Characterization of metalliferous sediment from a low-temperature hydrothermal environment on the Eastern Flank of the East Pacific Rise

Metalliferous deposits are described from the eastern flank of the East Pacific Rise (EPR) offshore Costa Rica, close to a basaltic seamount called “Dorado high”. Based on heat-flow data and porewater profiles, the site is an area of active low-temperature hydrothermal discharge. We focus on the mineralogical and chemical analysis from a 124 cm long gravity core (GC50), located on the northwestern slope of the 100 m high Dorado. In this core, the sediments consist of detrital clay minerals as well as authigenic minerals such as zeolites, apatites, and Fe/Mn-rich oxyhydroxides. In contrast, the reference sediments from adjacent areas without hydrothermal activity are olive gray hemipelagic muds composed of volcanic glass particles, clay minerals, siliceous microfossils, and some detrital quartz and feldspar. Bulk sediment chemistry and chemical enrichment factors calculated with respect to the reference sediment indicate that the most important chemical changes occurred at the base of the core from 100 to 124 cm bsf, with strong enrichments in MnO, CaO, P2O5, and Fe2O3. These enrichments are correlated with the occurrence of authigenic Fe-oxyhydroxide (goethite) and Mn oxide (todorokite and vernadite, at 100 cm bsf), and hydrothermal apatite (110–124 cm bsf). In the upper section of the core from 12 to 70 cm, the sediment is composed of abundant smectite and authigenic phillipsite, and only minor chemical changes can be observed with respect to the reference sediments. The ubiquitous presence of phillipsite suggests that the entire sedimentary column of core GC50 was first affected by diagenesis. However, below 70 cm bsf, these phillipsites are partially dissolved and Fe oxides occur from 110 to 124 cm, followed upward by Mn oxides at 100 cm. This transition from Fe to Mn-rich sediments can be interpreted in terms of an upward increasing redox potential. PAAS-normalized REY patterns of GC50 sediments present clearly negative Ce and positive Y anomalies inherited from seawater at the base of core GC50. These anomalies decrease upward, which we interpret together with the transition from Fe to Mn-rich sediments by an upward migrating low-temperature hydrothermal fluid. Thus, after a first stage of diagenesis, the discharge of a low-temperature hydrothermal fluid occurred through the sedimentary column, leading to the precipitation of hydrothermal compounds that are lacking towards the surface

Ab-initio density functional study of O on the Ag(001) surface

The adsorption of oxygen on the Ag(001) is investigated by means of density functional techniques. Starting from a characterization of the clean silver surfaces oxygen adsorption in several modifications (molecularly, on-surface, sub-surface, Ag$_2$O) for varying coverage was studied. Besides structural parameters and adsorption energies also work-function changes, vibrational frequencies and core level energies were calculated for a better characterization of the adsorption structures and an easier comparison to the rich experimental data.Comment: 26 pages, 8 figures, Surf. Sci. accepte

Second harmonic generation on self-assembled GaAs/Au nanowires with thickness gradient

Here we investigated the SH generation at the wavelength of 400 nm (pump laser at 800 nm, 120 fs pulses) of a "metasurface" composed by an alternation of GaAs nano-grooves and Au nanowires capping portions of flat GaAs. The nano-grooves depth and the Au nanowires thickness gradually vary across the sample. The samples are obtained by ion bombardment at glancing angle on a 150 nm Au mask evaporated on a GaAs plane wafer. The irradiation process erodes anisotropically the surface, creating Au nanowires and, at high ion dose, grooves in the underlying GaAs substrate (pattern transfer). The SHG measurements are performed for different pump linear polarization angle at different positions on the "metasurface" in order to explore the regions with optimal conditions for SHG efficiency. The pump polarization angle is scanned by rotating a half-wave retarder plate. While the output SH signal in reflection is analyzed by setting the polarizer in s or p configuration in front of the detector. The best polarization condition for SHG is obtained in the configuration where the pump and second harmonic fields are both p polarized, and the experiments show a SH polarization dependence of the same symmetry of bulk GaAs. Thus, the presence of gold contributes only as field localization effect, but do not contributes directly as SH generator

