Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Indian summer monsoon variations could have affected the early Holocene woodland expansion in the Near East

Postglacial expansion of deciduous oak woodlands of the Zagros—Anti-Taurus Mountains, a major biome of the Near East, was delayed until the middle Holocene at ~6300 cal. yr BP. The current hypotheses explain this delay as a consequence of a regional aridity during the early Holocene, slow migration rates of forest trees, and/or a long history of land use and agro-pastoralism in this region. In the present paper, support is given to a hypothesis that suggests different precipitation seasonalities during the early Holocene compared with the late Holocene. The oak species of the Zagros—Anti-Taurus Mts, particularly Quercus brantii Lindl., are strongly dependent on spring precipitation for regeneration and are sensitive to a long dry season. Detailed analysis of modern atmospheric circulation patterns in SW Asia during the late spring suggests that the Indian Summer Monsoon (ISM) intensification can modify the amount of late spring and/or early summer rainfall in western/northwestern Iran and eastern Anatolia, which could in turn have controlled the development of the Zagros—Anti-Taurus deciduous oak woodlands. During the early Holocene, the northwestward shift of the Inter-Tropical Convergence Zone (ITCZ) could have displaced the subtropical anticyclonic belt or associated high pressure ridges to the northwest. The latter could, in turn, have prevented the southeastward penetration of low pressure systems originating from the North Atlantic and Black Sea regions. Such atmospheric configuration could have reduced or eliminated the spring precipitation creating a typical Mediterranean continental climate characterized by winter-dominated precipitation. This scenario highlights the complexity of biome response to climate system interactions in transitional climatic and biogeographical regions.

Simulated variations in atmospheric CO2 over a Wisconsin forest using a coupled ecosystem-atmosphere model

Ecosystem fluxes of energy, water, and CO2 result in spatial and temporal variations in atmospheric properties. In principle, these variations can be used to quantify the fluxes through inverse modelling of atmospheric transport, and can improve the understanding of processes and falsifiability of models. We investigated the influence of ecosystem fluxes on atmospheric CO2 in the vicinity of the WLEF-TV tower in Wisconsin using an ecophysiological model (Simple Biosphere, SiB2) coupled to an atmospheric model (Regional Atmospheric Modelling System). Model parameters were specified from satellite imagery and soil texture data. In a companion paper, simulated fluxes in the immediate tower vicinity have been compared to eddy covariance fluxes measured at the tower, with meteorology specified from tower sensors. Results were encouraging with respect to the ability of the model to capture observed diurnal cycles of fluxes. Here, the effects of fluxes in the tower footprint were also investigated by coupling SiB2 to a high-resolution atmospheric simulation, so that the model physiology could affect the meteorological environment. These experiments were successful in reproducing observed fluxes and concentration gradients during the day and at night, but revealed problems during transitions at sunrise and sunset that appear to be related to the canopy radiation parameterization in SiB2.

Kinematical analysis of redundant drive wire mechanisms with velocity constraint

In this paper, we propose a new velocity constraint type for Redundant Drive Wire Mechanisms. The purpose of this paper is to demonstrate that the proposed velocity constraint module can fix the orientation of the movable part and to use the kinematical analysis method to obtain the moving direction of the movable part. First, we discuss the necessity of using this velocity constraint type and the possible applications of the proposed mechanism. Second, we derive the basic equations of a wire mechanism with this constraint type. Next, we present a method of motion analysis on active and passive constraint spaces, which is used to find the moving direction of a movable part. Finally, we apply the above analysis method on a wire mechanism with a velocity constraint module and on a wire mechanism with four double actuator modules. By evaluating the results, we prove the validity of the proposed constraint type.

Electrical signature in polar night cloud base variations

Layer clouds are globally extensive. Their lower edges are charged negatively by the fair weather atmospheric electricity current flowing vertically through them. Using polar winter surface meteorological data from Sodankyla ̈ (Finland) and Halley (Antarctica), we find that when meteorological diurnal variations are weak, an appreciable diurnal cycle, on average, persists in the cloud base heights, detected using a laser ceilometer. The diurnal cloud base heights from both sites correlate more closely with the Carnegie curve of global atmospheric electricity than with local meteorological measurements. The cloud base sensitivities are indistinguishable between the northern and southern hemispheres, averaging a (4.0 ± 0.5) m rise for a 1% change in the fair weather electric current density. This suggests that the global fair weather current, which is affected by space weather, cosmic rays and the El Nin ̃o Southern Oscillation, is linked with layer cloud properties.

