Ion Implants as Matrix‐Appropriate Calibrators for Geochemical Ion Probe Analyses

Ion microprobe elemental and isotopic determinations can be precise but difficult to quantify. Error is introduced when the reference material and the sample to be analysed have different compositions. Mitigation of such ‘matrix effects’ is possible using ion implants. If a compositionally homogeneous reference material is available which is ‘matrix‐appropriate’ (i.e., close in major element composition to the sample to be analysed, but having an unknown concentration of the element, E, to be determined) then ion implantation can be used to introduce a known amount of an E isotope, calibrating the E concentration and producing a matrix‐appropriate calibrator. Nominal implant fluences (ions cm^?2) are inaccurate by amounts up to approximately 30%. However, ion implantation gives uniform fluences over large areas; thus, it is possible to ‘co‐implant’ an additional reference material of any bulk composition having known amounts of E, independently calibrating the implant fluence. Isotope ratio measurement standards can be produced by implanting two different isotopes, but permil level precision requires postimplant calibration of the implant isotopic ratio. Examples discussed include (a) standardising Li in melilite; (b) calibrating a ²⁵Mg implant fluence using NIST SRM 617 glass and (c) using Si co‐implanted with ²⁵Mg alongside NIST SRM 617 to produce a calibrated measurement of Mg in Si.     

Modeling the attenuated total reflectance infrared (ATR-FTIR) spectrum of apatite

Attenuated total reflectance (ATR) infrared spectra were measured on a synthetic and a natural fluorapatite sample. A modeling approach based on the computation of the Fresnel reflection coefficient between the ATR crystal and the powder sample was used to analyze the line shape of the spectra. The dielectric properties of the samples were related to those of pure fluorapatite using an effective medium approach, based on Maxwell–Garnett and Bruggeman models. The Bruggeman effective medium model leads to a very good agreement with the experimental data recorded on the synthetic fluorapatite sample. The poorer agreement observed on the natural sample suggests a more significant heterogeneity of the sample at a characteristic length scale larger than the mid-infrared characteristic wavelength, i.e., about 10 micrometers. The results demonstrate the prominent role of macroscopic electrostatic effects over fine details of the microscopic structure in determining the line shape of strong ATR bands.     

Determination of Precise and Accurate 51V/50V Isotope Ratios by Multi‐Collector ICP‐MS,Part 2: Isotopic Composition of Six Reference Materials plus the Allende Chondrite and Verification Tests

We present the first measurements of vanadium (V) stable isotopes for six reference materials – USGS PCC‐1, BHVO‐2, BCR‐2, BIR‐1a, GSP‐2 and AGV‐2 – plus the widely available carbonaceous chondrite Allende. We present standard addition and matrix spiking tests to assess the robustness and reproducibility of our data. Standard addition utilised an enriched ⁵⁰V solution designated VISSOX (Vanadium Isotope Standard Solution OXford). We further assessed the veracity of the method by spiking collected sample matrices with the same amount of a V standard solution, whose isotopic composition was defined as 0‰. Standard addition and matrix spiking tests recorded no appreciable artificial isotope fractionation. We estimate that the best currently attainable long‐term reproducibility of stable ⁵¹V/⁵⁰V isotope measurements in complex matrices is 0.15‰, which is in the same order as the reproducibility achievable with standard solutions. Finally, a large range of ～ 1.2‰ in stable V isotopic composition was documented, with ～ 0.5‰ of that variation in high temperature igneous materials alone. The range and resolving power of V stable isotopes, with respect to igneous material, compared favourably with the magnitude of fractionation reported for other non‐traditional stable isotope systems, which bodes well for the utility of this new system.     

Characterization of site conditions (soil class,V<Subscript>S30</Subscript>, velocity profiles) for 33 stations from the French permanent accelerometric network (RAP) using surface-wave methods

Data provided by accelerometric networks are important for seismic hazard assessment. The correct use of accelerometric signals is conditioned by the station site metadata quality (i.e., soil class, V_S30, velocity profiles, and other relevant information that can help to quantify site effects). In France, the permanent accelerometric network consists of about 150 stations. Thirty-three of these stations in the southern half of France have been characterized, using surface-wave-based methods that allow derivation of velocity profiles from dispersion curves of surface waves. The computation of dispersion curves and their subsequent inversion in terms of shear-wave velocity profiles has allowed estimation of V_S30 values and designation of soil classes, which include the corresponding uncertainties. From a methodological point of view, this survey leads to the following recommendations: (1) perform both active (multi-analysis surface waves) and passive (ambient vibration arrays) measurements to derive dispersion curves in a broadband frequency range; (2) perform active acquisitions for both vertical (Rayleigh wave) and horizontal (Love wave) polarities. Even when the logistic contexts are sometimes difficult, the use of surface-wave-based methods is suitable for station-site characterization, even on rock sites. In comparison with previous studies that have mainly estimated V_S30 indirectly, the new values here are globally lower, but the EC8-A class sites remain numerous. However, even on rock sites, high frequency amplifications may affect accelerometric records, due to the shallow relatively softer layers.     

