Physical interpretation of the spectral radiative signature in the transition zone between cloud-free and cloudy regions

One-second-resolution zenith radiance measure- ments from the Atmospheric Radiation Measurement pro- gram’s new shortwave spectrometer (SWS) provide a unique opportunity to analyze the transition zone between cloudy and cloud-free air, which has considerable bearing on the aerosol indirect effect. In the transition zone, we find a re- markable linear relationship between the sum and difference of radiances at 870 and 1640 nm wavelengths. The intercept of the relationship is determined primarily by aerosol prop- erties, and the slope by cloud properties. We then show that this linearity can be predicted from simple theoretical con- siderations and furthermore that it supports the hypothesis of inhomogeneous mixing, whereby optical depth increases as a cloud is approached but the effective drop size remains un- changed.

Can we measure terrestrial photosynthesis from space directly, using spectral reflectance and fluorescence?

Attempts to estimate photosynthetic rate or gross primary productivity from remotely sensed absorbed solar radiation depend on knowledge of the light use efficiency (LUE). Early models assumed LUE to be constant, but now most researchers try to adjust it for variations in temperature and moisture stress. However, more exact methods are now required. Hyperspectral remote sensing offers the possibility of sensing the changes in the xanthophyll cycle, which is closely coupled to photosynthesis. Several studies have shown that an index (the photochemical reflectance index) based on the reflectance at 531 nm is strongly correlated with the LUE over hours, days and months. A second hyperspectral approach relies on the remote detection of fluorescence, which is a directly related to the efficiency of photosynthesis. We discuss the state of the art of the two approaches. Both have been demonstrated to be effective, but we specify seven conditions required before the methods can become operational.

Using meteorological wind data to estimate turbine generation output: a sensitivity analysis

Various studies investigating the future impacts of integrating high levels of renewable energy make use of historical meteorological (met) station data to produce estimates of future generation. Hourly means of 10m horizontal wind are extrapolated to a standard turbine hub height using the wind profile power or log law and used to simulate the hypothetical power output of a turbine at that location; repeating this procedure using many viable locations can produce a picture of future electricity generation. However, the estimate of hub height wind speed is dependent on the choice of the wind shear exponent a or the roughness length z0, and requires a number of simplifying assumptions. This paper investigates the sensitivity of this estimation on generation output using a case study of a met station in West Freugh, Scotland. The results show that the choice of wind shear exponent is a particularly sensitive parameter which can lead to significant variation of estimated hub height wind speed and hence estimated future generation potential of a region.

Testing the sustainability and sensitivity to climatic change of terrace agricultural systems in the Peruvian Andes: a pilot study

The results of an integrated geoarchaeological and palaeoecological pilot study of a prehistoric agricultural terrace and nearby mire basin are presented. They reveal two stages of terrace construction for the cultivation of Zea mays during the Middle Horizon (615–695 AD) and late, Late Intermediate Period (1200–1400 AD). These stages were strongly associated with evidence for vegetation succession, destabilisation and erosion of the surrounding landscape, and changes in mire surface wetness. The reasons for agricultural terrace abandonment and/or reconstruction are uncertain, with only circumstantial evidence for climatically induced agricultural change.

Variation in the autism candidate gene GABRB3 modulates tactile sensitivity in typically developing children

Background: Autism spectrum conditions have a strong genetic component. Atypical sensory sensitivities are one of the core but neglected features of autism spectrum conditions. GABRB3 is a well-characterised candidate gene for autism spectrum conditions. In mice, heterozygous Gabrb3 deletion is associated with increased tactile sensitivity. However, no study has examined if tactile sensitivity is associated with GABRB3 genetic variation in humans. To test this, we conducted two pilot genetic association studies in the general population, analysing two phenotypic measures of tactile sensitivity (a parent-report and a behavioural measure) for association with 43 SNPs in GABRB3. Findings: Across both tactile sensitivity measures, three SNPs (rs11636966, rs8023959 and rs2162241) were nominally associated with both phenotypes, providing a measure of internal validation. Parent-report scores were nominally associated with six SNPs (P <0.05). Behaviourally measured tactile sensitivity was nominally associated with 10 SNPs (three after Bonferroni correction). Conclusions: This is the first human study to show an association between GABRB3 variation and tactile sensitivity. This provides support for the evidence from animal models implicating the role of GABRB3 variation in the atypical sensory sensitivity in autism spectrum conditions. Future research is underway to directly test this association in cases of autism spectrum conditions.

