Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

An experimental study of lake water-sediment interaction rates

Dissolution rates of sediments obtained from the Oued Cherf reservoir were measured in closed-system batch reactors at 25 °C in fluids sampled concurrently from the same locations as the sediments. The BET surface areas of the sediments ranged from 16 to 45 m²/g and consisted primarily of quartz, calcite, and clay minerals. After a brief initial period, release rates of Si, Mg, Ca, Cl, SO₄, and NO₃ from these sediments are approximately linear with time over the course of the experiments, which lasted from 3 to 5 months. BET surface area normalized Si release rates ranged from 10^–17.4 to 10^–18.4 mol/cm²/s. These release rates match closely Si release rates from quartz and clay minerals determined from laboratory dissolution rates reported in the literature. This coherence suggests that laboratory measured silicate dissolution rates can be used with confidence to predict the dissolution behavior of sediments in natural surface waters.     

Genesis and solvus relations of submicroscopically intergrown paragonite and phengite in a blueschist from northern California

Electron microbeam techniques have been used to examine submicroscopically intergrown paragonite, phengite and chlorite from the South Fork Mountain Schist of the Franciscan Terrane of northern California, which was subjected to blueschist facies metamorphism. The sample also contains quartz, albite, lawsonite, and rutile. The subassemblage albite-lawsonite-rutile requires metamorphic conditions on the low-temperature side of the equilibrium albite+lawsonite+rutile=paragonite+sphene+quartz+H₂O (T<200° C and P<7.4 kbars based on thermodynamic data of Holland and Powell 1990). The white micas appear to be optically homogeneous, but back-scattered electron images can distinguish two different micas by their slight difference in contrast. Electron microprobe analyses (EMPA) of micas show Na/(Na+K) ranging from 0.2 to 0.8. The two micas are resolved by transmission electron microscopy (TEM) as packets of phengite and paragonite that range from 20 to several hundred nm in thickness. The compositions, determined by analytical electron microscopy (AEM), constrain the limbs of the phengite-paragonite solvus to values of Na/(Na+K)=<0.02 and 0.97, representing less mutual solid solution than ever reported by EMPA. The textural relations imply that the sheet silicates were derived from reactions between fluids and detrital clays and that they are in an intermediate stage of textural development. We caution that microprobe analyses of apparently homogeneous sheet silicates may yield erroneous data and lead to faulty conclusions using phengite barometry and paragonite-muscovite thermometry, especially in fine-grained rocks that formed at relatively low temperatures. Contribution no. 473 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan, USA     

Upper mantle structure of the South American continent and neighboring oceans from surface wave tomography

We present a new three-dimensional SV-wave velocity model for the upper mantle beneath South America and the surrounding oceans, built from the waveform inversion of 5850 Rayleigh wave seismograms. The dense path coverage and the use of higher modes to supplement the fundamental mode of surface waves allow us to constrain seismic heterogeneities with horizontal wavelengths of a few hundred kilometres in the uppermost 400 km of the mantle.The large scale features of our tomographic model confirm previous results from global and regional tomographic studies (e.g. the depth extent of the high velocity cratonic roots down to about 200–250 km).Several new features are highlighted in our model. Down to 100 km depth, the high velocity lid beneath the Amazonian craton is separated in two parts associated with the Guyana and Guapore shields, suggesting that the rifting episode responsible for the formation of the Amazon basin has involved a significant part of the lithosphere. Along the Andean subduction belt, the structure of the high velocity anomaly associated with the sudbduction of the Nazca plate beneath the South American plate reflects the along-strike variation in dip of the subducting plate. Slow velocities are observed down to about 100 km and 150 km at the intersection of the Carnegie and Chile ridges with the continent and are likely to represent the thermal anomalies associated with the subducted ridges. These lowered velocities might correspond to zones of weakness in the subducted plate and may have led to the formation of “slab windows” developed through unzipping of the subducted ridges; these windows might accommodate a transfer of asthenospheric mantle from the Pacific to the Atlantic ocean. From 150 to 250 km depth, the subducting Nazca plate is associated with high seismic velocities between 5°S and 37°S. We find high seismic velocities beneath the Paraná basin down to about 200 km depth, underlain by a low velocity anomaly in the depth range 200–400 km located beneath the Ponta Grossa arc at the southern tip of the basin. This high velocity anomaly is located southward of a narrow S-wave low velocity structure observed between 200 and 500–600 km depth in body wave studies, but irresolvable with our long period datasets. Both anomalies point to a model in which several, possibly diachronous, plumes have risen to the surface to generate the Paraná large igneous province (LIP).     

Coupled discrete element and finite volume solution of two classical soil mechanics problems

One dimensional solutions for the classic critical upward seepage gradient/quick condition and the time rate of consolidation problems are obtained using coupled routines for the finite volume method (FVM) and discrete element method (DEM), and the results compared with the analytical solutions. The two phase flow in a system composed of fluid and solid is simulated with the fluid phase modeled by solving the averaged Navier–Stokes equation using the FVM and the solid phase is modeled using the DEM. A framework is described for the coupling of two open source computer codes: YADE-OpenDEM for the discrete element method and OpenFOAM for the computational fluid dynamics. The particle–fluid interaction is quantified using a semi-empirical relationship proposed by Ergun [12]. The two classical verification problems are used to explore issues encountered when using coupled flow DEM codes, namely, the appropriate time step size for both the fluid and mechanical solution processes, the choice of the viscous damping coefficient, and the number of solid particles per finite fluid volume.     

