Micropaleontological and geochemical proxy studies of sediment core GeoB7926-2

[1] The low-latitude upwelling regime off the Mauritanian coast in the subtropical NE Atlantic accounts for a significant part of global export production. Although productivity variations in coastal upwelling areas are usually attributed to changes in wind stress and upwelling intensity, productivity dynamics off Mauritania are less straightforward because of the complex atmospheric and hydrographic setting. Here we integrate micropaleontological (diatoms) and geochemical (bulk biogenic sediment components, X-ray fluorescence, and alkenones) proxies to examine on submillennial-to-millennial changes in diatom production that occurred off Mauritania, NW Africa, for the last 25 ka. During the Last Glacial Maximum (LGM, 19.0-23.0 ka B.P.), moderate silicate content of upwelled waters coupled with weakened NE trade winds determined moderate diatom productivity. No significant cooling is observed during the LGM, suggesting that our alkenone-based SST reconstruction represents a local, upwelling-related signal rather than a global insolation related one. Extraordinary increases in diatom and opal concentrations during Heinrich event 1 (H1, 15.5-18.0 ka B.P.) and the Younger Dryas (YD, 13.5-11.5 ka B.P.) are attributed to enhanced upwelling of silica-rich waters and an enlarged upwelling filament, due to more intense NE trade winds. The synchronous increase of CaCO3 and K intensity and the decreased opal and diatoms values mark the occurrence of the Bølling/Allerød (BA, 13.5-15.5 ka B.P.) due to weakened eolian input and more humid conditions on land. Although the high export of diatoms is inextricably linked to upwelling intensity off Mauritania, variability in the nutrient content of the thermocline also plays a decisive role.

Stable oxygen isotope data of Globorotalia inflata and radiocarbon dates for sediment cores GeoB6211-2, GeoB13862-1, and GeoB6308-3

The Southern Westerly Winds (SWW) exert a crucial influence over the world ocean and climate. Nevertheless, a comprehensive understanding of the Holocene temporal and spatial evolution of the SWW remains a significant challenge due to the sparsity of high-resolution marine archives and appropriate SWW proxies. Here, we present a north-south transect of high-resolution planktonic foraminiferal oxygen isotope records from the western South Atlantic. Our proxy records reveal Holocene migrations of the Brazil- Malvinas Confluence (BMC), a highly sensitive feature for changes in the position and strength of the northern portion of the SWW. Through the tight coupling of the BMC position to the large-scale wind field, the records allow a quantitative reconstruction of Holocene latitudinal displacements of the SWW across the South Atlantic. Our data reveal a gradual poleward movement of the SWW by about 1-1.5° from the early to the mid-Holocene. Afterwards variability in the SWW is dominated by millennial-scale displacements in the order of 1° in latitude with no recognizable longer-term trend. These findings are confronted with results from a state-of-the-art transient Holocene climate simulation using a comprehensive coupled atmosphere-ocean general circulation model. Proxy-inferred and modeled SWW shifts compare qualitatively, but the model underestimates both orbitally forced multi-millennial and internal millennial SWW variability by almost an order of magnitude. The underestimated natural variability implies a substantial uncertainty in model projections of future SWW shifts.

Sedimentological, geochemical, micropaleontological and rock magnetic proxies of sediment core GeoB6211-2

Surface currents and sediment distribution of the SE South American upper continental margin are under influence of the South American Monsoon System (SAMS) and the Southern Westerly Wind Belt (SWWB). Both climatic systems determine the meridional position of the Subtropical Shelf Front (STSF) and probably also of the Brazil-Malvinas Confluence (BMC). We reconstruct the changing impact of the SAMS and the SWWB on sediment composition at the upper Rio Grande Cone off southern Brazil during the last 14 cal kyr combining sedimentological, geochemical, micropaleontological and rock magnetic proxies of marine sediment core GeoB 6211-2. Sharp reciprocal changes in ferri- and paramagnetic mineral content and prominent grain-size shifts give strong clues to systematic source changes and transport modes of these mostly terrigenous sediments. Our interpretations support the assumption that the SAMS over SE South America was weaker than today during most of the Late Glacial and entire Early Holocene, while the SWWB was contracted to more southern latitudes, resembling modern austral summer-like conditions. In consequence, the STSF and the BMC were driven to more southern positions than today's, favoring the deposition of Fe-rich but weakly magnetic La Plata River silts at the Rio Grande Cone. During the Mid Holocene, the northern boundary of the SWWB migrated northward, while the STSF reached its northernmost position of the last 14 cal kyr and the BMC most likely arrived at its modern position. This shift enabled the transport of Antarctic diatoms and more strongly magnetic Argentinean shelf sands to the Rio Grande Cone, while sediment contributions from the La Plata River became less important. During the Late Holocene, the modern El Niño Southern Oscillation set in and the SAMS and the austral tradewinds intensified, causing a southward shift of the STSF to its modern position. This reinforced a significant deposition of La Plata River silts at the Rio Grande Cone. These higher magnetic silts with intermediate Fe contents mirror the modern more humid terrestrial climatic conditions over SE South America.

Sedimentological, mineralogical, biogeochemical and micropaleontological parameters on sediment core PS69/849-2, Burton Basin, MacRobertson Shelf, East Antarctica

A multi-proxy study including sedimentological, mineralogical, biogeochemical and micropaleontological methods was conducted on sediment core PS69/849-2 retrieved from Burton Basin, MacRobertson Shelf, East Antarctica. The goal of this study was to depict the deglacial and Holocene environmental history of the MacRobertson Land-Prydz Bay region. A special focus was put on the timing of ice-sheet retreat and the variability of bottom-water formation due to sea ice formation through the Holocene. Results from site PS69/849-2 provide the first paleo-environmental record of Holocene variations in bottom-water production probably associated to the Cape Darnley polynya, which is the second largest polynya in the Antarctic. Methods included end-member modeling of laser-derived high-resolution grain size data to reconstruct the depositional regimes and bottom-water activity. The provenance of current-derived and ice-transported material was reconstructed using clay-mineral and heavy-mineral analysis. Conclusions on biogenic production were drawn by determination of biogenic opal and total organic carbon. It was found that the ice shelf front started to retreat from the site around 12.8 ka BP. This coincides with results from other records in Prydz Bay and suggests warming during the early Holocene optimum next to global sea level rise as the main trigger. Ice-rafted debris was then supplied to the site until 5.5 cal. ka BP, when Holocene global sea level rise stabilized and glacial isostatic rebound on MacRobertson Land commenced. Throughout the Holocene, three episodes of enhanced bottom-water activity probably due to elevated brine rejection in Cape Darnley polynya occured between 11.5 and 9 cal. ka BP, 5.6 and 4.5 cal. ka BP and since 1.5 cal. ka BP. These periods are related to shifts from warmer to cooler conditions at the end of Holocene warm periods, in particular the early Holocene optimum, the mid-Holocene warm period and at the beginning of the neoglacial. In contrast, between 7.7 and 6.7 cal. ka BP, brine rejection shut down, maybe owed to warm conditions and pronounced open-water intervals.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

Axial binding of 2-methylimidazole to the tetraarylcarboxylatodiruthenium (II, III) core: X-ray crystal structure of [Ru-2(O2CC6H4-p-OMe)(4)(2-mimH)(2)](ClO4). 1.75CH(2)Cl(2).H2O

Diruthenium (II. III) complexes of the type [Ru-2(O2CAr)(4) (2-mimH)(2)](ClO4) (Ar = C6H4-p-X : X=OMe,1, X=Me, 2, 2-mimH=2-methylimidazole) have been isolated from the reaction of Ru2Cl(O2CAr)(4) with 2-mimH in CH2Cl2 followed by the addition of NaClO4. The crystal structure of 1.1.75CH(2)Cl(2).H2O has been determined. The crystal belongs to the monoclinic space group p2(1)/c with the following unit cell dimensions for the C40H40N4O16ClRu2.1.75CH(2)Cl(2).H2O (M = 1237.0) : a = 12.347(3)Angstrom, b = 17.615(5)Angstrom, c = 26.148(2)Angstrom,beta = 92.88(1)degrees. v = 5679(2)Angstrom(3). Z=4, D-c = 1.45 g cm(-3). lambda(Mo-K-alpha) = 0.7107 Angstrom, mu(Mo-K-alpha) = 8.1 cm(-1), T = 293 K, R = 0.0815 (wR(2) = 0.2118) for 5834 reflections with 1 > 2 sigma(I). The complex has a tetracarboxylatodiruthenium (II, III) core and two axially bound 2-methylimidazole ligands. The Ru-Ru bond length is 2.290(1)Angstrom. The Ru-Ru bond order is 2.5 and the complex is three-electron paramagnetic. The complex shows an irreversible Ru-2(II,III)-->Ru-2(Il,II) reduction near -0.2 V vs SCE in CH2Cl2-0. 1 MTBAP. The complexes exemplify the first adduct of the tetracarboxylatodiruthenium (II,III) core having N-donor ligands

