Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

New-on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

Coding behavioural data for cladistic analysis: using dynamic homology without parsimony

Many of the controversies around the concept of homology rest on the subjectivity inherent to primary homology propositions. Dynamic homology partially solves this problem, but there has been up to now scant application of it outside of the molecular domain. This is probably because morphological and behavioural characters are rich in properties, connections and qualities, so that there is less space for conflicting character delimitations. Here we present a new method for the direct optimization of behavioural data, a method that relies on the richness of this database to delimit the characters, and on dynamic procedures to establish character state identity. We use between-species congruence in the data matrix and topological stability to choose the best cladogram. We test the methodology using sequences of predatory behaviour in a group of spiders that evolved the highly modified predatory technique of spitting glue onto prey. The cladogram recovered is fully compatible with previous analyses in the literature, and thus the method seems consistent. Besides the advantage of enhanced objectivity in character proposition, the new procedure allows the use of complex, context-dependent behavioural characters in an evolutionary framework, an important step towards the practical integration of the evolutionary and ecological perspectives on diversity. (C) The Willi Hennig Society 2010.

Dynamic Changes in the Mental Rotation Network Revealed by Pattern Recognition Analysis of fMRI Data

We investigated the temporal dynamics and changes in connectivity in the mental rotation network through the application of spatio-temporal support vector machines (SVMs). The spatio-temporal SVM [Mourao-Miranda, J., Friston, K. J., et al. (2007). Dynamic discrimination analysis: A spatial-temporal SVM. Neuroimage, 36, 88-99] is a pattern recognition approach that is suitable for investigating dynamic changes in the brain network during a complex mental task. It does not require a model describing each component of the task and the precise shape of the BOLD impulse response. By defining a time window including a cognitive event, one can use spatio-temporal fMRI observations from two cognitive states to train the SVM. During the training, the SVM finds the discriminating pattern between the two states and produces a discriminating weight vector encompassing both voxels and time (i.e., spatio-temporal maps). We showed that by applying spatio-temporal SVM to an event-related mental rotation experiment, it is possible to discriminate between different degrees of angular disparity (0 degrees vs. 20 degrees, 0 degrees vs. 60 degrees, and 0 degrees vs. 100 degrees), and the discrimination accuracy is correlated with the difference in angular disparity between the conditions. For the comparison with highest accuracy (08 vs. 1008), we evaluated how the most discriminating areas (visual regions, parietal regions, supplementary, and premotor areas) change their behavior over time. The frontal premotor regions became highly discriminating earlier than the superior parietal cortex. There seems to be a parcellation of the parietal regions with an earlier discrimination of the inferior parietal lobe in the mental rotation in relation to the superior parietal. The SVM also identified a network of regions that had a decrease in BOLD responses during the 100 degrees condition in relation to the 0 degrees condition (posterior cingulate, frontal, and superior temporal gyrus). This network was also highly discriminating between the two conditions. In addition, we investigated changes in functional connectivity between the most discriminating areas identified by the spatio-temporal SVM. We observed an increase in functional connectivity between almost all areas activated during the 100 degrees condition (bilateral inferior and superior parietal lobe, bilateral premotor area, and SMA) but not between the areas that showed a decrease in BOLD response during the 100 degrees condition.

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009

Speculative bubbles and contagion: analysis of volatility’s clusters during the DotCom bubble based on the dynamic conditional correlation model

Revendo a definição e determinação de bolhas especulativas no contexto de contágio, este estudo analisa a bolha do DotCom nos mercados acionistas americanos e europeus usando o modelo de correlação condicional dinâmica (DCC) proposto por Engle e Sheppard (2001) como uma explicação econométrica e, por outro lado, as finanças comportamentais como uma explicação psicológica. Contágio é definido, neste contexto, como a quebra estatística nos DCC’s estimados, medidos através das alterações das suas médias e medianas. Surpreendentemente, o contágio é menor durante bolhas de preços, sendo que o resultado principal indica a presença de contágio entre os diferentes índices dos dois continentes e demonstra a presença de alterações estruturais durante a crise financeira.

