Technical note: how accurate can stalagmite formation temperatures be determined using vapour bubble radius measurements in fluid inclusions?

Stalagmites are natural archives containing detailed information on continental climate variability of the past. Microthermometric measurements of fluid inclusion homogenisation temperatures allow determination of stalagmite formation temperatures by measuring the radius of stable laser-induced vapour bubbles inside the inclusions. A reliable method for precisely measuring the radius of vapour bubbles is presented. The method is applied to stalagmite samples for which the formation temperature is known. An assessment of the bubble radius measurement accuracy and how this error influences the uncertainty in determining the formation temperature is provided. We demonstrate that the nominal homogenisation temperature of a single inclusion can be determined with an accuracy of ±0.25 °C, if the volume of the inclusion is larger than 105 μm3. With this method, we could measure in a proof-of-principle investigation that the formation temperature of 10–20 yr old inclusions in a stalagmite taken from the Milandre cave is 9.87 ± 0.80 °C, while the mean annual surface temperature, that in the case of the Milandre cave correlates well with the cave temperature, was 9.6 ± 0.15 °C, calculated from actual measurements at that time, showing a very good agreement. Formation temperatures of inclusions formed during the last 450 yr are found in a temperature range between 8.4 and 9.6 °C, which corresponds to the calculated average surface temperature. Paleotemperatures can thus be determined within ±1.0 °C.

Reconstructing paleosalinity from δ18O: coupled model simulations of the Last Glacial Maximum, Last Interglacial and Late Holocene

Reconstructions of salinity are used to diagnose changes in the hydrological cycle and ocean circulation. A widely used method of determining past salinity uses oxygen isotope (δOw) residuals after the extraction of the global ice volume and temperature components. This method relies on a constant relationship between δOw and salinity throughout time. Here we use the isotope-enabled fully coupled General Circulation Model (GCM) HadCM3 to test the application of spatially and time-independent relationships in the reconstruction of past ocean salinity. Simulations of the Late Holocene (LH), Last Glacial Maximum (LGM), and Last Interglacial (LIG) climates are performed and benchmarked against existing compilations of stable oxygen isotopes in carbonates (δOc), which primarily reflect δOw and temperature. We find that HadCM3 produces an accurate representation of the surface ocean δOc distribution for the LH and LGM. Our simulations show considerable variability in spatial and temporal δOw-salinity relationships. Spatial gradients are generally shallower but within ∼50% of the actual simulated LH to LGM and LH to LIG temporal gradients and temporal gradients calculated from multi-decadal variability are generally shallower than both spatial and actual simulated gradients. The largest sources of uncertainty in salinity reconstructions are found to be caused by changes in regional freshwater budgets, ocean circulation, and sea ice regimes. These can cause errors in salinity estimates exceeding 4 psu. Our results suggest that paleosalinity reconstructions in the South Atlantic, Indian and Tropical Pacific Oceans should be most robust, since these regions exhibit relatively constant δOw-salinity relationships across spatial and temporal scales. Largest uncertainties will affect North Atlantic and high latitude paleosalinity reconstructions. Finally, the results show that it is difficult to generate reliable salinity estimates for regions of dynamic oceanography, such as the North Atlantic, without additional constraints.

Seasonality of westerly moisture transport in the East Asian summer monsoon and its implications for interpreting precipitation δ18O

East Asian summer monsoon (EASM) rainfall impacts the world's most populous regions. Accurate EASM rainfall prediction necessitates robust paleoclimate reconstructions from proxy data and quantitative linkage to modern climatic conditions. Many precisely dated oxygen isotope records from Chinese stalagmites have been interpreted as directly reflecting past EASM rainfall amount variability, but recent research suggests that such records instead integrate multiple hydroclimatic processes. Using a Lagrangian precipitation moisture source diagnostic, we demonstrate that EASM rainfall is primarily derived from the Indian Ocean. Conversely, Pacific Ocean moisture export peaks during winter, and the moisture uptake area does not differ significantly between summer and winter and is thus a minor contributor to monsoonal precipitation. Our results are substantiated by an accurate reproduction of summer and winter spatial rainfall distributions across China. We also correlate modern EASM rainfall oxygen isotope ratios with instrumental rainfall amount and our moisture source data. This analysis reveals that the strength of the source effect is geographically variable, and differences in atmospheric moisture transport may significantly impact the isotopic signature of EASM rainfall at the Hulu, Dongge, and Wanxiang Cave sites. These results improve our ability to isolate the rainfall amount signal in paleomonsoon reconstructions and indicate that precipitation across central and eastern China will directly respond to variability in Indian Ocean moisture supply.