Axonal velocity distributions in neural feld equations

By modelling the average activity of large neuronal populations, continuum mean field models (MFMs) have become an increasingly important theoretical tool for understanding the emergent activity of cortical tissue. In order to be computationally tractable, long-range propagation of activity in MFMs is often approximated with partial differential equations (PDEs). However, PDE approximations in current use correspond to underlying axonal velocity distributions incompatible with experimental measurements. In order to rectify this deficiency, we here introduce novel propagation PDEs that give rise to smooth unimodal distributions of axonal conduction velocities. We also argue that velocities estimated from fibre diameters in slice and from latency measurements, respectively, relate quite differently to such distributions, a significant point for any phenomenological description. Our PDEs are then successfully fit to fibre diameter data from human corpus callosum and rat subcortical white matter. This allows for the first time to simulate long-range conduction in the mammalian brain with realistic, convenient PDEs. Furthermore, the obtained results suggest that the propagation of activity in rat and human differs significantly beyond mere scaling. The dynamical consequences of our new formulation are investigated in the context of a well known neural field model. On the basis of Turing instability analyses, we conclude that pattern formation is more easily initiated using our more realistic propagator. By increasing characteristic conduction velocities, a smooth transition can occur from self-sustaining bulk oscillations to travelling waves of various wavelengths, which may influence axonal growth during development. Our analytic results are also corroborated numerically using simulations on a large spatial grid. Thus we provide here a comprehensive analysis of empirically constrained activity propagation in the context of MFMs, which will allow more realistic studies of mammalian brain activity in the future.

Summertime total ozone variations over middle and polar latitudes

The statistical relationship between springtime and summertime ozone over middle and polar latitudes is analyzed using zonally averaged total ozone data. Shortterm variations in springtime midlatitude ozone demonstrate only a modest correlation with springtime polar ozone variations. However by early summer, ozone variations throughout the extratropics are highly correlated. Analysis of correlation functions indicates that springtime midlatitude ozone, not polar ozone, is the best predictor for summertime polar ozone. Long-term total ozone trends at middle and high latitudes are also different for spring and nearly identical for summer. About 39% of the observed southern midlatitude ozone decline in December can be attributed to the polar ozone depletion up to November. In the Northern Hemisphere, the corresponding contribution is about 15%, but the error bars are too large to make an accurate estimate.

The influence of anthropogenic aerosol on multi-decadal variations of historical global climate

Analysis of single forcing runs from CMIP5 (the fifth Coupled Model Intercomparison Project) simulations shows that the mid-twentieth century temperature hiatus, and the coincident decrease in precipitation, is likely to have been influenced strongly by anthropogenic aerosol forcing. Models that include a representation of the indirect effect of aerosol better reproduce inter-decadal variability in historical global-mean near-surface temperatures, particularly the cooling in the 1950s and 1960s, compared to models with representation of the aerosol direct effect only. Models with the indirect effect also show a more pronounced decrease in precipitation during this period, which is in better agreement with observations, and greater inter-decadal variability in the inter-hemispheric temperature difference. This study demonstrates the importance of representing aerosols, and their indirect effects, in general circulation models, and suggests that inter-model diversity in aerosol burden and representation of aerosol–cloud interaction can produce substantial variation in simulations of climate variability on multi decadal timescales.

Sequential variations of phytoplankton growth and mortality in an NPZ model: a remote-sensing-based assessment

Radiometric data in the visible domain acquired by satellite remote sensing have proven to be powerful for monitoring the states of the ocean, both physical and biological. With the help of these data it is possible to understand certain variations in biological responses of marine phytoplankton on ecological time scales. Here, we implement a sequential data-assimilation technique to estimate from a conventional nutrient–phytoplankton–zooplankton (NPZ) model the time variations of observed and unobserved variables. In addition, we estimate the time evolution of two biological parameters, namely, the specific growth rate and specific mortality of phytoplankton. Our study demonstrates that: (i) the series of time-varying estimates of specific growth rate obtained by sequential data assimilation improves the fitting of the NPZ model to the satellite-derived time series: the model trajectories are closer to the observations than those obtained by implementing static values of the parameter; (ii) the estimates of unobserved variables, i.e., nutrient and zooplankton, obtained from an NPZ model by implementation of a pre-defined parameter evolution can be different from those obtained on applying the sequences of parameters estimated by assimilation; and (iii) the maximum estimated specific growth rate of phytoplankton in the study area is more sensitive to the sea-surface temperature than would be predicted by temperature-dependent functions reported previously. The overall results of the study are potentially useful for enhancing our understanding of the biological response of phytoplankton in a changing environment.

