Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.     

Alpine tectonics in the Calabrian–Peloritan belt (southern Italy): New 40Ar/39Ar data in the Aspromonte Massif area

This study provides new ⁴⁰Ar/³⁹Ar geochronological constraints on the age of the Alpine tectonics in the Aspromonte Massif (southern part of the Calabrian–Peloritan belt). This massif exposes the upper units of the Calabride Complex which originated from the European continental margin. The Calabride Complex was incorporated in the Alpine orogenic wedge and then integrated into the Apennines and Maghrebides fold-and-thrust belts. Throughout the Calabride Complex there is evidence for a two stage tectonic history, which remains however rather poorly dated: Alpine nappe stacking is followed by extensional reworking along the former thrust contacts or along new detachment surfaces. Our new ages suggest that exhumation of the uppermost units, which accompanied nappe stacking, probably started at 45 Ma and that the deepest units were almost completely exhumed at 33 Ma. This kinematics probably corresponds to syn-orogenic extension while the end of exhumation is clearly related to the extensional tectonics dated at 28.6 Ma along detachment structures.Our geochronological data reveal a very short lag time between accretional and extensional processes in this part of the Mediterranean Alpine orogenic belt. The direction of extension, when the units are restored to their initial position (i.e. before the opening of the Western Mediterranean basins and the bending of the arc) is NNE–SSW. Such a direction does not fit with the eastward slab-retreat model generally put forward to explain extension in the Western Mediterranean. In contrast, we provide evidence for roughly N–S middle Oligocene extension in the accretionary prism, not previously described in this part of the Mediterranean domain.     

Ca isotope cycling in a forested ecosystem

Reports of large Ca isotope fractionations between trees and soils prompted this study of a Boreal forest ecosystem near La Ronge, Saskatchewan, to improve understanding of this phenomenon. The results on five tree species (black spruce, trembling aspen, white spruce, jack pine, balsam poplar) confirm that nutrient Ca uptake by plants favors the light isotopes, thus driving residual Ca in plant available soil pools towards enrichment in the heavy isotopes. Substantial within-tree fraction occurs in tissues formed along the transpiration stream, with low δ⁴⁴Ca values in fine roots (2 mm), intermediate values in stemwood, and high values in foliage. Separation factors between different plant tissues are similar between species, but the initial fractionation step in the tips of the fine roots is species specific, and/or sensitive to the local soil environment. Soil water δ⁴⁴Ca values appear to increase with depth to at least 35 cm below the top of the forest floor, which is close to the deepest level of fine roots. The heavy plant fractionated signature of Ca in the finely rooted upper soils filters downward where it is retained on ion exchange sites, leached into groundwater, and discharged into surface waters.The relationship between Ca uptake by tree fine roots and the pattern of δ⁴⁴Ca enrichment with soil depth was modeled for two Ca pools: the forest floor (litter) and the underlying (upper B) mineral soil. Six study plots were investigated along two hillside toposequences trending upwards from a first order stream. We used allometric equations describing the Ca distribution in boreal tree species to calculate weighted average δ⁴⁴Ca values for the stands in each plot and estimate Ca uptake rates. The δ⁴⁴Ca value of precipitation was measured, and soil weathering signatures deduced, by acid leaching of lower B mineral soils. Steady state equations were used to derive a set of model Ca fluxes and fractionation factors for each plot. The model reproduces the increase in δ⁴⁴Ca with depth found in forest floor and upper B soil waters. Transient model runs show that the forest Ca cycle is sensitive to changes in plant Ca uptake rate, such as would occur during ontogeny or disturbance. Accordingly, secular records of δ⁴⁴Ca in tree ring cellulose have the potential to monitor changes in the forest Ca cycle through time, thus providing a new tool for evaluating natural and anthropogenic impacts on forest health. Another model run shows that by changing the size of the isotope fractionation factor and adjusting for differences in forest productivity, that the range in Ca isotope fractionation in forested ecosystems reported in the literature, thus far, is reproduced. As a quantitative tool, the Ca cycling model produces a reasonable set of relative Ca fluxes for the La Ronge site, consistent with Environment Canada’s measurements for wet deposition in the region and simulated Ca release from soil mineral weathering using the PROFILE model. But the sensitivity of the model is limited by the small range of fractionation observed in this boreal shield setting of ∼1‰, which limits accuracy. If the model were applied to a site with a greater range in δ⁴⁴Ca values among the principal Ca fluxes, it is capable of producing robust and reliable estimations of Ca fluxes that are otherwise difficult to measure in forested ecosystems.     

