Modélisation du transport des solutés neutres à travers des membranes de nanofiltration

L'exclusion engendrée par la présence de membranes de nanofiltration est due à la superposition de plusieurs mécanismes. Aussi, il est important de pouvoir distinguer ces différents modes de transports afin de les comprendre et de proposer des modèles adéquats. Cette étude s'attachera uniquement à la compréhension du transport de solutés neutres à travers des membranes de ce type. Trois sucres, le glucose, le saccharose et le raffinose, ont été utilisés pour caractériser deux membranes organiques fournies par la société Osmonics. Ce travail montre qu'un modèle simple, basé sur la diffusion, tenant compte des conditions hydrodynamiques du module, est en accord avec les résultats obtenus au laboratoire mais également trouvés dans la littérature. Une bonne adéquation entre le modèle et l'expérience est ainsi obtenue, à la fois sur des modules plans et tubulaires, pour des écoulements laminaires et turbulents.Although nanofiltration appeared at the end of the 1970s under various names, it was only really recognized as a useful separation process in the 1980s. Nanofiltration membranes are porous media with a mean pore diameter around 1 nanometer. These membranes do not obey the traditional solution-diffusion model given for reverse osmosis or the convection-diffusion model used to describe ultrafiltration. Although the technique has benefited from a fast technological development, the transport mechanisms are still misunderstood and for a particular separation the choice of a nanofiltration membrane remains empirical.The main objective of this work was to understand and to model the transport of neutral solutes through nanofiltration membranes. Neutral solutes were chosen to emphasise geometrical exclusions, to avoid any electrical interactions and to identify the preponderant transport mechanisms through these materials. The experiments were carried out with a laboratory filtration apparatus. The membranes were laid out in a parallel plane osmotic cell, which makes tangential filtration possible. The geometry of the filtration cell involved the choice of two organic membranes supplied as flat sheets: a BQ01 and a MX07 membrane. The filtration area was 86 cm2. The pressure varied from 7 to 30 bars. The temperature was maintained at 20°C whereas tangential velocity in the cell was fixed at 0.45 m×s-1 (the Reynolds number was 3350). As the solutions used were slightly concentrated, the pH remained close to neutral pH. Three sugars were chosen as solutes: glucose, saccharose and raffinose. These molecules have two advantages: they are electrically neutral and they have molecular weights close to the membranes' MWCO, as provided by the manufacturer.First, saccharose was studied on the two membranes with two different concentrations. These experiments showed that the separation of neutral solutes by nanofiltration membranes is due only to a sieving effect. In subsequent experiments a single concentration was used to characterize the retentions of both glucose and raffinose. The results of the filtrations carried out on the three sugars validated the molecular weight cut-off specified by the manufacturer: the MWCO of the BQ01 membrane was estimated to be 1000 Da, and that for the MX07 membrane was 200 estimated as 200 Da.Schematically, the solute transport can be divided into three stages: in the feed, at the feed/membrane interface, and within the membrane material. In the feed, one notes an increase in solute concentration if one approaches the membrane from upstream. This phenomenon, which is general to any selective transport, is called concentration polarization and is described by film theory. This theory stipulates the creation of an antagonistic diffusive flow, from the membrane towards the feed, seeking to restore the concentration balance within the feed solution. The modification of the concentration at the feed/membrane interface leads to the definition of two retention coefficients: a measured value, the observed retention (Robs), and a calculated value, the intrinsic retention (Rm). Steric exclusion based on the size difference between the pore and the solute is set up at the interface. Uncharged solutes can be visualised as rigid spheres and the membranes can be regarded as a bundle of cylindrical, parallel, rigid and right capillaries. Since the elements are rigid and the solutes are subjected to the same geometrical constraints at the entry and at the exit of a pore, the partition coefficients are identical at those two ends. Finally, lying between reverse osmosis and ultrafiltration, transport through nanofiltration membranes is often expressed as the sum of convective and diffusive phenomena. However, the experimental results show that the observed retentions are stable or increase when pressure increases. These observations also highlight the fact that the values of infinite retention are always compatible with values close to 1. These observations corroborate the idea that diffusion is the predominant transport mechanism of neutral species through the studied materials (BQ01, MX07). The transport equation of neutral solutes can then be simplified to its diffusive component. The expression of the intrinsic retention is obtained by using Fick's law, the definition of the retention coefficients and the definition of the partition coefficients:Rm= 1-(1 / 1+Jvα)The geometrical and physicochemical characteristics of the solutes and of the membranes merge into the α parameter.The results found with the theoretical relation were confronted with experimental data derived from film theory (in order to take into account concentration polarization). The simple one-parameter model was successful in correlating the results obtained in this work. The model was also tested with data coming from Combe et al. (1997), who studied filtrations of glucose, saccharose and raffinose in a laminar flow system by ceramic nanofiltration membranes laid out in the shape of tubular module. The results obtained show that the simple model also successfully correlates with the performances of these membranes.With the data obtained in our laboratory as well with the data found in literature, this study shows that a simple one-parameter model, based on the diffusional transport of the solutes within the membrane material, predicts the rejection of neutral solutes by nanofiltration membranes. The simple one-parameter model is able to simulate any filtration carried out by these membranes for different circulation conditions, for diverse geometrical shapes and for various materials