Paleogeographical restoration and ramp tectonic evidence in Tunisian Tellian domain: Ain El Bey-Bou Awen area

The imbrication’s area in northern Tunisia is the most external segment of Alpine range, where several associated folds types with thrust ramps are recognized within imbricate units beneath Numidian front slope. Their presence help to understand thrusting mechanisms installation through studied area. In fact, this zone was considered as a result of Paleogene gravitary slop (Kujawski (Ann Miner Géol Tunis (24):281, 1969); Caire (Ann Min Géol Tunis 26:87–110, 1973); Rouvier 1977), which is proved to be affected by major deep decollement, given rise to various structures, some are propagation folds, specific of foreland front, limited to this area, and those in more external position: Tunisian Atlas (Creusot et al. (C R Acad Sci Paris 314(Sér II):961–965, 1992); Ouali and Mercier (PII: S0191-8141(97):00048-5, 1997); Ouali 1984; Ahmadi et al. (J Struct Geol 28:721–728, 2006)). Various categories of fold ramps could be identified: frontal folds ramp NE–SW and others as lateral or oblique ramp with NW–SE trend (Aridhi et al. (C R Geosci 343:360–369, 2011)). The relation between various structures has been used as recognition tools of thrusting sequences and to propose a new deformation chronology. Delimited outcropping of these structures between two both parallel faults strikes with regional displacement, leads to interpret these faults as cogenetic tear faults of propagation thrusts; this fault separates two domains with different deformation styles from each other side.     

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.     

Variability of dissolved organic carbon in sediments of a seagrass bed and an unvegetated area within an estuary in Southern Texas

Pore-water dissolved organic carbon (PWDOC) concentrations were examined in vegetated and bare sediments of aHalodule wrightii seagrass bed, and in a mud bottom sediment of a southern Texas estuary. Temporal variability was examined at diel (dawn and noon) and bimonthly time scales. Distribution patterns of PWDOC were compared with physical, chemical, and biological factors thought to exert control on PWDOC. Concentration of PWDOC, bacterial production, and resultant PWDOC turnover times displayed statistically significant spatial and temporal variability. Concentration of PWDOC ranged from 14 mg C 1^?1 to 107 mg C 1^?1 of pore water, or 9–71 μg C cm^?3 wet sediment. PWDOC was more variable and was approximately 5 times higher than DOC concentrations in the water column. Low PWDOC concentrations (mean = 14.6 μg C cm^?3) and high bacterial production rates (mean = 1.92 μg C cm^?3 h^?1) were observed at the mud station, whereas PWDOC concentrations were high (mean = 24.6 μg C cm^?3) and bacterial production rates were low (mean = 0.43 μg C cm^?3 h^?1) at the bare station. PWDOC turnover times (T_t), assuming 50% bacterial growth efficiency (1–840 h) were shortest at the mud station (mean=13 h) and longest at the bare station (mean=180 h). In the overlying water column, T_t values were longer, ranging from 1,000–10,000 h. PWDOC concentrations were 25% higher in vegetated sediments than in neighboring bare sediments. This difference was probably due to inputs of labile photosynthetic excretia, since bacterial production rates in vegetated sediments displayed significant diel variability and were 4 times greater than that of bare sediments. Based upon the entire data set, PWDOC was significantly related to macrofaunal biomass, sediment POC, sediment C:N ratios, and oxygen metabolism, but was significantly correlated only to the latter two variables in stepwise multiple regression. Our findings suggest that organism activities and detrital quality are the major determinants controlling variability in PWDOC.     

Origins and evolution of rhyolitic magmas in the central Snake River Plain: insights from coupled high-precision geochronology,oxygen isotope,and hafnium isotope analyses of zircon

We present new high-precision CA-ID-TIMS and in situ U–Pb ages together with Hf and O isotopic analyses (analyses performed all on the same grains) from four tuffs from the 15?10 Ma Bruneau–Jarbidge center of the Snake River Plain and from three rhyolitic units from the Kimberly borehole in the neighboring 10?6 Ma Twin Falls volcanic center. We find significant intrasample diversity in zircon ages (ranges of up to 3 Myr) and in δ¹⁸O (ranges of up to 6‰) and ε_Hf (ranges of up to 24 ε units) values. Zircon rims are also more homogeneous than the associated cores, and we show that zircon rim growth occurs faster than the resolution of in situ dating techniques. CA-ID-TIMS dating of a subset of zircon grains from the Twin Falls samples reveals complex crystallization histories spanning 10⁴–10⁶ years prior to some eruptions, suggesting that magma genesis was characterized by the cyclic remelting of buried volcanic rocks and intrusions associated with previous magmatic episodes. Age-dependent trends in zircon isotopic compositions show that rhyolite production in the Yellowstone hotspot track is driven by the mixing of mantle-derived melts (normal δ¹⁸O and ε_Hf) and a combination of Precambrian basement rock (normal δ¹⁸O and ε_Hf down to ??60) and shallow Mesozoic and Cenozoic age rocks, some of which are hydrothermally altered (to low δ¹⁸O values) by earlier stages of Snake River Plain magmatism. These crustal melts hybridize with juvenile basalts and rhyolites to produce the erupted rhyolites. We also observe that the Precambrian basement rock is only an important component in the erupted magmas in the first eruption at each caldera center, suggesting that the accumulation of new intrusions quickly builds an upper crustal intrusive body which is isolated from the Precambrian basement and evolves towards more isotopically juvenile and lower-δ¹⁸O compositions over time.