How accurate are volcanic ash simulations of the 2010 Eyjafjallajökull eruption?

In the event of a volcanic eruption the decision to close airspace is based on forecast ash maps, produced using volcanic ash transport and dispersion models. In this paper we quantitatively evaluate the spatial skill of volcanic ash simulations using satellite retrievals of ash from the Eyja allajökull eruption during the period from 7 to 16 May 2010. We find that at the start of this period, 7–10 May, the model (FLEXible PARTicle) has excellent skill and can predict the spatial distribution of the satellite-retrieved ash to within 0.5∘ × 0.5∘ latitude/longitude. However, on 10 May there is a decrease in the spatial accuracy of the model to 2.5∘× 2.5∘ latitude/longitude, and between 11 and 12 May the simulated ash location errors grow rapidly. On 11 May ash is located close to a bifurcation point in the atmosphere, resulting in a rapid divergence in the modeled and satellite ash locations. In general, the model skill reduces as the residence time of ash increases. However, the error growth is not always steady. Rapid increases in error growth are linked to key points in the ash trajectories. Ensemble modeling using perturbed meteorological data would help to represent this uncertainty, and assimilation of satellite ash data would help to reduce uncertainty in volcanic ash forecasts.

Sparse block-Jacobi matrices with arbitrarily accurate Hausdorff dimension

We show that the Hausdorff dimension of the spectral measure of a class of deterministic, i.e. nonrandom, block-Jacobi matrices may be determined with any degree of precision, improving a result of Zlatos [Andrej Zlatos,. Sparse potentials with fractional Hausdorff dimension, J. Funct. Anal. 207 (2004) 216-252]. (C) 2010 Elsevier Inc. All rights reserved.

Accurate and Precise Zinc Isotope Ratio Measurements in Urban Aerosols

We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of delta(66)Zn determinations in aerosols is around 0.05% per atomic mass unit. The method was tested on aerosols collected in Sin Paulo City, Brazil. The measurements reveal significant variations in delta(66)Zn(Imperial) ranging between -0.96 and -0.37% in coarse and between -1.04 and 0.02% in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source. We present further delta(66)Zn(Imperial) data for the standard reference material NIST SRM 2783 (delta 66Z(Imperial) = 0.26 +/- 0.10%).

A Robust, Fully Adaptive Hybrid Level-Set/Front-Tracking Method for Two-Phase Flows with an Accurate Surface Tension Computation

We present a variable time step, fully adaptive in space, hybrid method for the accurate simulation of incompressible two-phase flows in the presence of surface tension in two dimensions. The method is based on the hybrid level set/front-tracking approach proposed in [H. D. Ceniceros and A. M. Roma, J. Comput. Phys., 205, 391400, 2005]. Geometric, interfacial quantities are computed from front-tracking via the immersed-boundary setting while the signed distance (level set) function, which is evaluated fast and to machine precision, is used as a fluid indicator. The surface tension force is obtained by employing the mixed Eulerian/Lagrangian representation introduced in [S. Shin, S. I. Abdel-Khalik, V. Daru and D. Juric, J. Comput. Phys., 203, 493-516, 2005] whose success for greatly reducing parasitic currents has been demonstrated. The use of our accurate fluid indicator together with effective Lagrangian marker control enhance this parasitic current reduction by several orders of magnitude. To resolve accurately and efficiently sharp gradients and salient flow features we employ dynamic, adaptive mesh refinements. This spatial adaption is used in concert with a dynamic control of the distribution of the Lagrangian nodes along the fluid interface and a variable time step, linearly implicit time integration scheme. We present numerical examples designed to test the capabilities and performance of the proposed approach as well as three applications: the long-time evolution of a fluid interface undergoing Rayleigh-Taylor instability, an example of bubble ascending dynamics, and a drop impacting on a free interface whose dynamics we compare with both existing numerical and experimental data.

Accurate velocity reconstruction for Discontinuous Galerkin approximations of two-phase porous media flows

We consider Discontinuous Galerkin approximations of two-phase, immiscible porous media flows in the global pressure/fractional flow formulation with capillary pressure. A sequential approach is used with a backward Euler step for the saturation equation, equal-order interpolation for the pressure and the saturation, and without any limiters. An accurate total velocity field is recovered from the global pressure equation to be used in the saturation equation. Numerical experiments show the advantages of the proposed reconstruction. To cite this article: A. Ern et al., C R. Acad. Sci. Paris, Ser. 1347 (2009). (C) 2009 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

The low-lying electronic states of BeP: a reliable and accurate quantum mechanical prediction

A very high level of theoretical treatment (complete active space self-consistent field CASSCF/MRCI/aug-cc-pV5Z) was used to characterize the spectroscopic properties of a manifold of quartet and doublet states of the species BeP, as yet experimentally unknown. Potential energy curves for 11 electronic states were obtained, as well as the associated vibrational energy levels, and a whole set of spectroscopic constants. Dipole moment functions and vibrationally averaged dipole moments were also evaluated. Similarities and differences between BeN and BeP were analysed along with the isovalent SiB species. The molecule BeP has a X (4)Sigma(-) ground state, with an equilibrium bond distance of 2.073 angstrom, and a harmonic frequency of 516.2 cm(-1); it is followed closely by the states (2)Pi (R(e) = 2.081 angstrom, omega(e) = 639.6 cm(-1)) and (2)Sigma(-) (R(e) = 2.074 angstrom, omega(e) = 536.5 cm(-1)), at 502 and 1976 cm(-1), respectively. The other quartets investigated, A (4)Pi (R(e) = 1.991 angstrom, omega(e) = 555.3 cm(-1)) and B (4)Sigma(-) (R(e) = 2.758 angstrom, omega(e) = 292.2 cm(-1)) lie at 13 291 and 24 394 cm(-1), respectively. The remaining doublets ((2)Delta, (2)Sigma(+)(2) and (2)Pi(3)) all fall below 28 000 cm(-1). Avoided crossings between the (2)Sigma(+) states and between the (2)Pi states add an extra complexity to this manifold of states.

Spectrophotometric determination of zinc in pharmaceutical and biological samples with di-2-pyridyl ketone benzoylhydrazone: A simple, fast, accurate and sensitive method

A simple, fast, accurate, and sensitive spectrophotometric method was developed to determine zinc(II). This method is based on the reaction of Zn(II) with di-2-pyridyl ketone benzoylhydrazone (DPKBH), at pH=5.5 and 50% (v/v) ethanol. Beers law was obeyed in the range 0.020-1.82 mu g mL(-1) with a molar apsorptivity of 3.64 x 10(4) L mol(-1) cm(-1), and a detection limit (3) of 2.29 mu g L-1. The action of some interfering ions was verified and the developed method applied to pharmaceutical and biological samples. The results were then compared with those obtained by using a flame atomic absorption technique.

Expedient, accurate methods for the determination of the degree of substitution of cellulose carboxylic esters: Application of UV-vis spectroscopy (dye solvatochromism) and FTIR

Two techniques, namely UV-vis- and FTIR spectroscopy, have been employed in order to calculate the degree of substitution (DS) of cellulose carboxylic esters, including acetates, CAs, butyrates, CBs, and hexanoates, CHs. Regarding UV-vis spectroscopy, we have employed a novel approach, based on measuring the dependence of lambda(max) of the intra-molecular charge-transfer bands of polarity probes adsorbed on DS of the ester films (solvatochromism). Additionally, we have revisited the use of FTIR for DS determination. Several methods have been used in order to plot Beer`s law graph, namely: Absorption of KBr pellets, pre-coated with CA: reflectance (DRIFTS) of CAs-KBr solid-solid mixtures with, or without the use of 1.4-dicyanobenzene as an internal reference; reflectance of KBr powder pre-coated with CA. The methods indicated are simple, fast, and accurate, requiring much less ester than the titration method. The probe method is independent of the experimental variables examined. (c) 2010 Published by Elsevier Ltd.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Implementation and role of device management Solutions to the end users

