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.     

Aspects of the Fine-Scale Climatology Over Lake Tanganyika as Resolved by a Mesoscale Model

Summary  An hourly averaged climatology at 0.05 ° horizontal resolution over the Lake Tanganyika region was created by making simulations with a mesoscale model (HIRLAM) using a high resolution physiography to represent the surface. Initial and boundary values were interpolated from ECMWF analyses. Climatologies for a typical dry season month (July 1994) and wet season month (March 1994) were created by 7-day segmenting. Model results were validated by utilizing a special coastal observation network. A number of experiments were made with changes to the physiography (mountains/no mountains, lake/no lake). The results reveal local channelling and blocking effects of the near-surface southeasterly trade winds by the high mountain chains in the region of the East African rift. Furthermore, surface winds display regular diurnal cycles in many places, due to slope winds over hills and lake-land-type breezes near the coast. The diurnal coastal winds (defined by the observation network) are reasonably well simulated. Precipitation patterns display the semi-annual march of the ITCZ across the area, plus considerable topographic effects. There is high evaporation from lakes and wetlands during the windy dry season, while evaporation from the moist land surface dominates the rainy season. Received October 15, 1998/Revised September 2, 1999     

Effects of water use on arsenic release to well water in a confined aquifer

Field-based experiments were designed to investigate the release of naturally occurring, low to moderate (< 50 microg/L) arsenic concentrations to well water in a confined sandstone aquifer in northeastern Wisconsin. Geologic, geochemical, and hydrogeologic data collected from a 115 m2 site demonstrate that arsenic concentrations in ground water are heterogeneous at the scale of the field site, and that the distribution of arsenic in ground water correlates to solid-phase arsenic in aquifer materials. Arsenic concentrations in a test well varied from 1.8 to 22 microg/L during experiments conducted under no, low, and high pumping rates. The quality of ground water consumed from wells under typical domestic water use patterns differs from that of ground water in the aquifer because of reactions that occur within the well. Redox conditions in the well can change rapidly in response to ground water withdrawals. The well borehole is an environment conducive to microbiological growth, and biogeochemical reactions also affect borehole chemistry. While oxidation of sulfide minerals appears to release arsenic to ground water in zones within the aquifer, reduction of arsenic-bearing iron (hydr)oxides is a likely mechanism of arsenic release to water having a long residence time in the well borehole.     

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.