Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Structure cristalline d'une ménéghinite naturelle pauvre en cuivre,Cu0,58Pb12,72(Sb7,04Bi0,24)S24Crystal structure of a Cu-poor natural meneghinite,Cu0.58Pb12.72(Sb7.04Bi0.24)S24

Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å³, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu_0.15Pb₂(Pb_0.53Sb_0.47)(Pb_0.46Sb_0.54)(Sb_0.75Pb_0.19Bi_0.06)S₆; the reduced one: Cu_0.58Pb_12.72(Sb_7.04Bi_0.24)S₂₄. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Reconstruction of the North–South Solar Asymmetry with a Kuramoto Model

This paper applies a Kuramoto model of coupled oscillators to investigate the north–south (N–S) solar asymmetry and properties of meridional circulation. We focus our study on the asymmetry of the 11-year phase, which is slight but persistent: only two changes of sign (around 1928 and 1968) are observed in the past century. We present a model of two non-linear coupled oscillators that links the hemispheric phase asymmetry of sunspots with the asymmetry of the meridional flow. We use a Kuramoto model with evolving frequencies and constant symmetric coupling to show how asymmetry in meridional circulation could produce a persistent phase lead of one solar hemisphere over the other. We associate the natural frequencies of the two oscillators with the velocities of the meridional flow cells in the northern and southern hemispheres. We assume the respective circulations to be independent and estimate the value of the relevant cross-equatorial coupling by the coupling coefficient in the Kuramoto model. We find that a persistent N–S asymmetry of sunspots and the change of the leading hemisphere could indeed both be the result of the evolving frequencies of meridional circulation; the necessary asymmetry of the meridional flow may be small; and the cross-equatorial coupling has an intermediate range value. Possible applications of these results in solar dynamo models are discussed.     

Slow and Fast Rotating Coronal Holes from Geomagnetic Indices

The evolution of the 27-day recurrence in the series of two solar indices (Wolf number WN and 10.7 cm radio flux F) and two geomagnetic indices (Dst and ζ, variance of the geomagnetic field recorded at a magnetic observatory) have been studied over the 1957 – 2007 time span. Spectral energies contained in two period domains (25 – 27.3 and 27.3 – 31 days), designated as E ₁ and E ₂, have been computed. Whereas the evolution of E ₁ is the same for the four indices, that of E ₂ is essentially different for WN and F on the one hand, Dst and ζ on the other hand. Some general conclusions on the dynamics of the solar outer layers are inferred from these results. First the solar activity, as measured by WN, and when averaged over a few years, evolves in the same way whatever the latitude. Second, two families of coronal holes (CHs) are identified; the rapidly and the slowly rotating CHs evolve quite differently.     

Particulate flux in the water column overlying Santa Monica Basin

Fluxes of particulate carbon, nitrogen, phytoplankton pigments, biogenic silica and dry mass were measured using free-floating and moored sediment trap arrays in the Santa Monica Basin during the period from October 1985 to August 1990 as part of the California Basin Study (CaBS) Program. In field testing for potential sources of sediment trap biases, we found little significant or consistent difference in rate estimates between short-term drifting traps and long-term moored traps, between preserved and unpreserved traps in short-term experiments, between different preservatives (mercury or formalin) in long-term experiments, between different designs of small cylindrical traps, and between deep-moored cylindrical traps and large conical traps. We did, however, find that sediment trap samples collected and analyzed on 0.45 μm silver filters gave estimates of carbon and nitrogen fluxes about 25% higher than samples collected on GF/F glass-fiber filters. Concurrent trap deployments at two stations 18km apart revealed low mesoscale variability in flux estimates. Seasonal patterns in carbon and nitrogen flux were not evident in our data, but strong seasonality, with spring maxima and summer minima, were observed for fluxes of phaeopigments and biogenic silica out of the euphotic zone.Time-averaged rates of particulate flux for long-term trap deployments from January to August 1990, were 121, 18.8, 1.5, 67 and 633mg m⁻²d⁻¹ at 110–135m for carbon, nitrogen, phaeopigment, biogenic silica and mass, respectively. Flux estimates to the basin floor (835–860m) were 50, 6.5, 0.64, 41.6 and 575mg m⁻²d⁻¹ for the same parameters. The former estimates are constrained by and in good agreement with independent assessments of new production from nitrate uptake in the euphotic zone. The latter agree with rates previously inferred from the sedimentary record using ²¹⁰Pb as a tracer. In addition, the difference in carbon estimates in the water column between the euphotic zone and the basin floor is consistent with the requirements for bacterial growth and metabolism at intermediate depths as measured by the thymidine method.     