A Finite Volume Scheme for the Transport of Radionucleides in Porous Media

The COUPLEX1 Test case (Bourgeat et al., 2003) is devoted to the comparison of numerical schemes on a convection–diffusion–reaction problem. We first show that the results of the simulation can be mainly predicted by a simple analysis of the data. A finite volume scheme, with three different treatments of the convective term, is then shown to deliver accurate and stable results under a low computational cost.     

Links between NAO fluctuations and inter-annual variability of winter-months precipitation in the Seine River watershed (north-western France)

The inter-annual to multi-decadal winter variability (DJFM) of precipitation on the Seine River watershed (France) was analysed using continuous wavelet transform analysis and compared to the winter North Atlantic Oscillation Index (NAOI). Nine weather stations were used over the 1951 to 2004 period and confirmed the homogeneity of inter-annual fluctuations for all stations but one. Wavelet coherence between SLP over the Icelandic and Azores regions and precipitation highlighted coherence for different scales of variability according to the centre of action considered. Segmentation and wavelet analysis and coherence between precipitation and NAOI over a long period of time (1873–2004) showed: i) increasing variability across the last century at most time scales, especially for NAOI; ii) the existence of change points for the mean and variance of both signals; iii) overall discontinuity of the coherence whatever the scale considered, especially between ∼1910 and ∼1955 for inter-decennial to pluri-decennial scales.     

Transport and deposition of suspended particles in saturated porous media: hydrodynamic effect

A laboratory study was undertaken to determine the transport and deposition rate of suspended particles in columns of saturated porous media (gravel and glass beads), where the porous media were subjected to steady-state flow. Silt particles with a mode of 14 μm diameter (used as the suspended particles) and fluorescein (as the conservative tracer) were injected into the columns in short pulses. The breakthrough curves were competently described with the analytical solution of a convection–dispersion equation with a first-order deposition rate. The experiments were performed using different flow rates. The suspended particle size distribution, the porous media, and the flow rates themselves were the main factors retained in this study to investigate the mechanisms governing the transport and deposition kinetics in detail. The results showed the existence of a flow rate, beyond which suspended particles travel faster than the conservative tracer. A decrease of the deposition rate of suspended particles beyond a critical flow velocity was also observed. Such behaviour led to consideration of the couple hydrodynamic-gravity forces at high flow rates. As the hydrodynamic force increases, particle deposition rates are reduced due to the effect of hydrodynamic forces inhibiting the deposition.     

Does stress transmission in forelands depend on structural style? Distinctive stress magnitudes during Sevier thin‐skinned and Laramide thick‐skinned layer‐parallel shortening in the Bighorn Basin (USA) revealed by stylolite and calcite twinning paleopiezometry

The Sheep Mountain‐Little Sheep Mountain Anticlines, Bighorn Basin (USA) formed as basement‐cored Laramide structures in the formerly undeformed foreland of the thin‐skinned Sevier orogen. We take advantage of the well‐constrained microstructural network there to reconstruct differential stress magnitudes that prevailed during both Sevier and Laramide layer‐parallel shortening (LPS), before the onset of large‐scale folding. Differential stress magnitudes determined from tectonic stylolites are compared and combined to previous stress estimates from calcite twinning paleopiezometry in the same formations. During stress loading related to LPS, differential stress magnitudes transmitted from the distant Sevier thin‐skinned orogen into the sedimentary cover of the Bighorn basin (11–43 MPa) are higher than the differential stress magnitudes accompanying the early stage of LPS related to the thick‐skinned Laramide deformation (2–19 MPa). This study illustrates that the tectonic style of an orogen affects the transmission of early orogenic stress into the stable continental interior.     

Ecosystem Responses of the Subtropical Kaneohe Bay,Hawaii, to Climate Change: A Nitrogen Cycle Modeling Approach

The global coastal zone is characterized by high biological productivity and serves as an important channel through which materials are transferred from land to the open ocean, yet little is known how it will be affected by climate change. Here, we use Kaneohe Bay, Hawaii, a semi-enclosed subtropical embayment partially surrounded by a mountainous watershed and fed by river runoff as an example to explore the potential impact of climate change on the pelagic and benthic cycling of nitrogen. We employ a nine-compartment nitrogen cycle biogeochemical box model and perturb it with a set of four idealized climate scenarios. We find that hydrological changes play a dominant role in determining the ecosystem structure, while temperature changes are more important for the trophic state and stability of the ecosystem. The ecosystem stability against storm events does not significantly change under any scenario. The system remains autotrophic in the future; however, it becomes significantly less autotrophic under drier climate, while it turns slightly more autotrophic under wetter climate. These findings may have implications for other high island watershed and coastal ecosystems in the tropics and subtropics.