Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.     

Threshold of motion and settling velocities of mollusc shell debris: Influence of faunal composition

Bioclastic particles derived from mollusc shell debris can represent a significant fraction of sandy to gravelly sediments in temperate and cool‐water regions with high carbonate productivity. Their reworking and subsequent transport and deposition by waves and currents is highly dependent on the shape and density of the particles. In this study, the hydrodynamic behaviour of shell debris produced by eight mollusc species is investigated for several grain sizes in terms of settling velocity (measurements in a settling tube) and threshold of motion under unidirectional current (flume experiments using an acoustic profiler). Consistent interspecific differences in settling velocity and critical bed shear stress are found, related to differences in shell density, shell structure imaged by scanning electron microscopy and grain shape. Drag coefficients are proposed for each mollusc species, based on an interpolation of settling velocity data. Depending on the shell species, the critical bed shear stress values obtained for bioclastic particles fall within or slightly below empirical envelopes established for siliciclastic particles, despite very low settling velocity values. The results suggest that settling velocity, often used to describe the entrainment of sediment particles through the equivalent diameter, is not a suitable parameter to predict the initiation of motion of shell debris. The influence of the flat shape of bioclastic particles on the initiation of motion under oscillatory flows and during bedload and saltation transport is yet to be elucidated.     

Synthesis and stability of the garnet calderite in the system Fe-Mn-Si-O

The rare garnet end member calderite, Mn ₃ ²⁺ Fe ₂ ³⁺ Si₃O₁₂, has been synthesized, under the oxygen fugacity of the hematite/magnetite buffer, at pressures not lower than 22 kbar. The synthetic crystals are generally zoned and may contain up to 3 mol% of the Fe²⁺-(=skiagite-) or 10 mol% of the Mn³⁺-(=blythite-) end members, but, under equilibrium conditions, the stable garnets have a restricted compositional range with about 1–4 mol% skiagite. Mn³⁺ represents only a residue of the Mn₂O₃ used in the starting material. At temperatures above 720° C (at 24 kbar) to 850° C (at 30 kbar) these garnets break down into coexisting pairs of magnetite-jacobsite and pyroxmangite-FeSiO₃ solid solutions. No indication for divariancy of this breakdown reaction could be established so that the observed coexistence of garnet and breakdown products over a PT interval must be due to disequilibrium. Although extrapolations of the high-pressure stability data towards lower pressures are hazardous, it is clear that nearly pure calderite garnets can only form in metamorphic environments characterized by geothermal gradients not exceeding some 10°–15° C/km, that is in subduction zone metamorphism. A low-pressure end of the calderite stability is likely because, at temperatures below 250°–300° C, pyroxmangite probably becomes unstable and hydrous Mn²⁺-silicates appear among the low-temperature breakdown products of calderite. Since the upper temperature stability limits of the common garnet end members spessartine and andradite lie some 800° C above that for calderite, solid solutions with these components will drastically stabilize the garnet phase towards both higher temperatures and lower pressures. This explains why garnets containing around 70 mol% calderite can be formed in amphibolitefacies metamorphism.     

Experimental constraints on the origin and evolution of mildly alkalic basalts from the Kerguelen Archipelago, Southeast Indian Ocean

This experimental study examines the role of clinopyroxene fractionation on major element trends and alkalinity variations in mildly alkalic basalts from the Kerguelen Archipelago, Southeast Indian Ocean. Equilibrium crystallization experiments were carried out on a natural basalt (MgO=5 wt.%, alkalinity index=0.10) over a range of pressures (0–1.43 GPa) and water contents (nominally dry to hydrous, 1.2 wt.% H₂O) under relatively oxidizing conditions (Δlog FMQ=+1 to +2) at 0 GPa and relatively reducing conditions (Δlog FMQ=0 to –2) at all higher pressures. The hydrous experiments at 0.93 GPa closely reproduce most of the compositional variations in the 24–25 Ma mildly alkalic lavas from the archipelago, which supports a major role for high-Al clinopyroxene fractionation (5–9 wt.% Al₂O₃) at pressures corresponding to the base of the Northern Kerguelen Plateau (15–20 km). However, clinopyroxene fractionation at depth fails to produce important changes in the alkalinity of the residual melts. The transition from tholeiitic to mildly alkalic basalts on the Kerguelen Archipelago thus reflects primarily changes in melting conditions (lower extents of partial melting at higher pressures), which is related to crustal and lithospheric thickening as distance from the Southeast Indian Ridge increased over time from 43 to 24 Ma.     