Imprints of wave climate and mean sea level variations in the dynamics of a coastal spit over the last 250 years: Cap Ferret,SW France

In coastal areas, sea level rise (SLR) and changing wave climates are expected to be the main oceanic drivers of shoreline adjustments. These drivers have been shown to vary on a wide spectrum of spatial and temporal scales. Nonetheless, a general rule about how this variability impacts global shorelines remains to be articulated. Here, we discuss the impacts of wave climate changes and SLR on the evolution of a barrier spit–inlet system over the last 250 years. The distal end of the Cap Ferret barrier spit, SW France, has undergone large-scale oscillations that were well correlated with variations of the decadal average of the winter North Atlantic Oscillation (NAO) index. The local wave climate hindcast supports that increased alongshore wave energy fluxes associated with the positive phase of the NAO were responsible for the updrift retreat of the spit. By opposition, the spit has elongated downdrift when waves were less energetic and more shore normal, as during the negative phase of the NAO. In addition, lower rates of SLR appeared to be necessary for the spit to develop, as higher rates of SLR very likely forced the adjacent inlet to enlarge, at the expense of the spit. These results should help to predict and detect coastal adjustments driven by climate change and by climate variability. © 2019 John Wiley & Sons, Ltd.     

A window on West Antarctic crustal boundaries: the junction between the Antarctic Peninsula, the Filchner Block, and Weddell Sea oceanic lithosphere

A new airborne magnetic survey of the southeastern Antarctic Peninsula and adjacent Weddell Sea embayment (WSE) region suggests a continuity of geological structure between the eastern Antarctic Peninsula and the attenuated continental crust of the Filchner Block. This has implications for the reconstructed position of the Ellsworth–Whitmore Mountains block in Gondwana, which is currently uncertain. Palaeomagnetic data indicate that it has migrated from a Palaeozoic position between South Africa and Coats Land to its current position as a microplate embedded in central West Antarctica. The most obvious route for migration is between the Antarctic Peninsula and the Weddell Sea embayment. Evidence that geological structures are continuous across the boundary places constraints on the timing and pathway of migration. Magnetic textures suggest the presence of shallow features extending from the Beaumont Glacier Zone (BGZ) in the west for at least 200 km into the Weddell Sea embayment. These data suggest that the Eastern Domain of the Antarctic Peninsula and the stretched continental crust of the Filchner Block share a common recent, probably post-Early Jurassic, history. However, examination of deep anomalies indicates differences in the magnetic characteristics of the two blocks. The boundary may mark either the edge of extended continental crust, or a discontinuity between two, once separated, blocks. This discontinuity, or pre-Late Jurassic Antarctic Peninsula terrane boundaries to the west, may have allowed the passage of the Ellsworth–Whitmore Mountains block to its present location.     

An explanation for salinity- and SPM-induced vertical countergradient buoyancy fluxes

Measurements of turbulent fluctuations of velocity, salinity, and suspended particulate matter (SPM) are presented. The data show persistent countergradient buoyancy fluxes. These countergradient fluxes are controlled by the ratio of vertical turbulent kinetic energy (VKE) and available potential energy (APE) terms in the buoyancy flux equation. The onset of countergradient fluxes is found to approximately coincide with larger APE than VKE. It is shown here that the ratio of VKE to APE can be written as the square of a vertical Froude number. This number signifies the onset of the dynamical significance of buoyancy in the transport of mass. That is when motions driven by buoyancy begin to actively determine the vertical turbulent transport of mass. Spectral and quadrant analyses show that the occurrence of countergradient fluxes coincides with a change in the relative importance of turbulent energetic structures and buoyancy-driven motions in the transport of mass. Furthermore, these analyses show that with increasing salinity-induced Richardson number (Ri), countergradient contributions expand to the larger scales of motions and the relative importance of outward and inward interactions increases. At the smaller scales, at moderate Ri, the countergradient buoyancy fluxes are physically associated with an asymmetry in transport of fluid parcels by energetic turbulent motions. At the large scales, at large Ri, the countergradient buoyancy fluxes are physically associated with convective motions induced by buoyancy of incompletely dispersed fluid parcels which have been transported by energetic motions in the past. Moreover, these convective motions induce restratification and enhanced settling of SPM. The latter is generally the result of salinity-induced convective motions, but SPM-induced buoyancy is also found to play a role.     

Enriched back-arc basin basalts from the northern Mariana Trough: implications for the magmatic evolution of back-arc basins

The composition of basalts erupted at the earliest stages in the evolution of a back-arc basin permit unique insights into the composition and structure of the sub-arc mantle. We report major and trace element chemical data and O-, Sr-, Nd-, and Pb- isotopic analyses for basalts recovered from four dredge hauls and one ALVIN dive in the northern Mariana Trough near 22°N. The petrography and major element chemistry of these basalts (MTB-22) are similar to tholeiites from the widest part of the Trough, near 18°N (MTB-18), except that MTB-22 have slightly more K₂O and slightly less TiO₂. The trace element data exhibit a very strong arc signature in MTB-22, including elevated K, Rb, Sr, Ba, and LREE contents; relatively lowK/Ba and highBa/La andSr/Nd. The Sr- and Nd- isotopic data plot in a field displaced from that of MTB-18 towards Mariana arc lavas, and the Pb-isotopic composition of MTB-22 is indistinguishable from Mariana arc lavas and much more homogeneous than MTB-18. Mixing of 50–90% Mariana arc component with a MORB component is hypothesized. We cannot determine whether this resulted from physical mixing of arc mantle and MORB mantle, or whether the arc component is introduced by metasomatism of MORB-like mantle by fluids released from the subducted lithosphere. The strong arc signature in back-arc melts from the Mariana Trough at 22°N, where the back-arc basin is narrow, supports general models for back-arc basin evolution whereby early back-arc basin basalts have a strong arc component which diminishes in importance relative to MORB as the back-arc basin widens.     

Reference Samples for Electron Microprobe Analysis*

The chemical analyses of twenty-six minerals, four natural glasses, and one synthetic glass prepared for use as microprobe reference samples are presented. New chemical analyses of minerals and revised analyses of several minerals published previously are included. Details of sample preparation are described and the homogeneity of the samples has been tested by the homogeneity index.