analyses under various conditions of temperature, pyrite particles size, H₂ pressure and pH. When pH is controlled by calcite, the reaction presents all the characteristics of a coupled dissolution-precipitation mechanism occurring at the pyrite-pyrrhotite interface. By considering the chemical affinity of the coupled reaction as a function of reaction extent, we demonstrate that the spatial coupling is induced both by pyrite as a substrate for pyrrhotite nucleation and by the role of fluid chemistry at the reaction front. Far from equilibrium with respect to pyrite, the kinetics of sulfide production associated with the reaction are linearly related to the square root of time with an activation energy of 53 kJ/mol. This value is higher than what is expected for a diffusion-controlled kinetic regime. We suggest that the reaction rate is controlled both by pyrite reductive dissolution and by sulfide diffusion through the porous pyrrhotite microstructure. We provide a simple sulfide production-rate expression on the basis of our measured rate constants that can be used in geochemical modeling to further evaluate the impact of hydrogen on pyrite under nuclear waste disposal conditions.     

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.     

Use of micro-XRF chemical analysis for mapping volcanogenic massive sulfide related hydrothermal alteration: Application to the subaqueous felsic dome-flow complex of the Cap d'Ours section,Glenwood rhyolite,Rouyn-Noranda,Québec,Canada

A new analytical method using micro-X-ray fluorescence (XRF) is presented for the in situ analysis of major elements in rock samples. This approach has allowed for a separate study of hydrothermal alteration of matrix versus fragments in volcaniclastic material (i.e. flow breccia). This is particularly important for volcanogenic massive sulfide (VMS) exploration in subaqueous felsic dome-flow complexes, where brecciated facies are omnipresent and the imprint of hydrothermal alteration is typically heterogeneous. In this study, eleven elements are measured with a 1.7 by 1.3 mm window considered to be representative of each sample, based on replicate analyses. An average is calculated for the analyzed window and yields a nearly complete analysis with the exception of loss of ignition (LOI). Micro-XRF data were validated using whole rock XRF analyses performed on the same sample block. The application of this chemical method has been tested successfully on thin sections from the Cap d'Ours section of the Glenwood rhyolite in the Rouyn-Noranda region of Québec, Canada. With 58 samples spaced at approximately 50 m intervals, two styles of alteration zoning were recognized: (1) a lateral and concordant zoning expressed by vent-proximal silicification in the west grading toward vent-distal chlorite–sericite alteration to the east, and (2) vertical and discordant zoning expressed by stronger sericitization in the upper part of later volcanic quartz- and feldspar-phyric endogenous lobes. The former is typical of cooling induced by seawater interaction at the lava–water interface at temperatures greater than 400 °C, whereas the latter is related to lower temperature (< 300 °C) hydrothermal mineralization associated with endogenous lobe emplacement within the volcanic pile. The presented results clearly demonstrate the potential use of the micro-XRF data for characterizing weak to intense hydrothermal alteration in highly fragmented volcanic rocks.     

Determination of chemical weathering rates from U series nuclides in soils and weathering profiles: Principles,applications and limitations

The development of U-series nuclides for investigating weathering processes has been significantly stimulated by the analytical improvement made over the last decades in measuring the ²³⁸U series with intermediate half-lives (i.e., ²³⁴U–²³⁰Th–²²⁶Ra). It is proposed in this paper to present principles and methods that are now being developed to determine weathering rates from the study of U-series nuclides in soils and weathering profiles. Mathematical approaches, developed to calculate such rates, are based on some implicit assumptions that are also presented and must be kept in mind if one wants to correctly interpret the obtained ages.     

Insight into the development of a carbonate platform through a multi-disciplinary approach: a case study from the Upper Devonian slope deposits of Mount Freikofel (Carnic Alps,Austria/Italy)

The development and behavior of million year-scaled depositional sequences recorded within Palaeozoic carbonate platform has remained poorly examined. Therefore, the understanding of palaeoenvironmental changes that occur in geological past is still limited. We herein undertake a multi-disciplinary approach (sedimentology, conodont biostratigraphy, magnetic susceptibility (MS), and geochemistry) of a long-term succession in the Carnic Alps, which offers new insights into the peculiar evolution of one of the best example of Palaeozoic carbonate platform in Europe. The Freikofel section, located in the central part of the Carnic Alps, represents an outstanding succession in a fore-reef setting, extending from the Latest Givetian (indet. falsiovalis conodont zones) to the Early Famennian (Lower crepida conodont zone). Sedimentological analysis allowed to propose a sedimentary model dominated by distal slope and fore-reef-slope deposits. The most distal setting is characterized by an autochthonous pelagic sedimentation showing local occurrence of thin-bedded turbiditic deposits. In the fore-reef slope, in a more proximal setting, there is an accumulation of various autochthonous and allochthonous fine- to coarse-grained sediments originated from the interplay of gravity-flow currents derived from the shallow-water and deepwater area. The temporal evolution of microfacies in the Freikofel section evolves in two main steps corresponding to the Freikofel (Unit 1) and the Pal (Unit 2) limestones. Distal slope to fore-reef lithologies and associate changes are from base to top of the section: (U1) thick bedded litho- and bioclastic breccia beds with local fining upward sequence and fine-grained mudstone intercalations corresponding, in the fore-reef setting, to the dismantlement of the Eifelian–Frasnian carbonate platform during the Early to Late Frasnian time (falsiovalis to rhenana superzones) with one of the causes being the Late Givetian major rift pulse; (U2) occurrence of thin-bedded red nodular and cephalopod-bearing limestones with local lithoclastic grainstone intercalations corresponding to a significant deepening of the area and the progressive withdrawal of sedimentary influxes toward the basin, in relation with Late Frasnian sea-level rise. MS and geochemical analyses were also performed along the Freikofel section and demonstrate the inherent parallel link existing between variation in MS values and proxy for terrestrial input. Interpretation of MS in terms of palaeoenvironmental processes reflects that even though distality remains the major parameter influencing MS values, carbonate production and water agitation also play an important role.     

Carbon and oxygen stable isotope compositions of late Pleistocene mammal teeth from dolines of Ajoie (Northwestern Switzerland)

Fossils of megaherbivores from eight late Pleistocene ¹⁴C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ¹³C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C₃ plant-dominated environment. Enamel δ¹⁸O_PO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ¹⁸O_PO4–δ¹⁸O_H2O-calibrations for modern mammals and a present-day precipitation δ¹⁸O_H2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures.