Variable sequence of events during the past seven terminations in two deep-sea cores from the Southern Ocean

The relationships among internally consistent records of summer sea-surface temperature (SSST), winter sea ice (WSI), and diatomaceous stable isotopes were studied across seven terminations over the last 660 ka in sedimentary cores from ODP sites 1093 and 1094. The sequence of events at both sites indicates that SSST and WSI changes led the carbon and nitrogen isotopic changes in three Terminations (TI, TII and TVI) and followed them in the other four Terminations (TIII, TIV, TV and TVII). In both TIII and TIV, the leads and lags between the proxies were related to weak glacial mode, while in TV and TVII they were due to the influence of the mid-Pleistocene transition. We show that the sequence of events is not unique and does not follow the same pattern across terminations, implying that the processes that initiated climate change in the Southern Ocean has varied through time

Double oscillating diffusion encoding and sensitivity to microscopic anisotropy

PURPOSE: To introduce a novel diffusion pulse sequence, namely double oscillating diffusion encoding (DODE), and to investigate whether it adds sensitivity to microscopic diffusion anisotropy (µA) compared to the well-established double diffusion encoding (DDE) methodology. METHODS: We simulate measurements from DODE and DDE sequences for different types of microstructures exhibiting restricted diffusion. First, we compare the effect of varying pulse sequence parameters on the DODE and DDE signal. Then, we analyse the sensitivity of the two sequences to the microstructural parameters (pore diameter and length) which determine µA. Finally, we investigate specificity of measurements to particular substrate configurations. RESULTS: Simulations show that DODE sequences exhibit similar signal dependence on the relative angle between the two gradients as DDE sequences, however, the effect of varying the mixing time is less pronounced. The sensitivity analysis shows that in substrates with elongated pores and various orientations, DODE sequences increase the sensitivity to pore diameter, while DDE sequences are more sensitive to pore length. Moreover, DDE and DODE sequence parameters can be tailored to enhance/suppress the signal from a particular range of substrates. CONCLUSIONS: A combination of DODE and DDE sequences maximize sensitivity to µA, compared to using just the DDE method. Magn Reson Med, 2016. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine

Experimental and Theoretical Studies of the Environmental Sensitivity of the Absorption Spectra and Photochemistry of Nitenpyram and Analogs

Neonicotinoid (NN) pesticides have widespread use, largely replacing other pesticides such as the carbamates. Hence, there is a need to understand their environmental fates at a molecular level in various media, especially water. We report here the studies of a nitroenamine NN, nitenpyram (NPM), in aqueous solution where the absorption cross sections in the actinic region above 290 nm are observed to dramatically decrease compared to those in nonaqueous solvents. Quantum chemical calculations show that addition of a proton to the tertiary amine nitrogen in NPM breaks the conjugation in the chromophore, shifting the absorption to shorter wavelengths, consistent with experiment. However, surprisingly, adding a proton to the secondary amine nitrogen leads to its immediate transfer to the NO2 group, preserving the conjugation. This explains why the UV absorption of ranitidine (RAN), which has a similar chromophore but only secondary amine nitrogens, does not show a similar large blue shift in water. Photolysis quantum yields in aqueous NPM solutions were measured to be φ = 0.18 ± 0.07 at 254 nm, (9.4 ± 1.6) × 10-2 with broadband radiation centered at 313 nm and (5.2 ± 1.1) × 10-2 for broadband radiation centered at 350 nm (errors are 2σ). The major products in aqueous solutions are an imine that was also formed in the photolysis of the solid and a carboxylic acid derivative that is unique to the photolysis in water. Combining the larger quantum yields in water with the reduced absorption cross sections results in a calculated lifetime of NPM of only 5 min at a solar zenith angle of 35°, typical of 40°N latitude on April 1. The products do not absorb in the actinic region and hence will be long-lived with respect to photolysis

An oxygen isotope record of lacustrine opal from a European Maar indicates climatic stability during the Last Interglacial

The penultimate temperate period, 127–110 ka before present (BP), bracketed by abrupt shifts of the global climate system initiating and terminating it, is considered as an analogue of the Holocene because of a similar low global ice‐volume. Ice core records as well as continental and marine records exhibit conflicting evidence concerning the climate variability within this period, the Last Interglacial. We present, for the first time, a high‐resolution record of oxygen isotopes in diatom opal of the Last Interglacial obtained from the Ribains Maar in France (44°50′09″N 3°49′16″E). Our results indicate that the Last Interglacial in southwestern Europe was generally a period of climatic stability. The record shows that the temperate period was initiated by an abrupt warm event followed midway by a minor climatic transition to a colder climate. An abrupt isotopic depletion that occurs simultaneously with abrupt changes in pollen and diatom assemblages marks the end of the temperate period, and is correlative with the Melisey I stadial. Variations in the isotopic composition of lake‐water related to the isotopic composition of precipitation and evaporation dominate the biogenic opal oxygen isotope record

Polarization sensitive spectroscopy of charged Quantum Dots

We present an experimental and theoretical study of the polarized photoluminescence spectrum of single semiconductor quantum dots in various charge states. We compare our high resolution polarization sensitive spectral measurements with a new many-carrier theoretical model, which was developed for this purpose. The model considers both the isotropic and anisotropic exchange interactions between all participating electron-hole pairs. With this addition, we calculate both the energies and polarizations of all optical transitions between collective, quantum dot confined charge carrier states. We succeed in identifying most of the measured spectral lines. In particular, the lines resulting from singly-, doubly- and triply- negatively charged excitons and biexcitons. We demonstrate that lines emanating from evenly charged states are linearly polarized. Their polarization direction does not necessarily coincide with the traditional crystallographic direction. It depends on the shells of the single carriers, which participate in the recombination process.Comment: 11 pages, 9 figures. Revised versio

Oceanic distribution of inorganic germanium relative to silicon: Germanium discrimination by diatoms

Seventeen inorganic germanium and silicon concentration profiles collected from the Atlantic, southwest Pacific, and Southern oceans are presented. A plot of germanium concentration versus silicon concentration produced a near-linear line with a slope of 0.760 × 10−6 (±0.004) and an intercept of 1.27 (±0.24) pmol L−1 (r2 = 0.993, p < 0.001). When the germanium-to-silicon ratios (Ge/Si) were plotted versus depth and/or silicon concentrations, higher values are observed in surface waters (low in silicon) and decreased with depth (high in silicon). Germanium-to-silicon ratios in diatoms (0.608–1.03 × 10−6) and coupled seawater samples (0.471–7.46 × 10−6) collected from the Southern Ocean are also presented and show clear evidence for Ge/Si fractionation between the water and opal phases. Using a 10 box model (based on PANDORA), Ge/Si fractionation was modeled using three assumptions: (1) no fractionation, (2) fractionation using a constant distribution coefficient (KD) between the water and solid phase, and (3) fractionation simulated using Michaelis-Menten uptake kinetics for germanium and silicon via the silicon uptake system. Model runs indicated that only Ge/Si fractionation based on differences in the Michaelis-Menten uptake kinetics for germanium and silicon can adequately describe the data. The model output using this fractionation process produced a near linear line with a slope of 0.76 × 10−6 and an intercept of 0.92 (±0.28) pmol L−1, thus reflecting the oceanic data set. This result indicates that Ge/Si fractionation in the global ocean occurs as a result of subtle differences in the uptake of germanium and silicon via diatoms in surface waters

Mineral maturity and crystallinity index are distinct characteristics of bone mineral

The purpose of this study was to test the hypothesis that mineral maturity and crystallinity index are two different characteristics of bone mineral. To this end, Fourier transform infrared microspectroscopy (FTIRM) was used. To test our hypothesis, synthetic apatites and human bone samples were used for the validation of the two parameters using FTIRM. Iliac crest samples from seven human controls and two with skeletal fluorosis were analyzed at the bone structural unit (BSU) level by FTIRM on sections 2–4 lm thick. Mineral maturity and crystallinity index were highly correlated in synthetic apatites but poorly correlated in normal human bone. In skeletal fluorosis, crystallinity index was increased and maturity decreased, supporting the fact of separate measurement of these two parameters. Moreover, results obtained in fluorosis suggested that mineral characteristics can be modified independently of bone remodeling. In conclusion, mineral maturity and crystallinity index are two different parameters measured separately by FTIRM and offering new perspectives to assess bone mineral traits in osteoporosis

The Molecular Clockwork of the Fire Ant Solenopsis invicta

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