Studies on the structure of tricyclohexyltin-2-(1,2-dithioethylene)methylene-3-oxo-5-aryl-4-pentenicate

Three title compounds were prepared and the structure of title compound 2 was characterized by IR, H-1 NMR, C-13 NMR, Sn-119 NMR spectroscopy and the crystal structure of compound 2a was determined by X-ray analysis with the final R indices[I >2 sigma (I)] R-1 = 0.0350 and R-2,R-omega = 0.0888. The crystal of compound 2a belongs to triclinic system, space group P1 with a = 1.0598(6) nm, b = 1.307 4(10) nm, c = 1.378 6(10) nm, alpha = 62.666(7)degrees, beta = 72.530(2)degrees, gamma = 80. 680(2)degrees, V = 1.618 0 nm(3), D-x = 1. 444 g (.) cm(-3), Z = 1, F (000) = 728. The bond length of Sn1-O1 is 0. 2076 nm and Sn1 . . . O2 distance is 0.301 3 nm. The coordination about the tin atom can be considered as a distorted tetrahedral. The detail values of H-1 NMR, C-13 NMR, Sn-119 NMR, (2)J(119Sn-1H) and J(119Sn-13C) were obtained. delta (119Sn) = 23.836, (2)J(119Sn-1H) = 88.0 Hz, (1)J(119Sn-13C) = 347.1 Hz, (2)J(119Sn-13C) = 45.6 Hz.

A new dinuclear molybdenum(V)-sulfur complex containing citrate ligand: synthesis and characterization of K2.5Na2NH4[Mo2O2S2(cit)(2)].5H(2)O

The complex, K2.5Na2NH4[Mo2O2S2(cit)(2)]. 5H(2)O (1), was obtained by crystallization from a solution of (NH4)(2)MoS4, potassium citrate (K(3)cit) and hydroxyl sodium in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The crystals are triclinic, space group , a = 7.376 (3)Angstrom, b = 14.620 (2) Angstrom, c = 14.661 (1) Angstrom, alpha = 71.10 (1)degrees, beta = 81.77 (1)degrees, gamma = 78.27(2)degrees, R = 0.0584 for 2545 observed (I > 2 sigma (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with two bridging sulfur atoms and a terminal oxygen atom completes distorted coordination octahedron around each molybdenum atom. Principal dimensions are: Mo = O-t, 1.707 Angstrom (av); Mo-S-b, 2.341 Angstrom (av); Mo-O-(hydroxyl), 2.021 Angstrom (av); Mo-O(alpha-carboxyl), 2.1290 Angstrom (av) and Mo-O(beta-carboxyl), 2.268(av) Angstrom. IR spectrum is in agreement with the structure.

高阶无静差采样控制系统的动态综合

本文利用“最小响应法”给出了 N≥2阶无静差采样控制系统的设计公式.作者指出:对于某类闭环控制系统,在给定阶跃响应最大超调量σ_(max)的条件下,可以找出最佳比值T/T_(T 为系统的采样周期,T_(?)为对象的不便克服的等效小时间常数之和),使系统获得相应阶最大误差系数 K_(N+1),从而可使系统达到快速精密的控制指标。为了在工程设计中应用方便,文中还给出了二至六阶无静差的σ_(max),T/T_(?),K_(N+1)T(?)最佳参数组,使得这类闭环控制系统的设计最佳化和简易化.