Precision Spectroscopy at Heavy Ion Ring Accelerator SIS300

Unique spectroscopic possibilities open up if a laser beam interacts with relativistic lithium-like ions stored in the heavy ion ring accelerator SIS300 at the future Facility for Antiproton and Ion Research FAIR in Darmstadt, Germany. At a relativistic factor gamma = 36 the 2P 1/2 level can be excited from the 2S 1/2 ground state for any element with frequency doubled dye-lasers in collinear geometry. Precise transition energy measurements can be performed if the fluorescence photons, boosted in forward direction into the X-ray region, are energetically analyzed with a single crystal monochromator. The hyperfine structure can be investigated at the 2P 1/2 - 2S 1/2 transition for all elements and at the 2P 3/2 - 2S 1/2 transition for elements with Z < 50. Isotope shifts and nuclear moments can be measured with unprecedented precision, in principle even for only a few stored radioactive species with known nuclear spin. A superior relative line width in the order of 5E-7 may be feasible after laser cooling, and even polarized external beams may be prepared by optical pumping

Highly charged ion X-rays from Electron-Cyclotron Resonance Ion Sources

Radiation from the highly-charged ions contained in the plasma of Electron-Cyclotron Resonance Ion Sources constitutes a very bright source of X-rays. Because the ions have a relatively low kinetic energy ($\approx 1$ eV) transitions can be very narrow, containing only small Doppler broadening. We describe preliminary accurate measurements of two and three-electron ions with Z=16--18. We show how these measurement can test sensitively many-body relativistic calculations or can be used as X-ray standards for precise measurements of X-ray transitions in exotic atoms

High Resolution He-like Argon And Sulfur Spectra From The PSI ECRIT

We present new results on the X-ray spectroscopy of multicharged argon, sulfur and chlorine obtained with the Electron Cyclotron Resonance Ion Trap (ECRIT) in operation at the Paul Scherrer Institut (Villigen, Switzerland). We used a Johann-type Bragg spectrometer with a spherically-bent crystal, with an energy resolution of about 0.4 eV. The ECRIT itself is of a hybrid type, with a superconducting split coil magnet, special iron inserts which provides the mirror field, and a permanent magnetic hexapole. The high frequency was provided by a 6.4 GHz microwave emitter. We obtained high intensity X-ray spectra of multicharged F-like to He-like argon, sulfur and chlorine with one 1s hole. In particular, we observed the 1s2s^{3}S_1 \to 1s^2^{1}S_0 M1 and 1s2p^{3}P_2 \to 1s^2^{1}S_0 M2 transitions in He-like argon, sulfur and chlorine with unprecedented statistics and resolution. The energies of the observed lines are being determined with good accuracy using the He-like M1 line as a reference

Impacts of Climate Change on indirect human exposure to pathogens and chemicals from agriculture

Objective: Climate change is likely to affect the nature of pathogens and chemicals in the environment and their fate and transport. Future risks of pathogens and chemicals could therefore be very different from those of today. In this review, we assess the implications of climate change for changes in human exposures to pathogens and chemicals in agricultural systems in the United Kingdom and discuss the subsequent effects on health impacts. Data sources: In this review, we used expert input and considered literature on climate change ; health effects resulting from exposure to pathogens and chemicals arising from agriculture ; inputs of chemicals and pathogens to agricultural systems ; and human exposure pathways for pathogens and chemicals in agricultural systems. Data synthesis: We established the current evidence base for health effects of chemicals and pathogens in the agricultural environment ; determined the potential implications of climate change on chemical and pathogen inputs in agricultural systems ; and explored the effects of climate change on environmental transport and fate of different contaminant types. We combined these data to assess the implications of climate change in terms of indirect human exposure to pathogens and chemicals in agricultural systems. We then developed recommendations on future research and policy changes to manage any adverse increases in risks. Conclusions: Overall, climate change is likely to increase human exposures to agricultural contaminants. The magnitude of the increases will be highly dependent on the contaminant type. Risks from many pathogens and particulate and particle-associated contaminants could increase significantly. These increases in exposure can, however, be managed for the most part through targeted research and policy changes

