Synthesis of Alkaline Earth Diazenides MAEN2 (MAE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

The alkaline earth diazenides MAEN2 with MAE = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at highpressure/ high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) Å, c = 5.9844(9) Å, Z = 2, wRp = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN2 and BaN2. Accordingly, CaN2 is isotypic with SrN2 (space group I4/mmm (no. 139), a = 3.8054(2) Å, c = 6.8961(4) Å, Z = 2, wRp = 0.057) and the corresponding alkaline earth acetylenides (MAEC2) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) Å, b = 4.3776(3) Å, c = 7.2188(4) Å, β = 104.9679(33)°, Z = 4 and wRp = 0.049). The N−N bond lengths of 1.202(4) Å in CaN2 (SrN2 1.239(4) Å, BaN2 1.23(2) Å) correspond well with a double-bonded dinitrogen unit confirming a diazenide ion [N2]2−. Temperature-dependent in situ powder X-ray diffractometry of the three alkaline earth diazenides resulted in formation of the corresponding subnitrides MAE2N (MAE = Ca, Sr, Ba) at higher temperatures. FTIR spectroscopy revealed a band at about 1380 cm−1 assigned to the N−N stretching vibration of the diazenide unit. Electronic structure calculations support the metallic character of alkaline earth diazenides

A reference time scale for Site U1385 (Shackleton Site) on the SW Iberian Margin

Weproduced a composite depth scale and chronology for Site U1385 on the SWIberianMargin. Using log(Ca/Ti)measured by core scanning XRF at 1-cm resolution in all holes, a composite section was constructed to166.5 meter composite depth (mcd) that corrects for stretching and squeezing in each core. Oxygen isotopesof benthic foraminifera were correlated to a stacked d18O reference signal (LR04) to produce an oxygen isotopestratigraphy and age model.Variations in sediment color contain very strong precession signals at Site U1385, and the amplitude modulationof these cycles provides a powerful tool for developing an orbitally-tuned agemodel.We tuned the U1385 recordby correlating peaks in L* to the local summer insolation maxima at 37°N. The benthic d18O record of Site U1385,when placed on the tuned agemodel, generally agrees with other time scaleswithin their respective chronologicuncertainties.The age model is transferred to down-core data to produce a continuous time series of log(Ca/Ti) that reflectrelative changes of biogenic carbonate and detrital sediment. Biogenic carbonate increases during interglacialand interstadial climate states and decreases during glacial and stadial periods. Much of the variance in thelog(Ca/Ti) is explained by a linear combination of orbital frequencies (precession, tilt and eccentricity), whereasthe residual signal reflects suborbital climate variability. The strong correlation between suborbital log(Ca/Ti)variability and Greenland temperature over the last glacial cycle at Site U1385 suggests that this signal can beused as a proxy for millennial-scale climate variability over the past 1.5 Ma.Millennial climate variability, as expressed by log(Ca/Ti) at Site U1385, was a persistent feature of glacial climatesover the past 1.5Ma, including glacial periods of the early Pleistocene (‘41-kyrworld’)when boundary conditionsdiffered significantly from those of the late Pleistocene (‘100-kyr world’). Suborbital variability was suppressedduring interglacial stages and enhanced during glacial periods, especially when benthic d18O surpassed ~3.3–3.5‰. Each glacial inception was marked by appearance of strong millennial variability and each deglaciatio

Prediction of alcohol use and negative drinking-related consequences among university undergraduates

[7], 116 leaves ; 28 cm.Includes bibliographical references (p. 107-116).Current alcohol research tends to be atheoretical and concerned almost exclusively with etiology. In their attempts to explain why individuals drink, researchers have progressed from simple correlational studies identifying related variables to examinations of multiple factors using multiple regression and causal modeling methodologies. The present study contributes to the understanding of alcohol use and problem drinking by college studnets. Three hundred undergraduates from two Nova Scotia universities comprised the sample. Pearson Product Moment correlation coefficients identified significant relationships between the Quantity-Frequency Index of alcohol use (Q-F) and peer drinking, gender, age, the Alcohol Expectancy Questionnaire (AEQ), the number of observed college sporting events, and the number of college social functions attended. The Straus-Bacon Problem Drinking Scale (S-BPDS) was significantly related to the AEQ, gender, peer drinking, the Hassles Scale, percentage of times having drunk alcohol with people living nearby, and the number of participant sporting events attended. The present correlational findings corroborate previous research identifying these variables to be related to alcohol use and to problem drinking. The multiple regression findings contribute to previous research in suggesting different reasons why young men and women drink and experience negative drinking related consequences

Enhanced climate instability in the North Atlantic and southern Europe during the Last Interglacial

Considerable ambiguity remains over the extent and nature of millennial/centennial-scale climate instability during the Last Interglacial (LIG). Here we analyse marine and terrestrial proxies from a deep-sea sediment sequence on the Portuguese Margin and combine results with an intensively dated Italian speleothem record and climate-model experiments. The strongest expression of climate variability occurred during the transitions into and out of the LIG. Our records also document a series of multi-centennial intra-interglacial arid events in southern Europe, coherent with cold water-mass expansions in the North Atlantic. The spatial and temporal fingerprints of these changes indicate a reorganization of ocean surface circulation, consistent with low-intensity disruptions of the Atlantic meridional overturning circulation (AMOC). The amplitude of this LIG variability is greater than that observed in Holocene records. Episodic Greenland ice melt and runoff as a result of excess warmth may have contributed to AMOC weakening and increased climate instability throughout the LIG

Thermodynamic ground states of platinum metal nitrides

We have systematically studied the thermodynamic stabilities of various phases of the nitrides of the platinum metal elements using density functional theory. We show that for the nitrides of Rh, Pd, Ir and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability can extend up to 17 GPa for PtN{sub 2}. Furthermore, we show that according to calculations using the local density approximation, these new compounds are also thermodynamically stable at ambient pressure and thus may be the ground state phases for these materials. We further discuss the fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures

A reference time scale for Site U1385 (Shackleton Site) on the SW Iberian Margin

Variations in sediment color contain very strong precession signals at Site U1385, and the amplitude modulation of these cycles provides a powerful tool for developing an orbitally-tuned age model. We tuned the U1385 record by correlating peaks in L* to the local summer insolation maxima at 37°N. The benthic δ18O record of Site U1385, when placed on the tuned age model, generally agrees with other time scales within their respective chronologic uncertainties. The age model is transferred to down-core data to produce a continuous time series of log(Ca/Ti) that reflect relative changes of biogenic carbonate and detrital sediment. Biogenic carbonate increases during interglacial and interstadial climate states and decreases during glacial and stadial periods. Much of the variance in the log(Ca/Ti) is explained by a linear combination of orbital frequencies (precession, tilt and eccentricity), whereas the residual signal reflects suborbital climate variability. The strong correlation between suborbital log(Ca/Ti) variability and Greenland temperature over the last glacial cycle at Site U1385 suggests that this signal can be used as a proxy for millennial-scale climate variability over the past 1.5 Ma. Millennial climate variability, as expressed by log(Ca/Ti) at Site U1385, was a persistent feature of glacial climates over the past 1.5 Ma, including glacial periods of the early Pleistocene (‘41-kyr world’) when boundary conditions differed significantly from those of the late Pleistocene (‘100-kyr world’). Suborbital variability was suppressed during interglacial stages and enhanced during glacial periods, especially when benthic δ18O surpassed ~ 3.3–3.5‰. Each glacial inception was marked by appearance of strong millennial variability and each deglaciation was preceded by a terminal stadial event. Suborbital variability may be a symptomatic feature of glacial climate or, alternatively, may play a more active role in the inception and/or termination of glacial cycles