Multi-proxy record of planktonic and benthic foraminiferal d18O, and Mg/Ca-derived surface and lower thermocline temperatures in sediment core SO18471 (GIK18471), Timor Sea

Paleostudies of the Indonesian Throughflow (ITF) are largely based on temperature and salinity reconstructions of its near surface component, whereas the variability of its lower thermocline flow has rarely been investigated. We present a multi-proxy record of planktonic and benthic foraminiferal d18O, Mg/Ca-derived surface and lower thermocline temperatures, X-ray fluorescence (XRF)-derived runoff and sediment winnowing for the past 130 ka in marine sediment core SO18471. Core SO18471, retrieved from a water depth of 485 m at the southern edge of the Timor Strait close to the Sahul Shelf, sits in a strategic position to reconstruct variations in both the ITF surface and lower thermocline flow as well as to investigate hydrological changes related to monsoon variability and shelf dynamics over time. Sediment winnowing demonstrates that the ITF thermocline flow intensified during MIS 5d-a and MIS 1. In contrast during MIS 5e, winnowing was reduced and terrigenous input increased suggesting intensification of the local wet monsoon and a weaker ITF. Lower thermocline warming during globally cold periods (MIS 4 - MIS 2) appears to be related to a weaker and contracted thermocline ITF and advection of warm and salty Indian Ocean waters.

The role of impurities in the shape, structure and physical properties of semiconducting oxide nanostructures grown by thermal evaporation

A thermal evaporation method developed in the research group enables to grow and design several morphologies of semiconducting oxide nanostructures, such as Ga_2O_3, GeO_2 or Sb_2O_3, among others, and some ternary oxide compounds (ZnGa_2O_4, Zn_2GeO_4). In order to tailor physical properties, a successful doping of these nanostructures is required. However, for nanostructured materials, doping may affect not only their physical properties, but also their morphology during the thermal growth process. In this paper, we will show some examples of how the addition of impurities may result into the formation of complex structures, or changes in the structural phase of the material. In particular, we will consider the addition of Sn and Cr impurities into the precursors used to grow Ga_2O_3, Zn_2GeO_4 and Sb_2O_3 nanowires, nanorods or complex nanostructures, such as crossing wires or hierarchical structures. Structural and optical properties were assessed by electron microscopy (SEM and TEM), confocal microscopy, spatially resolved cathodoluminescence (CL), photoluminescence, and Raman spectroscopies. The growth mechanisms, the luminescence bands and the optical confinement in the obtained oxide nanostructures will be discussed. In particular, some of these nanostructures have been found to be of interest as optical microcavities. These nanomaterials may have applications in optical sensing and energy devices.

Interdigitating organic bilayers direct the short interlayer spacing in hybrid organic–inorganic layered vanadium oxide nanostructures

Layered metal oxides provide a single-step route to sheathed superlattices of atomic layers of a variety of inorganic materials, where the interlayer spacing and overall layered structure forms the most critical feature in the nanomaterials’ growth and application in electronics, health, and energy storage. We use a combination of computer simulations and experiments to describe the atomic-scale structure, dynamics and energetics of alkanethiol-intercalated layered vanadium oxide-based nanostructures. Molecular dynamics (MD) simulations identify the unusual substrate-constrained packing of the alkanethiol surfactant chains along each V2O5 (010) face that combines with extensive interdigitation between chains on opposing faces to maximize three-dimensional packing in the interlayer regions. The findings are supported by high resolution electron microscopy analyses of synthesized alkanethiol-intercalated vanadium oxide nanostructures, and the preference for this new interdigitated model is clarified using a large set of MD simulations. This dependency stresses the importance of organic–inorganic interactions in layered material systems, the control of which is central to technological applications of flexible hybrid nanomaterials.

Giant enhancement of n-type carrier mobility in highly strained germanium nanostructures

First-principles electronic structure methods are used to predict the rate of n-type carrier scattering due to phonons in highly-strained Ge. We show that strains achievable in nanoscale structures, where Ge becomes a direct bandgap semiconductor, cause the phonon-limited mobility to be enhanced by hundreds of times that of unstrained Ge, and over a thousand times that of Si. This makes highly tensile strained Ge a most promising material for the construction of channels in CMOS devices, as well as for Si-based photonic applications. Biaxial (001) strain achieves mobility enhancements of 100 to 1000 with strains over 2%. Low temperature mobility can be increased by even larger factors. Second order terms in the deformation potential of the Gamma valley are found to be important in this mobility enhancement. Although they are modified by shifts in the conduction band valleys, which are caused by carrier quantum confinement, these mobility enhancements persist in strained nanostructures down to sizes of 20 nm.

d11B and metal/Ca ratios versus size fractions in the Surface and deep dwelling species, ODP Holes 130-806B and 108-664C

We have assessed the reliability of several foraminifer-hosted proxies of the ocean carbonate system (d11B, B/Ca, and U/Ca) using Holocene samples from the Atlantic and Pacific oceans. We examined chemical variability over a range of test sizes for two surface-dwelling foraminifers (Globigerinoides sacculifer and Globigerinoides ruber). Measurements of d11B in G. ruber show no significant relationship with test size in either Atlantic or Pacific sites and appear to provide a robust proxy of surface seawater pH. Likewise there is no significant variability in the d11B of our Atlantic core top G. sacculifer, but we find that d11B increases with increasing test size for G. sacculifer in the Pacific. These systematic differences in d11B are inferred to be a consequence of isotopically light gametogenic calcite in G. sacculifer and its preferential preservation during postdepositional dissolution. The trace element ratio proxies of ocean carbonate equilibria, U/Ca and B/Ca, show systematic increases in both G. ruber and G. sacculifer with increasing test size, possibly as a result of changing growth rates. This behavior complicates their use in paleoceanographic reconstructions. In keeping with several previous studies we find that Mg/Ca ratios increase with increasing size fraction in our well-preserved Atlantic G. sacculifer but not in G. ruber. In contrast to previous interpretations we suggest that these observations reflect a proportionally larger influence of compositionally distinct gametogenic calcite in small individuals compared to larger ones. As with d11B this influences G. sacculifer but not G. ruber, which has negligible gametogenic calcite.

Mg/Ca ratio, Sr/Ca ratio and stable isotopes of the foraminifera Oridorsalis umbonatus in surface sediment samples

We investigate the influence of carbonate system parameters (carbonate ion concentration, [CO3**2-]; carbonate ion saturation, Delta [CO3**2-]) on the trace element and stable isotope ratios in the endobenthic foraminifera Oridorsalis umbonatus. Data from modern core top samples from the Namibian continental slope suggest that the shell composition of this species is influenced by the chemistry of the pore-water. For these organic-rich sediments, the impact of ocean bottom water properties on both pore-water and shell chemistry is surprisingly small. Sr/Ca correlates positively with [CO3**2-] and to a lesser extent with Delta [CO3**2-], which is opposed to previous results. A [CO3**2-] decrease of 10 µmol/kg leads to an increase of 0.05 mmol/mol in Sr/Ca. We observe a correlation between shell d18O (corrected for temperature and d18O seawater) and [CO3**2-], however, the variability of the corrected d18O is close to the analytical limit. No clear dependences were observed for d13C and Mg/Ca.

Benthic (C. wuellerstorfi) d18O, d13C and Cd/Ca in sediment core NEAP 4K across the last deglaciation

We present evidence that the characteristic chemical signature (based on coupled benthic foraminiferal Cd/Ca and d13C) of Antarctic Intermediate waters (AAIW) penetrated throughout the intermediate depths of the Atlantic basin to the high-latitude North Atlantic during the abrupt cooling events of the last deglaciation: Heinrich 1 and the Younger Dryas. AAIW may play the dynamic counterpart to the "bipolar seesaw" when near-freezing salty bottom waters from the Antarctic (AABW) sluggishly ventilate the deep ocean. Our data reinforce the concept that interglacial circulation is stabilized by salinity feedbacks between salty northern sourced deep waters (NADW) and fresh southern sourced waters (AABW and AAIW). Further, the glacial ocean may be susceptible to the more finely balanced relative densities of NADW and AAIW, due to either freshwater input or a reversal of the salinity gradient, such that the ocean is poised for NADW collapse via a negative salinity feedback. The unstable climate of the glacial period and its termination may arise from the closer competition for ubiquity at intermediate depths between northern and southern sourced intermediate waters.

Nd/Ca ratios in plankton-towed and core top foraminifera

Planktic foraminifera have been used as recorders of the neodymium (Nd) isotopic composition of seawater, although there is still controversy over the precise provenance of the Nd signal. We present an extensive, multispecific plankton tow Nd/Ca data set from several geographic locations (SE Atlantic, NE Atlantic, Norwegian Sea, and western Mediterranean), together with core top samples from the Mediterranean region. The range of Nd/Ca ratios in plankton-towed foraminifera, cleaned only of organic material, from all regions (0.01-0.7 µmol/mol), is similar to previously published analyses of sedimentary foraminifera cleaned using both oxidative and reductive steps, with distribution coefficients (Kd) ranging between 4 and 302. For the Mediterranean, where core top and plankton tow data are both available, the range for plankton tows (0.05-0.7 µmol/mol) is essentially identical to that for the core tops (0.1-0.5 µmol/mol). Readsorption of Nd during cleaning is ruled out by the fact that the plankton tow samples underwent only an oxidative cleaning process. We find a relationship between manganese (Mn) and Nd in plankton tow samples that is mirrored by a similar correlation in core top samples. This relationship suggests that Fe-Mn coatings are of negligible importance to the Nd budgets of foraminifera as the Nd/Mn ratio it implies is over an order of magnitude greater than that seen in other Fe-Mn oxide phases. Rather, since both plankton tows and core tops present a similar behavior, the Nd/Mn relationship must originate in the upper water column. The data are consistent with the acquisition of Nd and Mn from the water column by binding to organic material and the fact that intratest organic material is shielded from both aggressive cleaning and diagenetic processes. Collectively, the results help to explain two abiding puzzles about Nd in sedimentary planktic foraminifera: their high REE contents and the fact that they record a surface water Nd isotopic signal, regardless of the cleaning procedure used.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.