Zinc-rich clays in supergene non-sulfide zinc deposits

International audienceThe nature and the origin of zinc clays are poorly understood. With the example of the Bou Arhous Zn-Pb ore deposit in the Moroccan High Atlas, this study presents new data for the mineralogical and chemical characterization of barren and zinc clays associated with non-sulfide zinc ores. In the field, white to ocher granular clays are associated with willemite (Zn2SiO4), while red clays fill karst-related cavities cutting across the non-sulfide ore bodies. Red clays (kaolinite, chlorite, illite, and smectite) present evidence of stratification that reflects internal sedimentation processes during the karst evolution. White clays contain 7-Å clay mineral/smectite irregular interstratified minerals with less than 20 % of smectite layers. Willemite is partially dissolved and is surrounded by authigenic zinc clay minerals. Together with XRD results, WDS analyses on newly formed clay aggregates suggest that this interstratified mineral is composed of fraipontite and sauconite. CEC measurements support that zinc is only located within the octahedral sheets. These new results support the following process: (i) dissolution of willemite, leading to release of Si and Zn, (ii) interaction between Zn-Si-rich solutions and residual-detrital clays, and (iii) dissolution of kaolinite and formation of interstratified zinc clay minerals that grew over detrital micas

Self-Organized Nanogratings for Large-Area Surface Plasmon Polariton Excitation and Surface-Enhanced Raman Spectroscopy Sensing

Surface plasmon polaritons (SPP) are exploited due to their intriguing properties for the fabrication and miniaturization of photonic circuits, for surface-enhanced spectroscopy and imaging beyond the diffraction limit. However, excitation of these plasmonic modes by direct illumination is forbidden by energy/momentum conservation rules. One strategy to overcome this limitation relies on diffraction gratings to match the wavevector of the incoming photons with that of propagating SPP excitations. The main limit of the approaches so far reported in the literature is that they rely on highly ordered diffraction gratings fabricated by means of demanding nanolithographic processes. In this work, we demonstrate that an innovative, fully self-organized method based on wrinkling-assisted ion-beam sputtering can be exploited to fabricate large-area (cm2 scale) nanorippled soda lime templates, which conformally support ultrathin Au films deposited by physical deposition. The self-organized patterns act as quasi-one-dimensional (1D) gratings characterized by a remarkably high spatial order, which properly matches the transverse photon coherence length. The gratings can thus enable the excitation of hybrid SPP modes confined at the Au/dielectric interfaces, with a resonant wavelength that can be tuned by modifying the grating period, photon incidence angle, or, potentially, the choice of the thin-film conductive material. Surface-enhanced Raman scattering experiments show promising gains in the range of 103, which are competitive, even before a systematic optimization of the sample fabrication parameters, with state-of-the art lithographic systems, demonstrating the potential of such templates for a broad range of optoelectronic applications aiming at plasmon-enhanced photon harvesting for molecular or biosensing

Formation of chlorite during thrust fault reactivation. Record of fluid origin and P-T conditions in the Monte Perdido thrust fault (southern Pyrenees)

The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous-Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ18O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P-T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic condition

Self-Organized Nanorod Arrays for Large-Area Surface-Enhanced Infrared Absorption

Capabilities of highly sensitive surface-enhanced infrared absorption (SEIRA) spectroscopy are demonstrated by exploiting large-area templates (cm2) based on self-organized (SO) nanorod antennas. We engineered highly dense arrays of gold nanorod antennas featuring polarization-sensitive localized plasmon resonances, tunable over a broadband near- and mid-infrared (IR) spectrum, in overlap with the so-called "functional group" window. We demonstrate polarization-sensitive SEIRA activity, homogeneous over macroscopic areas and stable in time, by exploiting prototype self-assembled monolayers of IR-active octadecanthiol (ODT) molecules. The strong coupling between the plasmonic excitation and molecular stretching modes gives rise to characteristic Fano resonances in SEIRA. The SO engineering of the active hotspots in the arrays allows us to achieve signal amplitude improved up to 5.7%. This figure is competitive to the response of lithographic nanoantennas and is stable when the optical excitation spot varies from the micro- to macroscale, thus enabling highly sensitive SEIRA spectroscopy with cost-effective nanosensor devices

Asymmetric transmission and anomalous refraction in metal nanowires metasurface

Here we investigated the asymmetric transmission and the anomalous refraction introduced by a metasurface of bent gold nanowires. The refraction follows the generalized Snell's law that takes into account the resonant behavior of metallic nanostructures located at the interface between two dielectrics. Measurements performed in the linear optical regime reveal a large sensitivity to the subwavelength features of the gold nanostructures

Light absorption enhancement in thin film hydrgenated amorphus Si solar cells

In this paper, light absorption enhancement in thin film solar cell (SC) is reported and analyzed. The suggested design is based on a nanostructured pattern that increases the diffuse scattered component of radiation and hence the absorption through the active layer. An ion beam sputtering (lBS) approach is used to texture large areas of the glass substrate with high aspect-ratio ripples in order to increase light scattering. Then, thin film SC supported on the textured glass is simulated and analyzed using 3D finite difference time domain (FDTD) method. The suggested SC can offer an ultimate efficiency of 19.26% with short circuit current of 15.76 mA/cm2 with an enhancement of 31.435% over the SC without texturing surface