Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.     

Crowdsourcing a cyclist perspective on suggested recreational paths in real-world networks

ABSTRACT

Routing and navigation services for leisure activities are conditioned by special needs and trade-offs. The advent of online communities and large crowdsourced datasets offers opportunities to improve the adoption of a user’s perspective in these suggested paths. This paper focuses on achieving two goals. First, the presented methodology analyses a dataset of 190,610 historical GPS traces to gain insights into the appreciation or attractiveness of each edge in a real-world network for a specific leisure activity (i.e. road cycling). Second, as literature on these leisure activities is still sparse, we want to create a thorough understanding of the activities at hand for future work. An appreciation model is proposed and the spread of this score is analyzed in shortest-path alternatives of popular routing engines for this activity. This analysis successfully discriminates these shortest paths based on the scoring value and three morphological parameters of the path. However, the robustness of the model should be improved to ensure the viability of the proposed approach in future work. More specifically, further research on the local optimality of the route choices will be imperative.     

Coastal response to the Holocene transgression in the Bahamas: episodic sedimentation versus continuous sea-level rise

Sedimentological and petrographic study of Holocene deposits in the Eastern Bahamas shows that sedimentation occurred episodically during this period of continually rising sea-level.

The Holocene stratigraphic record exposed on the islands of San Salvador, Lee Stocking and Cat consists of two distinctive units separated by a paleosol: (1) 5000 year-old oolitic eolianites deposited when sea-level was lower than today, and (2) 3000 to 500 year-old bioclastic paleo-beaches and dunes that are congruent with the present stand of sea-level.

A five-stage model that reconciles intermittent sedimentation pattern with continuous sea-level rise is presented. Pre-Holocene topography and changes in the rate of the transgression seem to regulate local⁴ hydrodynamic conditions, which in turn control onset and offset of sedimentary processes.

This Holocene example of episodic sedimentation during an uninterrupted transgression should be considered when studying ancient discontinuities that are systematically interpreted in terms of relative sea-level fall.     

Anharmonicity and high-temperature heat capacity of crystals: the examples of Ca2GeO4, Mg2GeO4 and CaMgGeO4 olivines

Drop-calorimetry determinations of the isobaric heat capacity (C_P) of Mg₂GeO₄, Ca₂GeO₄ and CaMgGeO₄ have been made up to 1700 K. The thermal expansion coefficient (α) of these olivine germanates has been determined from high-temperature X-ray measurements up to 1500 K. From these measurements and available compressibility data, one calculates that the isochoric heat capacity (C_V) exceeds the harmonic limit of Dulong and Petit above 1000–1200 K. Such an intrinsic anharmonic behaviour can be accounted for by introducing anharmonic parameters a_i=(? ln v _i/?T)_V in vibrational modelling of C_V. These parameters are calculated from pressure and temperature shifts of the vibrational frequencies as measured by Raman spectroscopy up to 10 GPa at room temperature and up to 1300 K at 1 bar. A comparison of the Raman spectra of the three germanates with those of natural olivines justifies once again the use of germanates as silicate analogues. Extensive Ca,Mg disordering likely takes place in CaMgGeO₄, beginning at about 1100 K and leading to unusually high increases of the heat capacity and thermal expansion coefficient.     

Seismic analysis of non-linearly base-isolated soil-structure interacting reactor building by way of the hybrid frequency-time-domain procedure

The seismic analysis of a reactor building on a sliding-type base isolation is performed by way of the hybrid frequency-time-domain procedure. The frequency dependence of the foundation stiffness coefficients is duly accounted for in the analysis, although the problem is non-linear. The response results are shown to be reliable by way of comparison with the results of a time-stepping algorithm in the specialized case of constant foundation stiffness coefficients. The fact that such an analysis can be performed is an outstanding result, particularly when considering that no difficulties are encountered in the implementation and in the calculation. The flow chart used to implement the procedure is presented in the paper. The reactor building is analysed for three different sites with each site having three sets of material properties. It appears that the structural response is not strongly affected by the frequency dependence of the foundation stiffness coefficients. This also holds true as far as the response of equipment attached to the superstructure is concerned. For all practical purposes this frequency dependence may be disregarded in favour of constant spring and damping coefficients.     

A gap in the North American Central Plains conductivity anomaly

The palaeotectonic models of the North American continent have been deeply influenced by the concept of a North American Central Plains conductivity anomaly (NACPCA) which was postulated as a result of large area, wide-spaced, array studies, using the Magnetic Deep Sounding (MDS) method.

A recent closely spaced magnetotelluric (MT) survey across this proposed anomaly near the Canadian-U.S. boundary by Jones and Savage (1986) failed to detect the NACPCA at the location suggested by the MDS. However, this survey did verify a conductivity anomaly discovered by Rankin and Kao (1979) and a new anomaly 75 km east of NACPCA. Our present study verifies this latter anomaly and quantitative results are presented. The striking isotropy in apparent resistivity does not prevent the interpretation of anomalous resistivity distributions. This is discussed in the text.

The failure of the MDS array studies to detect our anomaly is readily explainable by the wide station spacing; however, the failure of the MT survey to detect the NACPCA leads us to the conclusion that it may not be a continuous feature.     

Study of two alteration systems as natural analogues for radionuclide release and migration

U-deposit hosted in hydrothermally altered tuffs in Mexico, together with weathering profiles from Cameroon were studied as natural analogues of radionuclide release and migration. Using petrological and spectroscopic methods (infrared and electron paramagnetic resonance), we have distinguished successive secondary mineral parageneses and the behaviour of radionuclides.

In the U-deposit, the mineral parageneses show that uranium migration is mainly controlled by the redox potential and silica activity of the altering solutions. The high silica content of the solutions is caused by the intense alteration of volcanic rocks. Two types of secondary clay mineral parageneses are evidenced: a kaolinization, intense where uranium is accumulated in the welded tuffs, and a smectitization mainly developed in the underlying weakly welded tuffs.

Several types of kaolinite have been defined according to their genesis (fillings in fissures and feldspar pseudomorphs), their location relative to a breccia pipe where uranium has accumulated (core and rim of the pipe; surrounding rhyolitic tuffs), and particle morphology, structural order and substitutional Fecontent. It is shown that the variations of the concentration of paramagnetic defect centres, always more than ten times as important than those measured in weathering kaolinites, are only correlated to the location of the kaolinites. The highest values correspond to the breccia pipe kaolinites, e.g. kaolinites located in the uranium accumulation zones. Moreover, one or two main defects centres are detected depending on the intimate association of kaolinites with uranium-bearing minerals. Besides, in weathering kaolinites from U-depleted laterites, defect centre concentrations are correlated to the total Fe203 content in bulk samples. This means that the defect centre acts as a memory of the travel of uranium when this element was sorbed onto iron gels in the first stage of weathering.

It is concluded that paramagnetic defect centres in kaolinites might allow an efficient fingerprint of successive irradiations in the natural analogues under study and could be an useful tool to control radionuclides migration through kaolinite-containing clayey materials such as those used for waste repository.

A better understanding of radiation efficiency as well as accurate dose-ratekaolinite-containing clayey materials such as those used for waste reposit estimation are needed for a quantitative tracing of the migration ofA better understanding of radiation efficiency as well as accurate dose-ratekaolin radionuclide elements. With this aim, a simulation has been undertaken withestimation are needed for a quantitative tracing of the migration of various radiations sources. We have determined for each irradiation the parameters of the paramagnetic centres created in order to understand the way they are forming. The knowledge of the parameters governing the formation and the stability of the radiation centres in kaolinites allow to use this mineral as a natural dosimeter.