A history of ENSO events since A.D. 1525: implications for future climate change

Reconstructions of past climate are important for providing a historical context for evaluating the nature of 20th century climate change. Here, a number of percentile-based palaeoclimate reconstructions were used to isolate signals of both phases of El Niño–Southern Oscillation (ENSO). A total of 92 (82) El Niño (La Niña) events were reconstructed since A.D. 1525. Significantly, we introduce the most comprehensive La Niña event record compiled to date. This annual record of ENSO events can now be used for independent verification of climate model simulations, reconstructions of ENSO indices and as a chronological control for archaeologists/social scientists interested in human responses to past climate events. Although extreme ENSO events are seen throughout the 478-year ENSO reconstruction, approximately 43% of extreme and 28% of all protracted ENSO events (i.e. both El Niño and La Niña phase) occur in the 20th century. The post-1940 period alone accounts for 30% of extreme ENSO years observed since A.D. 1525. These results suggest that ENSO may operate differently under natural (pre-industrial) and anthropogenic background states. As evidence of stresses on water supply, agriculture and natural ecosystems caused by climate change strengthens, studies into how ENSO will operate under global warming should be a global research priority.     

Expression of the Early Toarcian negative carbon-isotope excursion in separated carbonate microfractions (Jurassic,Paris Basin)

The causes of the pronounced negative excursion in carbon-isotope values that was recorded during the Early Toarcian Oceanic Anoxic Event (T-OAE) are still under debate, particularly with regard to the local versus global pattern of the excursion, and the extent to which recorded signals are under a diagenetic control. In this study we employ a novel microseparation technique in order to investigate the isotopic and mineralogical characteristics of different size fractions of the carbonate content from a Toarcian section recovered from the Sancerre–Couy borehole, southern Paris Basin. Beyond the recognition of a ? 6‰ δ¹³C excursion in the bulk carbonate content, our data also demonstrate that biogenic particles (such as coccoliths) and inorganic grains precipitated as early diagenetic phases (including dolomite) both record the excursion with the same magnitude. Although several black shales occur through the Paris Basin Toarcian section, it is only that associated with the onset of the OAE that coincides with a large negative carbon-isotope excursion. Taken together these observations indicate that during this event, the entire water column was characterized by homogeneous carbon-isotope values; such a pattern is incompatible with the idea that the negative excursion was generated simply through the upwelling of bottom waters enriched in re-mineralized organic carbon (cf. “the Küspert model”), since this would have required a strong vertical gradient in the water column. Additionally, the Paris Basin data show that the decrease in carbonate δ¹³C values during the OAE occurred in several discrete steps (each of some ? 2‰), as has previously been found for organic carbon substrates in other European sections. The stepped nature of the isotopic profile, which is part of a stratigraphic signature previously ascribed to Milankovitch forcing, is compatible with regular pulsed input of light carbon into the whole atmosphere–ocean system from a climatically sensitive source such as gas hydrate, or from thermal methanogenesis of organic-rich sediments in the Karoo–Ferrar large igneous province. Contrasts in the amplitude of the negative carbon-isotope excursion on a regional scale remain an important unexplained aspect of the Toarcian record.     

Variabilité isotopique des précipitations sahéliennes à différentes échelles de temps à Niamey (Niger) entre 1992 et 1999 : implication climatiqueIsotopic variability of Sahelian rainfall at different time steps in Niamey (Niger, 1992–1999): climatic implications

The isotopic content of rainfall was measured in Niamey (Niger) over a period of eight years (1992–1999). Seasonal distribution of rainy events depends on the monsoon movement over the region. At the beginning and at the end of the rainy season, low rainfall, high temperatures and low relative humidity favour isotopic enrichment. In the middle of the rainy season, heavy rainfall, low temperatures and relative humidity close to saturation lead to isotopically depleted contents because of the mass effect; moreover, in the case of low rainfall, marked vertical convective development favours high altitude condensation. How far the Intertropical Front moves north, determines the quality of the rainy season and influences the isotopic contents. Thus the isotopic contents of rainfall are good climatic indicators. To cite this article: J.-D. Taupin et al., C. R. Geoscience 334 (2002) 43–50