Speculative bubbles and contagion: analysis of volatility's clusters during the DotCom bubble based on the dynamic conditional correlation model

Reviewing the de nition and measurement of speculative bubbles in context of contagion, this paper analyses the DotCom bubble in American and European equity markets using the dynamic conditional correlation (DCC) model proposed by (Engle and Sheppard 2001) as on one hand as an econometrics explanation and on the other hand the behavioral nance as an psychological explanation. Contagion is de ned in this context as the statistical break in the computed DCCs as measured by the shifts in their means and medians. Even it is astonishing, that the contagion is lower during price bubbles, the main nding indicates the presence of contagion in the di¤erent indices among those two continents and proves the presence of structural changes during nancial crisis

Physical-chemical analysis of the cerebrospinal fluid of healthy dogs submitted to different storage periods and temperatures

Disfunções envolvendo o sistema nervoso são de grande importância na Medicina Veterinária, pois tratam-se de enfermidades de elevada incidência e com poucos subsídios auxiliares no seu diagnóstico, prognóstico e na avaliação de terapias empregadas. Ainda hoje, o diagnóstico baseia-se, em grande parte, no histórico e no exame clínico neurológico. Dessa forma, a análise dos constituintes do fluido cefalorraquidiano torna-se uma das poucas alternativas de acesso clínico ao sistema nervoso central (SNC). Mesmo com a grande utilidade do exame físico-químico e citoscópico do liquor na neurologia veterinária, poucos são os estudos sobre a estabilidade dos seus constituintes sob estocagem. Dessa forma, o presente trabalho teve como finalidade verificar a influência da temperatura e do tempo de conservação nas características físico-químicas do liquor de cães hígidos. Para tanto, foram coletadas amostras de LCR, através da punção da cisterna cerebelo-medular de cães clinicamente sadios, as quais foram submetidas à análise da densidade específica, do pH, da glicorraquia, das proteínas totais e das atividades das enzimas creatina quinase (CK) e aspartato aminotransferase (AST), após conservá-las em diferentes temperaturas (25°C, 4°C e -4°C) e por diferentes períodos de tempo (logo após a colheita, 24 horas, 48 horas, uma semana e um mês). Dentre os resultados obtidos, foi possível verificar, principalmente, que houve estabilidade dos parâmetros estudados por até um mês de estocagem nas amostras mantidas sob a temperaturas de congelamento de -4°C.

Supercritical fluid extraction for pesticide multiresidue analysis in honey: determination by gas chromatography with electron-capture and mass spectrometry detection

An analytical procedure using supercritical fluid extraction (SFE) and capillary gas chromatography with electron-capture detection was developed to determine simultaneously residues of different pesticides (organochlorine, organophosphorus, organonitrogen and pyrethroid) in honey samples. Fortification experiments were conducted to test conventional extraction (liquid-liquid) and optimize the extraction procedure in SFE by varying the CO2-modifier, temperature, extraction time and pressure. Best efficiency was achieved at 400 bar using acetonitrile as modifier at 90 degreesC. For the clean-up step, Florisil cartridges were used for both methods LLE and SFE. Recoveries for majority of pesticides from fortified samples of honey at fortification level of 0.01-0.10 mg/kg ranged 75-94% from both methods. Limits of detection found were less than 0.01 mg/kg for ECD and confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in selected-ion monitoring mode. The multiresidue methods in real honey samples were applied and the results of developed methods were compared. (C) 2004 Elsevier B.V. All rights reserved.

Multiresidue analysis of pesticides in soil by supercritical fluid extraction/gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry

The applicability of supercritical fluid extraction (SFE) in pesticide multiresidue analysis (organohalogen, organonitrogen, organophosphorus, and pyrethroid) in soil samples was investigated. Fortification experiments were conducted to test the conventional extraction (solid-liquid) and to optimize the extraction procedure in SFE by varying the CO2 Modifier, temperature, extraction time, and pressure. The best efficiency was achieved at 400 bar using methanol as modifier at 60 degreesC. For the SFE method, C-18 cartridges were used for the cleanup. The analytical screening was performed by gas chromatography equipped with electron-capture detection (ECD). Recoveries for the majority of pesticides from spiked samples of soil at different residence times were 1, 20, and 40 days at the fortification level of 0.04-0.10 mg/kg ranging from 70 to 97% for both methods. The detection limits found were <0.01 mg/kg for ECD, and the confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in a selected-ion monitoring mode. Multiresidue methods were applied in real soil samples, and the results of the methods developed were compared.

Numerical analysis of refrigerant flow along non-adiabatic capillary tubes using a two-fluid model

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Highly Sensitive Neurotransmitters Analysis at Platinum-Ultramicroelectrodes Arrays

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)