Petrographic, REE, fluid inclusion and stable isotope study of magnesite from the Upper Triassic Burano Evaporites (Secchia Valley, northern Apennines): contributions from sedimentary, hydrothermal and metasomatic sources

Sparry and microcrystalline magnesite are minor constituents of the Upper Triassic Burano Evaporite Formation of the northern Apennines in Italy. Petrography and geochemistry of magnesite suggest three modes of formation. (1) Evaporitic precipitation of stratified microcrystalline magnesite layers associated with sulfate and carbonate rocks. Most REE are below ICP-MS detection limits. '¹⁸O is +20.2‰ (SMOW) and '¹³C is -2.6‰ (PDB). (2) Hydrothermal infill of Fe-rich (9.78 wt% FeO) lenticular sparry magnesite. This type of magnesite is characterized by very low LREE concentrations, whereas HREEs are relatively high. The fluid inclusion composition is NaCl-MgCl₂-H₂O, salinity is ~30 wt% NaCl equiv., and total homogenization temperatures range from 204-309 °C; '¹⁸O is +17.5‰ and '¹³C is +1‰. (3) The partial or total replacement of dolostones by lenticular sparry magnesite. LREEs are lower in magnesite compared with the partly replaced dolostones. Magnesite yields '¹⁸O and '¹³C compositions of +17.3 to +23.6‰ and +0.5 to +1.4‰, respectively, whereas the partly replaced dolostones yield '¹⁸O and '¹³C values of +25.0 to +26.2 and +1.3 to +1.9, respectively. Complete replacement of dolostones produced massive lenticular sparry magnesite rock containing ooids and axe-head anhydrite relicts; LREEs are depleted compared to unaffected dolostones; '¹⁸O and '¹³C compositions range from +16.4 to +18.4‰ and +0.4 to +0.9‰, respectively. These data and the association between fracture-filling and replacive magnesite suggests a metasomatic system induced by hydrothermal circulation of hot and saline Mg-rich fluids. These processes probably occurred in the Oligocene-Miocene, when the Burano Formation acted as main detachment horizon for the Tuscan Nappe during the greenschist facies metamorphism of the Apuane complex. Thrusting over the Apuane zone produced large scale fluid flow focused at the Tuscan Nappe front. Sources of Mg-rich fluids were metamorphic reactions in the Apuane complex and dissolution of Mg-salts at the thrust front. Considering a maximum tectonic burial depth of 10 km, as inferred from the geometry of the chain, the pressure-corrected temperature of magnesite precipitation (380 to 400 °C) and the calculated fluid composition ('¹⁸O=+13.3ǃ.2‰) are in the range of the published Apuane metamorphic temperatures (300-450 °C) and fluid compositions ('¹⁸O=7-16‰). The results of this study support the hydrothermal-metasomatic model for the formation of sparry magnesite deposits at the expense of dolostone units involved in thrusting and low-grade metamorphism, as proposed for the Northern Graywacke Zone (Alps) and the Eugui deposit (western Pyrenees).     

Mesozoic and Cenozoic vertical movements in the Atlas system (Algeria, Morocco, Tunisia): An overview

The E-W trending Atlas System of Maghreb consists of weakly shortened, intra-continental fold belts associated with plateau areas (“Mesetas”), extending between the south-westernmost branch of the Mediterranean Alpine Belt (Rif-Tell) and the Sahara Platform. Although the Atlas system has been erected contemporaneously from Morocco to Algeria and Tunisia during the Middle Eocene to Recent, it displays a conspicuous longitudinal asymmetry, with i) Paleozoic outcrops restricted to its western part; ii) highest elevation occurring in the west, both in the Atlas System and its foreland (Anti-Atlas); iii) low elevation corridors (e.g. Hodna) and depressed foreland (Tunisian Chotts and Sahel area) in the east. We analyse the origin of these striking contrasts in relation with i) the Variscan heritage; ii) crustal vertical movements during the Mesozoic; iii) crustal shortening during the Cenozoic and finally, iv) the occurrence of a Miocene-Quaternary hot mantle anomaly in the west. The Maghreb lithosphere was affected by the Variscan orogeny, and thus thickened only in its western part. During the Late Permian-Triassic, a paleo-high formed in the west between the Central Atlantic and Alpine Tethys rift systems, giving birth to the emergent/poorly subsident West Moroccan Arch. During the late Middle Jurassic-Early Cretaceous, Morocco and western Algeria were dominantly emergent whereas rifting lasted on in eastern Algeria and Tunisia. We ascribe the uplift of the western regions to thermal doming, consistent with the Late Jurassic and Barremian gabbroic magmatism observed there. After the widespread transgression of the high stand Cenomanian-Turonian seas, the inversion of the Atlas System began during the Senonian as a consequence of the Africa-Eurasia convergence. Erosion affected three ENE-trending uplifted areas of NW Africa, which we consider as lithospheric anticlines related to the incipient Africa-Europe convergence. In contrast, in eastern Algeria and Tunisia a NW-trending rift system developed contemporaneously (Sirt rifting), normal to the general trend of the Atlas System. The general inversion and orogenesis of the Atlas System occurred during two distinct episodes, Middle-Late Eocene-Oligocene and Late Miocene-Pliocene, respectively, whereas during the intervening period, the Africa-Europe convergence was mainly accommodated in the Rif-Tell system. Inversion tectonics and crustal thickening may account for the moderate uplift of the eastern Atlas System, not for the high elevation of the western mountain ranges (Middle Atlas, High Atlas, Anti-Atlas). In line with previous authors, we ascribe part of the recent uplift of the latter regions to the occurrence of a NE-trending, high-temperature mantle anomaly, here labelled the Moroccan Hot Line (MHL), which is also marked by a strip of late Miocene-Quaternary alkaline magmatism and significant seismicity.     