Mono- and dimethyl-1,2,4-triazolate as ligands for the mercuric ion in the cationic three-dimensional coordination polymer of [Hg-2(Mmt)(Dmt)(2)](NO3)(H2O))

Colourless crystals of [Hg-2(Mmt)(Dmt)(2)](NO3)(H2O) were obtained from a reaction of mercuric nitrate with nionomethyl- and dimethyl-1,2.4-triazolate (Mmt(-) and Dmt(-), respectively). In the crystal structure (monoclinic, C2/c (no. 15), a = 2579.4(4) b = 1231.1(2), c = 1634.8(2) pm, beta = 128.32(1)degrees V = 4073.3(11).10(6).pm(3): Z = 8, R-1 [I-0 > 2 sigma(I-0)]: 0.0355), half of the mercuric ions are essentially two-coordinate (Hg-N: 210-215 pm), the other half are tetrahedrally surrounded by N-donor atoms (Hg-N: 221, 225 pm) of the Mmt(-) and Dmt(-) anions. These three-N ligands construct a three-dimensional framework.

Mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2)

Single crystals of mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2), were obtained from aqueous solutions of 1,2,4-triazole and Hg(NO3)(2)center dot 2H(2)O. The crystal structure [monoclinic, P2(1)/c (no. 14), a = 499.6(2), b = 1051.2(4), c = 711.1(3) pm, beta = 117.55(1)degrees, Z = 2, R, for 890 reflections with I-0 > 2 sigma(I-0): 0.0369] contains linear centrosymmetric Hg(Imf)(2) molecules with Hg-N distances of only 203.5(7)pm. Two plus two intra- and intermolecular nitrogen atoms add to an effective coordination number of 6.

Tetrahedra and vertex-sharing double tetrahedra in the ammonium iodomercurates(II) (NH4)(7)[HgI4](2)[Hg2I7](H2O) and (NH4)(3)[Hg2I7]

The new ammonium iodomercurates(II), (NH4)(7)[HgI4](2)[Hg2I7](H2O) (1) and (NH4)(3)[Hg2I7] (2) contain isolated tetrahedra and vertex-sharing double tetrahedra as the anions. The crystal structures were determined from single-crystal X-ray diffraction data: 1: orthorhombic, Pnma (no. 62), a = 2175.9(2), b = 1781.8(2), c = 1256.2(2) pm, Z = 4. R-1 [I-0 > 2 sigma(I-0)] = 0.0520; 2: monoclinic, P2(1)/c (no. 14), a = 1259.0(2), b = 773.2(1), c = 2172.4(3) pm, beta = 101.18(2)degrees, Z = 4, R, [I-0 > 2 sigma(I-0)] = 0.0308.

Shape and Rotation Modeling and Thermophysical Analysis of Near-Earth Asteroid (1917) Cuyo

We are conducting an ESO Large Program that includes optical photometry, thermal-IR observations, and optical-NIR spectroscopy of selected NEAs. Among the principal goals of the program are shape and spin-state modeling, and searching for YORP-induced changes in rotation periods. One of our targets is asteroid (1917) Cuyo, a near-Earth asteroid from the Amor group. We carried out an extensive observing campaign on Cuyo between April 2010 and April 2013, operating primarily at the ESO 3.6m NTT for optical photometry, and the 8.2m VLT at Paranal for thermal-IR imaging. Further optical observations were acquired at the ESO 2.2m telescope, the Palomar 200" Hale telescope (California), JPL’s Table Mountain Observatory (California) and the Faulkes Telescope South (Australia). We obtained optical imaging data for rotational lightcurves throughout this period, as the asteroid passed through a wide range of observational geometries, conducive to producing a good shape model and spin state solution. The preliminary shape and spin state model indicates a nearly spherical shape and a rotation pole at ecliptic longitude λ = 53° ± 20° and latitude β = -37° ± 10° (1-sigma error bars are approximate). The sidereal rotation period was measured to be 2.6899522 ± (3 × 10^-7) hours. Linkage with earlier lightcurve data shows possible evidence of a small change in rotation rate during the period 1989-2013. We applied the NEATM thermal model (Harris A., Icarus 131, 291, 1998) to our VLT thermal-IR measurements (8-19.6 μm), obtained in September and December 2011. The derived effective diameter ranges from 3.4 to 4.2 km, and the geometric albedo is 0.16 (+0.07, -0.04). Using the shape model and thermal fluxes we will perform a detailed thermophysical analysis using the new Advanced Thermophysical Model (Rozitis, B. & Green, S.F., MNRAS 415, 2042, 2011; Rozitis, B. & Green, S.F., MNRAS 423, 367, 2012). This work was performed in part at the Jet Propulsion Laboratory under a contract with NASA.