Three-dimensional cultured ampullae from rats as a screening tool for vestibulotoxicity: Proof of concept using styrene.

peer reviewedNumerous ototoxic drugs, such as some antibiotics and chemotherapeutics, are both cochleotoxic and vestibulotoxic (causing hearing loss and vestibular disorders). However, the impact of some industrial cochleotoxic compounds on the vestibular receptor, if any, remains unknown. As in vivo studies are long and expensive, there is considerable need for predictive and cost-effective in vitro models to test ototoxicity. Here, we present an organotypic model of cultured ampullae harvested from rat neonates. When cultured in a gelatinous matrix, ampulla explants form an enclosed compartment that progressively fills with a high-potassium (K+) endolymph-like fluid. Morphological analyses confirmed the presence of a number of cell types, sensory epithelium, secretory cells, and canalar cells. Treatments with inhibitors of potassium transporters demonstrated that the potassium homeostasis mechanisms were functional. To assess the potential of this model to reveal the toxic effects of chemicals, explants were exposed for either 2 or 72 h to styrene at a range of concentrations (0.5-1 mM). In the 2-h exposure condition, K+ concentration was significantly reduced, but ATP levels remained stable, and no histological damage was visible. After 72 h exposure, variations in K+ concentration were associated with histological damage and decreased ATP levels. This in vitro 3D neonatal rat ampulla model therefore represents a reliable and rapid means to assess the toxic properties of industrial compounds on this vestibular tissue, and can be used to investigate the specific underlying mechanisms

An in vitro model to assess the peripheral vestibulotoxicity of aromatic solvents.

peer reviewedEpidemiological and experimental studies indicate that a number of aromatic solvents widely used in the industry can affect hearing and balance following chronic exposure. Animal studies demonstrated that long-term exposure to aromatic solvents directly damages the auditory receptor within the inner ear: the cochlea. However, no information is available on their effect on the vestibular receptor, which shares many structural features with the cochlea and is also localized in inner ear. The aim of this study was to use an in vitro approach to assess and compare the vestibular toxicity of different aromatic solvents (toluene, ethylbenzene, styrene and ortho-, meta-, para-xylene), all of which have well known cochleotoxic properties. We used a three-dimensional culture model of rat utricles ("cysts") with preserved functional sensory and secretory epithelia, and containing a potassium-rich (K+) endolymph-like fluid for this study. Variations in K+ concentrations in this model were considered as biomarkers of toxicity of the substances tested. After 72 h exposure, o-xylene, ethylbenzene and styrene decreased the K+ concentration by 78 %, 37 % and 28 %, respectively. O- xylene and styrene both caused histopathological alterations in secretory and sensory epithelial areas after 72 h exposure, whereas no anomalies were observed in ethylbenzene-exposed samples. These in vitro results suggest that some widely used aromatic solvents might have vestibulotoxic properties (o-xylene, styrene and ethylbenzene), whereas others may not (p-xylene, m-xylene, toluene). Our results also indicate that variations in endolymphatic K+ concentration may be a more sensitive marker of vestibular toxicity than histopathological events. Finally, this study suggests that cochleotoxic solvents might not be necessarily vestibulotoxic, and vice versa

Relativistic Calculation of two-Electron one-Photon and Hypersatellite Transition Energies for 12≤Z≤3012\leq Z\leq30 Elements

Energies of two-electron one-photon transitions from initial double K-hole states were computed using the Dirac-Fock model. The transition energies of competing processes, the K$\alpha$ hypersatellites, were also computed. The results are compared to experiment and to other theoretical calculations.Comment: accepted versio

Programmable active memories in real-time tasks: implementing data-driven triggers for LHC experiments

The future Large Hadron Collider (LHC), to be built at CERN, presents among other technological challenges a formidable problem of real-time data analysis. At a primary event rate of 40 MHz, a multi-stage trigger system has to analyze data to decide which is the fraction of events that should be preserved on permanent storage for further analysis. We report on implementations of local algorithms for feature extraction as part of triggering, using the detectors of the proposed ATLAS experiment as a model. The algorithms were implemented for a decision frequency of 100 kHz, on different data-driven programmable devices based on structures of field- programmable gate arrays and memories. The implementations were demonstrated at full speed with emulated input, and were also integrated into a prototype detector running in a test beam at CERN, in June 1994