The influence of paleoclimatic events on the functioning of an alpine thermal system (France): the contribution of hydrodynamic–thermal modeling

Numerical models of the Aix-les-Bains thermal aquifer (France) were used to investigate the influence of Quaternary paleoclimatic events on the current thermal state of the groundwater. Initial numerical tests were successful in that present-day fluid flows (heads and flow rates) and the resulting velocities were compatible with residence time data. Water flowing through an aquifer cools the rock mass; therefore, the rate of water flow governs the outlets temperature. For the Aix-les-Bains aquifer, applying present-day flow rates to the entire history of the aquifer leads to much more substantial cooling of the rock mass than is indicated by the outlets temperature (i.e. present-day flow rates are 10 times too high). This suggests that the aquifer may have gone through alternating functioning phases, during which the rock mass cooled, and blocked phases, during which the aquifer reheated. Other results indicate that the main parameters affecting thermal behavior during a functioning phase are the total inflow volume, rather than individual inflow rates, and the initial heat field. As phenomena linked to glaciation can lead to the blocking of infiltration zones and aquifer outlets, the findings suggest that the hypothesis of intermittent aquifer functioning related to glaciations is compatible with the current thermal field.     

Complete Trace Elemental Characterisation of Granitoid (USGS G-2, GSP-2) Reference Materials by High Resolution Inductively Coupled Plasma-Mass Spectrometry

The United States Geological Survey granitic and granodioritic reference materials G‐2 and GSP‐2 were decomposed in high‐pressure bombs using both HF‐HNO₃ and HF‐HNO₃‐HClO₄ in order to evaluate the feasibility of characterising the entire suite of geologically relevant trace elements through direct analysis with a high‐resolution inductively coupled plasma‐mass spectrometer (HR‐ICP‐MS). The digested samples were diluted to the appropriate levels and analysed at low, medium and high resolution depending on the required sensitivity and potential interferences for each element. Memory effects during analysis of the high field strength elements (HFSE) were negligible when analysed using an all‐Teflon, uncooled sample introduction system and combined with adequate wash times with 4% v/v aqua regia + 0.5% v/v HF between samples. The concentration of the remaining lithophile elements was determined with a conventional, cooled, Scott‐type spray chamber using a wash solution of 1% v/v HNO₃. Total procedural blanks contributed between 0.01 to 0.5% to final sample concentrations and blank subtractions were typically unnecessary. Abundances for Li, Hf, Ba, Zr, Ga, Rb, Sr, La, Ce, Th and U were systematically higher, while those for the heavy rare earth elements (HREEs), Cu and Y were systematically lower in this study compared to USGS values for G‐2 and GSP‐2. This is likely to be related to, respectively, higher recoveries from more efficient digestion of refractory phases (i.e., zircon, tourmaline), and better resolution of interferences when using a HR‐ICP‐MS. Sample digestion experiments also showed that perchloric acid digestion in high pressure bombs resulted in superior recoveries and better precision for the bulk of the trace elements analysed. The concentration of the remaining elements overlapped within uncertainty with recommended reference values and with values determined in other studies using isotope‐dilution TIMS, ICP‐MS and XRF. Concentrations for the elements Cd, Sn, Sb, Ta, Bi, Tb, Ni and Mo are also reported for G‐2 and GSP‐2 reference materials. Our study shows therefore that it is feasible to determine thirty‐nine geologically relevant trace elements accurately and directly in granitoid sample digests when using a HR‐ICP‐MS, thereby negating the need for ion exchange or isotopic spiking.