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the ‘Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance’ (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10 000 cm−1 with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.

Spectral analysis of diffusions with jump boundary

In this paper we consider one-dimensional diffusions with constant coefficients in a finite interval with jump boundary and a certain deterministic jump distribution. We use coupling methods in order to identify the spectral gap in the case of a large drift and prove that there is a threshold drift above which the bottom of the spectrum no longer depends on the drift. As a corollary to our result we are able to answer two questions concerning elliptic eigenvalue problems with non-local boundary conditions formulated previously by Iddo Ben-Ari and Ross Pinsky.

On the spectral gap of Brownian motion with jump boundary

In this paper we consider the Brownian motion with jump boundary and present a new proof of a recent result of Li, Leung and Rakesh concerning the exact convergence rate in the one-dimensional case. Our methods are dierent and mainly probabilistic relying on coupling methods adapted to the special situation under investigation. Moreover we answer a question raised by Ben-Ari and Pinsky concerning the dependence of the spectral gap from the jump distribution in a multi-dimensional setting.

Spectral theory of Toeplitz and Hankel operators on the Bergman space A1

The Fredholm properties of Toeplitz operators on the Bergman space A2 have been well-known for continuous symbols since the 1970s. We investigate the case p=1 with continuous symbols under a mild additional condition, namely that of the logarithmic vanishing mean oscillation in the Bergman metric. Most differences are related to boundedness properties of Toeplitz operators acting on Ap that arise when we no longer have 1

Sensitivity and out-of-sample error in continuous time data assimilation

Data assimilation refers to the problem of finding trajectories of a prescribed dynamical model in such a way that the output of the model (usually some function of the model states) follows a given time series of observations. Typically though, these two requirements cannot both be met at the same time–tracking the observations is not possible without the trajectory deviating from the proposed model equations, while adherence to the model requires deviations from the observations. Thus, data assimilation faces a trade-off. In this contribution, the sensitivity of the data assimilation with respect to perturbations in the observations is identified as the parameter which controls the trade-off. A relation between the sensitivity and the out-of-sample error is established, which allows the latter to be calculated under operational conditions. A minimum out-of-sample error is proposed as a criterion to set an appropriate sensitivity and to settle the discussed trade-off. Two approaches to data assimilation are considered, namely variational data assimilation and Newtonian nudging, also known as synchronization. Numerical examples demonstrate the feasibility of the approach.

Sensitivity of an Earth system climate model to idealized radiative forcing

We diagnose forcing and climate feedbacks in benchmark sensitivity experiments with the new Met Office Hadley Centre Earth system climate model HadGEM2-ES. To identify the impact of newly-included biogeophysical and chemical processes, results are compared to a parallel set of experiments performed with these processes switched off, and different couplings with the biogeochemistry. In abrupt carbon dioxide quadrupling experiments we find that the inclusion of these processes does not alter the global climate sensitivity of the model. However, when the change in carbon dioxide is uncoupled from the vegetation, or when the model is forced with a non-carbon dioxide forcing – an increase in solar constant – new feedbacks emerge that make the climate system less sensitive to external perturbations. We identify a strong negative dust-vegetation feedback on climate change that is small in standard carbon dioxide sensitivity experiments due to the physiological/fertilization effects of carbon dioxide on plants in this model.

N-(Aryl)picolinamide complexes of rhodium : synthesis, structure and, spectral and electrochemical properties

Reaction of a series of N-(aryl)picolinamide ligands (HL-R, where II denotes the acidic proton and R (R = OCH3, CH3, H, Cl and NO2) is the para substituent in the aryl fragment) with RhCl3 center dot 3H(2)O in refluxing ethanal in the presence of a base (NEt3) affords two groups of yellow complexes of type [Rh(H-R)(L-R)Cl-2] and [Rh(L-R)(2)(H2O)Cl]. In [Rh(HL-R)(L-R)Cl-2], HL-R is coordinated as neutral N,O-donor and L-R as monoanionic N,N-donor, and the two chlorides are mutually trans. In [Rh(L-R)(2)(H2O)CI] both the amide ligands are coordinated as monoanionic N,N-donor, and the chloro and aquo ligands are mutually cis. Structures of the [Rh(HL-OCH3)(L-CH3)Cl-2] and [Rh(L-Cl)(2)(H2O)CI] complexes have been determined by X-ray crystallography. All the complexes show characteristic H-1 NMR signals and intense LLCT transitions in the ultraviolet region. Cyclic voltammetry on the complexes shows an oxidation of the coordinated amide ligand within 0.78-1.80 V vs SCE and a reductive response within -0.20 to -0.75 V vs SCE. DFT calculations have been done to explain the electronic spectral and electrochemical properties.

Complexes of palladium using di-2-pyridyl ketone as ligand: synthesis, structure and, spectral and catalytic properties

During the reaction of di-2-pyridyl ketone (dpk) with Na(2)[PdCl(4)] in alcoholic media, the C=O fragment of dpk undergoes facile solvolysis and the transformed di-2-pyridyl ketone (dpk(ROH), R = Me or H) binds to palladium as NN-donor. When the reaction is carried out in refluxing methanol, a mono-complex of type [Pd(dpk(MeOH))Cl(2)] is obtained. A similar reaction in ethanol affords a bis-complex of type [Pd(dpk(ROH))(2)]Cl(2). Structure of both the complexes have been determined by X-ray crystallography. In acetonitrile solution the [pd(dpk(MeOH))Cl(2)] and [pd(dpk(ROH))(2)]Cl(2) complexes show intense absorptions in the visible and ultraviolet region, origin of which has been probed through uvr calculations. These two palladium complexes are found to be efficient catalysts for Suzuki cross-coupling reactions.

Ruthenium mediated C–H activation of benzaldehyde thiosemicarbazones: Synthesis, structure and, spectral and electrochemical properties of the resulting complexes

Reaction of five 4R-benzaldehyde thiosemicarbazones (R = OCH3, CH3, H, Cl and NO2) with [ Ru(PPh3)(3)(-CO)(H) Cl] in refluxing methanol in the presence of a base (NEt3) affords complexes of two different types, viz. 1-R and 2-R. In the 1-R complexes the thiosemicarbazone is coordinated to ruthenium as a dianionic tridentate C,N,S-donor via C-H bond activation. Two triphenylphosphines and a carbonyl are also coordinated to ruthenium. The tricoordinated thiosemicarbazone ligand is sharing the same equatorial plane with ruthenium and the carbonyl, and the PPh3 ligands are mutually trans. In the 2-R complexes the thiosemicarbazone ligand is coordinated to ruthenium as a monoanionic bidentate N, S-donor forming a four-membered chelate ring with a bite angle of 63.91(11)degrees. Two triphenylphosphines, a carbonyl and a hydride are also coordinated to ruthenium. The coordinated thiosemicarbazone ligand, carbonyl and hydride constitute one equatorial plane with the metal at the center, where the carbonyl is trans to the coordinated nitrogen of the thiosemicarbazone and the hydride is trans to the sulfur. The two triphenylphosphines are trans. Structures of the 1-CH3 and 2-CH3 complexes have been determined by X-ray crystallography. All the complexes show intense transitions in the visible region, which are assigned, based on DFT calculations, to transitions within orbitals of the thiosemicarbazone ligand. Cyclic voltammetry on the complexes shows two oxidations of the coordinated thiosemicarbazone on the positive side of SCE and a reduction of the same ligand on the negative side.

A method for incorporating climate variability in climate change impact assessments: sensitivity of river flows in the Eden catchment to precipitation scenarios

Interest in the impacts of climate change is ever increasing. This is particularly true of the water sector where understanding potential changes in the occurrence of both floods and droughts is important for strategic planning. Climate variability has been shown to have a significant impact on UK climate and accounting for this in future climate cahgne projections is essential to fully anticipate potential future impacts. In this paper a new resampling methodology is developed which includes the variability of both baseline and future precipitation. The resampling methodology is applied to 13 CMIP3 climate models for the 2080s, resulting in an ensemble of monthly precipitation change factors. The change factors are applied to the Eden catchment in eastern Scotland with analysis undertaken for the sensitivity of future river flows to the changes in precipitation. Climate variability is shown to influence the magnitude and direction of change of both precipitation and in turn river flow, which are not apparent without the use of the resampling methodology. The transformation of precipitation changes to river flow changes display a degree of non-linearity due to the catchment's role in buffering the response. The resampling methodology developed in this paper provides a new technique for creating climate change scenarios which incorporate the important issue of climate variability.