The impact of diurnal variability in sea surface temperature on the atlantic air-sea CO2 flux

The effect of diurnal variations in sea surface temperature (SST) on the air-sea flux of CO2 over the central Atlantic ocean and Mediterranean Sea (60 S–60 N, 60 W–45 E) is evaluated for 2005–2006. We use high spatial resolution hourly satellite ocean skin temperature data to determine the diurnal warming (ΔSST). The CO2 flux is then computed using three different temperature fields – a foundation temperature (Tf, measured at a depth where there is no diurnal variation), Tf, plus the hourly ΔSST and Tf, plus the monthly average of the ΔSSTs. This is done in conjunction with a physically-based parameterisation for the gas transfer velocity (NOAA-COARE). The differences between the fluxes evaluated for these three different temperature fields quantify the effects of both diurnal warming and diurnal covariations. We find that including diurnal warming increases the CO2 flux out of this region of the Atlantic for 2005–2006 from 9.6 Tg C a−1 to 30.4 Tg C a−1 (hourly ΔSST) and 31.2 Tg C a−1 (monthly average of ΔSST measurements). Diurnal warming in this region, therefore, has a large impact on the annual net CO2 flux but diurnal covariations are negligible. However, in this region of the Atlantic the uptake and outgassing of CO2 is approximately balanced over the annual cycle, so although we find diurnal warming has a very large effect here, the Atlantic as a whole is a very strong carbon sink (e.g. −920 Tg C a−1 Takahashi et al., 2002) making this is a small contribution to the Atlantic carbon budget.

Reconstruction and prediction of variations in the open solar magnetic flux and interplanetary conditions

Historic geomagnetic activity observations have been used to reveal centennial variations in the open solar flux and the near-Earth heliospheric conditions (the interplanetary magnetic field and the solar wind speed). The various methods are in very good agreement for the past 135 years when there were sufficient reliable magnetic observatories in operation to eliminate problems due to site-specific errors and calibration drifts. This review underlines the physical principles that allow these reconstructions to be made, as well as the details of the various algorithms employed and the results obtained. Discussion is included of: the importance of the averaging timescale; the key differences between “range” and “interdiurnal variability” geomagnetic data; the need to distinguish source field sector structure from heliospherically-imposed field structure; the importance of ensuring that regressions used are statistically robust; and uncertainty analysis. The reconstructions are exceedingly useful as they provide calibration between the in-situ spacecraft measurements from the past five decades and the millennial records of heliospheric behaviour deduced from measured abundances of cosmogenic radionuclides found in terrestrial reservoirs. Continuity of open solar flux, using sunspot number to quantify the emergence rate, is the basis of a number of models that have been very successful in reproducing the variation derived from geomagnetic activity. These models allow us to extend the reconstructions back to before the development of the magnetometer and to cover the Maunder minimum. Allied to the radionuclide data, the models are revealing much about how the Sun and heliosphere behaved outside of grand solar maxima and are providing a means of predicting how solar activity is likely to evolve now that the recent grand maximum (that had prevailed throughout the space age) has come to an end.

On the generalized eigenvalue problem for the Rossby wave vertical velocity in the presence of mean flow and topography

In a series of papers, Killworth and Blundell have proposed to study the effects of a background mean flow and topography on Rossby wave propagation by means of a generalized eigenvalue problem formulated in terms of the vertical velocity, obtained from a linearization of the primitive equations of motion. However, it has been known for a number of years that this eigenvalue problem contains an error, which Killworth was prevented from correcting himself by his unfortunate passing and whose correction is therefore taken up in this note. Here, the author shows in the context of quasigeostrophic (QG) theory that the error can ulti- mately be traced to the fact that the eigenvalue problem for the vertical velocity is fundamentally a non- linear one (the eigenvalue appears both in the numerator and denominator), unlike that for the pressure. The reason that this nonlinear term is lacking in the Killworth and Blundell theory comes from neglecting the depth dependence of a depth-dependent term. This nonlinear term is shown on idealized examples to alter significantly the Rossby wave dispersion relation in the high-wavenumber regime but is otherwise irrelevant in the long-wave limit, in which case the eigenvalue problems for the vertical velocity and pressure are both linear. In the general dispersive case, however, one should first solve the generalized eigenvalue problem for the pressure vertical structure and, if needed, diagnose the vertical velocity vertical structure from the latter.

Optimization of a sea ice model using basinwide observations of Arctic sea ice thickness, extent, and velocity

A stand-alone sea ice model is tuned and validated using satellite-derived, basinwide observations of sea ice thickness, extent, and velocity from the years 1993 to 2001. This is the first time that basin-scale measurements of sea ice thickness have been used for this purpose. The model is based on the CICE sea ice model code developed at the Los Alamos National Laboratory, with some minor modifications, and forcing consists of 40-yr ECMWF Re-Analysis (ERA-40) and Polar Exchange at the Sea Surface (POLES) data. Three parameters are varied in the tuning process: Ca, the air–ice drag coefficient; P*, the ice strength parameter; and α, the broadband albedo of cold bare ice, with the aim being to determine the subset of this three-dimensional parameter space that gives the best simultaneous agreement with observations with this forcing set. It is found that observations of sea ice extent and velocity alone are not sufficient to unambiguously tune the model, and that sea ice thickness measurements are necessary to locate a unique subset of parameter space in which simultaneous agreement is achieved with all three observational datasets.