Re-Os Isotopic Measurements at the Femtomole Level in Natural Samples

Here we describe a new chemical separation method for Os and an improved mass spectrometric procedure for Re and Os. This technique is based on the selective extraction of OsO₄ from aqueous solution in liquid bromine. Among other advantages, this procedure avoids the cumbersome distillation procedure for Os and uses only commercial "off the shelf" PFA teflon labware. Blank levels for 0.5 g sample sizes are: 0.06 pg and 0.5 pg for Os and Re respectively. Samples containing as little as 1 pg g⁻¹ Os can be analysed reliably with this method. Adaptation to other dissolution methods is also discussed.     

Nouvelles données pour l’histoire des fluctuations holocènes du niveau du lac de Neuchatel (Suisse): la séquence sédimentaire de Marin-Les Piécettes

Resume. Les fouilles archéologiques réalisées de 1998 à 2002 sur le site néolithique de Marin-Les Piécettes sur la rive nord-ouest du lac de Neuchatel ont offert l’opportunité d’observer deux séquences sédimentaires intéressantes pour la reconstitution des variations holocènes du niveau du lac, en particulier au cours de la période correspondant au changement de cours de l’Aar en direction du nord-est, vers 5650–5500 cal BP. La géométrie des corps sédimentaires et les changements lithologiques permettent de reconna?tre plusieurs phases majeures de bas niveaux relatifs du plan d’eau vers 6870, 5660, 5060–3990, 3580, 2280, 1640 et 1170 cal BP. Le site néolithique de Marin-Les Piécettes s’est développé vers 5454–5433 cal BP à la faveur d’un court épisode de bas niveau du lac qui a interrompu une importante phase de haut niveau au début du Subboréal. Les événements paléohydrologiques identifiés à Marin-Les Piécettes apparaissent cohérents avec ceux reconstitués sur le site de Montilier au bord du lac de Morat, ainsi qu’avec les variations paléohydrologiques reconstituées à partir des lacs du Jura, du Plateau suisse et des Préalpes du Nord fran?aises. Ceci suggère qu’ils témoignent d’un signal climatique. La séquence sédimentaire de Marin-Les Piécettes met enfin en évidence la formation d’un cordon littoral sur la rive nord-ouest du lac juste après 5660 cal BP. Manuscrit re?u le 22 septembre 2004 Révision acceptée le 11 mars 2005     

Trace element geochemistry of CR chondrite metal

We report trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) of metal grains from nine different CR chondrites, distinguishing grains from chondrule interior (“interior grains”), chondrule surficial shells (“margin grains”), and the matrix (“isolated grains”). Save for a few anomalous grains, Ni‐normalized trace element patterns are similar for all three petrographic settings, with largely unfractionated refractory siderophile elements and depleted volatile Au, Cu, Ag, S. All three types of grains are interpreted to derive from a common precursor approximated by the least‐melted, fine‐grained objects in CR chondrites. This also excludes recondensation of metal vapor as the origin of the bulk of margin grains. The metal precursors were presumably formed by incomplete condensation, with evidence for high‐temperature isolation of refractory platinum‐group‐element (PGE)‐rich condensates before mixing with lower temperature PGE‐depleted condensates. The rounded shape of the Ni‐rich, interior grains shows that they were molten and that they equilibrated with silicates upon slow cooling (1–100 K h^?1), largely by oxidation/evaporation of Fe, hence their high Pd content, for example. We propose that Ni‐poorer, amoeboid margin grains, often included in the pyroxene‐rich periphery common to type I chondrules, result from less intense processing of a rim accreted onto the chondrule subsequent to the melting event recorded by the interior grains. This means either that there were two separate heating events, which formed olivine/interior grains and pyroxene/margin grains, respectively, between which dust was accreted around the chondrule, or that there was a single high‐temperature event, of which the chondrule margin records a late “quenching phase,” in which case dust accreted onto chondrules while they were molten. In the latter case, high dust concentrations in the chondrule‐forming region (at least three orders of magnitude above minimum mass solar nebula models) are indicated.     

Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Elastoplastic model with loading memory surfaces (LMS) for monotonic and cyclic behaviour of geomaterials

A new elastoplastic model called loading memory surface based on the critical state concept and the multi‐surface framework is proposed for geomaterials. The model uses a hypoelastic formulation and two plastic mechanisms. The formulations of the model are made in three‐dimensional stress–strain space and work under both monotonic and cyclic loadings. A newly introduced formalism makes it possible to obtain the cyclic response directly from the monotonic loading one. This formalism gives a three‐dimensional generalization of the well‐known Masing rule. The model has been validated against test results of Hostun sand under several conditions: monotonic and cyclic, drained and undrained, tests in compression and in extension, and at different confining pressures and different densities. Copyright © 2014 John Wiley & Sons, Ltd.     

Inorganic arsenic speciation in the waters of the Penzé estuary (NW France): Seasonal variations and fluxes to the coastal area

Over this one-year study, the variations of inorganic As species were examined monthly along the salinity gradient of the Penzé estuary (NW France) in relation with different biogeochemical parameters. In most cases, dissolved As exhibited a non-conservative behaviour which resulted from the competition between two major processes. In the upstream section of the estuary, a strong input of both total inorganic As and As(III) occurred. Then, the removal of the same species, under precipitation of iron oxides/oxyhydroxides, was observed in the low-salinity range (S < 10). Using our experimental data, the fluxes of the various As species were estimated for the first time in estuarine waters. Inputs from the river were mainly constituted of particulate As (∼70%). Conversely, dissolved species were predominant in the net fluxes (∼65%) and As(III) accounted for ∼15% of the dissolved net flux.     

Revisiting wintertime cold air intrusions at the east of the Andes: propagating features from subtropical Argentina to Peruvian Amazon and relationship with large-scale circulation patterns

This study investigates the spatial and temporal characteristics of cold surges that propagates northward along the eastern flank of the Andes from subtropical to tropical South America analysing wintertime in situ daily minimum temperature observations from Argentina, Bolivia and Peru and ERA-40 reanalysis over the 1975–2001 period. Cold surges usually last 2 or 3 days but are generally less persistent in the southern La Plata basin compared to tropical regions. On average, three to four cold surges are reported each year. Our analysis reveals that 52 % of cold episodes registered in the south of La Plata basin propagate northward to the northern Peruvian Amazon at a speed of around 20 m s^?1. In comparison to cold surges that do not reach the tropical region, we demonstrate that these cold surges are characterized, before they reach the tropical region, by a higher occurrence of a specific circulation pattern associated to southern low-level winds progression toward low latitudes combined with subsidence and dry condition in the middle and low troposphere that reinforce the cold episode through a radiative effect. Finally, the relationship between cold surges and atmosphere dynamics is illustrated for the two most severe cold intrusions that reached the Peruvian and Bolivian Amazon in the last 20 years.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.