This research is based on consumer complaints with respect to recently purchased consumer electronics. This research document will investigate the instances of development and device management as a tool used to aid consumer and manage consumer’s mobile products in order to resolve issues in or before the consumers is aware one exists. The problem at the present time is that mobile devices are becoming very advanced pieces of technology, and not all manufacturers and network providers have kept up the support element of End users. As such, the subject of the research is to investigate how device management could possibly be used as a method to promote research and development of mobile devices, and provide a better experience for the consumer. The wireless world is becoming increasingly complex as revenue opportunities are driven by new and innovative data services. We can no longer expect the customer to have the knowledge or ability to configure their own device. Device Management platforms can address the challenges of device configuration and support through new enabling technologies. Leveraging these technologies will allow a network operator to reduce the cost of subscriber ownership, drive increased ARPU (Average Revenue per User) by removing barriers to adoption, reduce churn by improving the customer experience and increase customer loyalty. DM technologies provide a flexible and powerful management method but are managing the same device features that have historically been configured manually through call centers or by the end user making changes directly on the device. For this reason DM technologies must be treated as part of a wider support solution. The traditional requirement for discovery, fault finding, troubleshooting and diagnosis are still as relevant with DM as they are in the current human support environment yet the current generation of solutions do little to address this problem. In the deployment of an effective Device Management solution the network operator must consider the integration of the DM platform, interfacing with many areas of the business, supported by knowledge of the relationship between devices, applications, solutions and services maintained on an ongoing basis. Complementing the DM solution with published device information, setup guides, training material and web based tools will ensure the quality of the customer experience, ensuring that problems are completely resolved, driving data usage by focusing customer education on the use of the wireless service In this way device management becomes a tool used both internally within the network or device vendor and by the customer themselves, with each user empowered to effectively manage the device without any prior knowledge or experience, confident that changes they apply will be relevant, accurate, stable and compatible. The value offered by an effective DM solution with an expert knowledge service will become a significant differentiator for the network operator in an ever competitive wireless market. This research document is intended to highlight some of the issues the industry faces as device management technologies become more prevalent, and offers some potential solutions to simplify the increasingly complex task of managing devices on the network, where device management can be used as a tool to aid customer relations and manage customer’s mobile products in order to resolve issues before the user is aware one exists. The research is broken down into the following, Customer Relationship Management, Device management, the role of knowledge with the DM, Companies that have successfully implemented device management, and the future of device management and CRM. And it also consists of questionnaires aimed at technical support agents and mobile device users. Interview was carried out with CRM managers within support centre to further the evidence gathered. To conclude, the document is to consider the advantages and disadvantages of device management and attempt to determine the influence it will have over customer support centre, and what methods could be used to implement it.

Children's status and children's rights, historically and cross-culturally

In this thesis, my goal is to construct a vision of an ideal setting for children. By examining different ways of thinking about children and childhood, and by considering different approaches which have worked or do work practically, I will seek to envision something better for children. Trying to reach a better context for children will also include an inherent criticism of current conditions. Based on these criticisms, I will identify the elements that I believe can contribute to an ideal setting in which children can not only lead safe, healthy and happy lives, but also develop their own unique potential. The discipline of the history of childhood as well as cross-cultural studies show the relativistic nature of childhood. The concept of childhood, expectations of children, and societal roles for children have changed drastically over time and differ across cultures today. Children's advocates and the children's rights movement both reflect and promote changes in the context of childhood. As attitudes about childhood change, efforts arise to bring reality into line with the new ideals and images. Efforts toward improving children's rights also spread new ideas about children through the society.