Pore-water squeezing from indurated shales

High-pressure mechanical squeezing was applied to sample pore waters from a sequence of highly indurated and overconsolidated sedimentary rocks in a drillcore from a deep borehole in NE Switzerland. The rocks are generally rich in clay minerals (28–71 wt.%), with low water contents of 3.5–5.6 wt.%, resulting in extremely low hydraulic conductivities of 10− 14–10− 13 m/s. First pore-water samples could generally be taken at 200 MPa, and further aliquots were obtained at 300, 400 and 500 MPa. Chemical and isotopic compositions of squeezed waters evolve with increasing pressure. Decreasing concentrations of Cl−, Br−, Na+ and K+ are explained by ion filtration due to the collapse of the pore space during squeezing. Increasing concentrations of Ca2 + and Mg2 + are considered to be a consequence of pressure-dependent solubilities of carbonate minerals in combination with sorption/desorption reactions. The pressure dependence was studied by model calculations considering equilibrium with carbonate minerals and the exchanger population on clay surfaces, and the trends observed in the experiments could be confirmed. The compositions of the squeezed waters were compared with results of independent methods, such as aqueous extraction and in-situ sampling of ground and pore waters. On this basis, it is concluded that the chemical and isotopic composition of pore water squeezed at the lowest pressure of 200 MPa closely represents that of the in-situ pore water. The feasibility of sampling pore waters with water contents down to 3.5 wt.% and possibly less opens new perspectives for studies targeted at palaeo-hydrogeological investigations using pore-water compositions in aquitards as geochemical archives.

The mobility of Nb in rutile-saturated NaCl- and NaF-bearing aqueous fluids from 1-6.5 GPa and 300-800 °C

Rutile (TiO2) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 degrees C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300-500 degrees C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at similar to 1 GPa and 700-800 degrees C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 mu g/g as temperature increases from 300 to 500 degrees C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 mu g/g at 300 to 500 degrees C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. The Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 mu g/g as temperature increases from 300 to 500 degrees C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 degrees C at >= 2 GPa, but there is no observed dependence on pressure. Together, the data demonstrate that the hydrothermal mobility of Nb is strongly controlled by the composition of the fluid, consistent with published data for Ti. At all experimental conditions, however, the concentration of Nb in the fluid is always lower than coexisting rutile, consistent with a role for rutile in moderating the Nb budget of arc rocks.

Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−¹, compared to chemisorption which ranges from 100 to 1000 kJ mol−¹. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO₂, CH₄, and H₂O. The CO₂ results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO₂ and H₂O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO₂ amount adsorbed (5.8 × 1019 CO₂ molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH₄ and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO₂, ranging from 0.0014 to 0.0184 ppm °C−¹ for steel cylinders and −0.0002 to −0.0003 ppm °C−¹ for aluminium cylinders. The reversed temperature dependence for aluminium cylinders points to significantly lower desorption energies than for steel cylinders and due to the small values, they might at least partly be influenced by temperature, permeation from/to sealing materials, and gas-consumption-induced pressure changes. Temperature coefficients for CH₄, CO, and H₂O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high-precision calibration purposes such as requested in trace gas applications.

Competition between disorder and exchange splitting in superconducting ZrZn2

We propose a simple picture for the occurrence of superconductivity and the pressure dependence of the superconducting critical temperature, T-SC, in ZrZn2. According to our hypothesis the pairing potential is independent of pressure, but the exchange splitting, E-xc leads to a pressure dependence in the (spin dependent) density of states at the Fermi level, D-sigma (epsilon(F)). Assuming p-wave pairing T-SC is dependent on D-sigma (epsilonF) which ensures that, in the absence of non-magnetic impurities, T-SC decreases as pressure is applied until it reaches a minimum in the paramagnetic state. Disorder reduces this minimum to zero, this gives the illusion that the superconductivity disappears at the same pressure as ferromagnetism does.

Estudos de renaturação de proteínas agregadas utilizando altas pressões hidrostáticas

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

Pressure and time dependence of the cardiopulmonary reflex response in patients with hypertensive cardiomyopathy

The first minutes of the time course of cardiopulmonary reflex control evoked by lower body negative pressure (LBNP) in patients with hypertensive cardiomyopathy have not been investigated in detail. We studied 15 hypertensive patients with left ventricular dysfunction (LVD) and 15 matched normal controls to observe the time course response of the forearm vascular resistance (FVR) during 3 min of LBNP at -10, -15, and -40 mmHg in unloading the cardiopulmonary receptors. Analysis of the average of 3-min intervals of FVR showed a blunted response of the LVD patients at -10 mmHg (P = 0.03), but a similar response in both groups at -15 and -40 mmHg. However, using a minute-to-minute analysis of the FVR at -15 and -40 mmHg, we observed a similar response in both groups at the 1st min, but a marked decrease of FVR in the LVD group at the 3rd min of LBNP at -15 mmHg (P = 0.017), and -40 mmHg (P = 0.004). Plasma norepinephrine levels were analyzed as another neurohumoral measurement of cardiopulmonary receptor response to LBNP, and showed a blunted response in the LVD group at -10 (P = 0.013), -15 (P = 0.032) and -40 mmHg (P = 0.004). We concluded that the cardiopulmonary reflex response in patients with hypertensive cardiomyopathy is blunted at lower levels of LBNP. However, at higher levels, the cardiopulmonary reflex has a normal initial response that decreases progressively with time. As a consequence of the time-dependent response, the cardiopulmonary reflex response should be measured over small intervals of time in clinical studies.

Estimation of lower flammability limits of C-H compounds in air at atmospheric pressure, evaluation of temperature dependence and diluent effect

Estimation of the lower flammability limits of C-H compounds at 25 degrees C and 1 atm; at moderate temperatures and in presence of diluent was the objective of this study. A set of 120 degrees C H compounds was divided into a correlation set and a prediction set of 60 compounds each. The absolute average relative error for the total set was 7.89%; for the correlation set, it was 6.09%; and for the prediction set it was 9.68%. However, it was shown that by considering different sources of experimental data the values were reduced to 6.5% for the prediction set and to 6.29% for the total set. The method showed consistency with Le Chatelier's law for binary mixtures of C H compounds. When tested for a temperature range from 5 degrees C to 100 degrees C , the absolute average relative errors were 2.41% for methane; 4.78% for propane; 0.29% for iso-butane and 3.86% for propylene. When nitrogen was added, the absolute average relative errors were 2.48% for methane; 5.13% for propane; 0.11% for iso-butane and 0.15% for propylene. When carbon dioxide was added, the absolute relative errors were 1.80% for methane; 5.38% for propane; 0.86% for iso-butane and 1.06% for propylene. (C) 2014 Elsevier B.V. All rights reserved.

Fragility and glassy dynamics of 2Ca(NO(3))(2)center dot 3KNO(3) under pressure: Molecular dynamics simulations

Molecular dynamics simulations of the glass-forming liquid 2Ca(NO(3))(2)center dot 3KNO(3) (CKN) were performed from high temperature liquid states down to low temperature glassy states at six different pressures from 10(-4) to 5.0 GPa. The temperature dependence of the structural relaxation time indicates that the fragility of liquid CKN changes with pressure. In line with recent proposal [Scopigno , Science 302, 849 (2003)], the change on liquid fragility is followed by a proportional change of the nonergodicity factor of the corresponding glass at low temperature. (c) 2008 American Institute of Physics.

Auditor independence and fee dependence

This study investigates whether fee dependence within the audit firms' offices jeopardises auditor independence. Fee dependence is examined at both the national audit firm level as well as the local office level and in a setting where public disclosure of fees is mandatory. We focus our tests on audit fee dependence and at the same time we control for the effects of non-audit service fee dependence post the 1989 mergers. We operationalise the exercise of independent judgement in auditing by the propensity to issue qualified audit opinions. If fee dependence affects auditors' independent judgement, then auditors are less likely to qualify the accounts. The study's results show that the level of auditor fee dependence does not affect auditor propensity to issue unqualified audit opinions. The findings remain robust to a number of sensitivity tests including the analyses controlling for the effects of non-audit service fee dependence and other settings in which there is heightened pressure on auditors to confront the effects of fee dependence on exercising independent audit judgement. (C) 2002 Elsevier Science B.V. All rights reserved.

Pulse wave analysis of aortic pressure: diastole should also be considered.

BACKGROUND: : The systolic augmentation index (sAix), calculated from the central aortic pulse wave (reconstructed from the noninvasive recording of the radial pulse with applanation tonometry), is widely used as a simple index of central arterial stiffness, but has the disadvantage of also being influenced by the timing of the reflected with respect to the forward pressure wave, as shown by its inverse dependence on heart rate (HR). During diastole, the central aortic pulse also contains reflected waves, but their relationship to arterial stiffness and HR has not been studied. METHODS: : In 48 men and 45 women, all healthy, with ages ranging from 19 to 70 years, we measured pulse wave velocity (PWV, patients supine), a standard evaluator of arterial stiffness, and carried out radial applanation tonometry (patients sitting and supine). The impact of reflected waves on the diastolic part of the aortic pressure waveform was quantified in the form of a diastolic augmentation index (dAix). RESULTS: : Across ages, sexes, and body position, there was an inverse relationship between the sAix and the dAix. When PWV and HR were added as covariates to a prediction model including age, sex and body position as main factors, the sAix was directly related to PWV (P < 0.0001) and inversely to HR (P < 0.0001). With the same analysis, the dAix was inversely related to PWV (P < 0.0001) and independent of HR (P = 0.52). CONCLUSION: : The dAix has the same degree of linkage to arterial stiffness as the more conventional sAix, while being immune to the confounding effect of HR. The quantification of diastolic aortic pressure augmentation by reflected waves could be a useful adjunct to pulse wave analysis.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P)=I0exp(-P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature