Produit de solubilité de la calcite et constantes de dissociation de CaHCO3+ et CaCO30 entre 5 et 75 °C

Les valeurs du produit de solubilité de la calcite et des constantes de dissociation de CaHCO3+ et CaCO30, notées K3 et K4, ont été déterminées à différentes températures comprises entre 5 et 75 °C (la calcite est instable aux températures plus élevées) à partir des mesures [(Ca2+)T, pH] de solubilité de ce sel dans l'eau carboniquement pure. Les résultats obtenus ont permis d'établir les relations empiriques suivantes :pKs= 7,8156 + 0,03111 T + (1 502/T) - 5,518 log TpK3= 6,2447 + 0,00437 T + (864,479/T) - 0,363 log TpK4= 2,89636 + 0,00707 T + (102,87/T) - 0,44176 log Texpressions dans lesquelles T désigne la température absolue (K) et log le logarithme décimal.Des variations de pKS avec la température nous avons déduit, à 25 °C, les grandeurs thermodynamiques relatives à la dissolution de la calcite :∆H0 = -2510 cal. mol-1, ∆S0 = -47,2 cal. mol-1. K-1et ∆C∘p = -73,9 cal. mol-1. K-1The values of the solubility product of calcite and dissociation constants of CaHCO3+ and CaCO30, K3 and K4 respectively, were determined at several temperatures between 5 and 75 °C (calcite becomes unstable at higher temperatures) from measurements [(Ca2+)T, pH] of calcite solubility using carbonically pure water. The results obtained lead to the following empirical expressions for the dependence of equilibrium constants on the temperature :pKs= 7,8156 + 0,03111 T + (1 502/T) - 5,518 log TpK3= 6,2447 + 0,00437 T + (864,479/T) - 0,363 log TpK4= 2,89636 + 0,00707 T + (102,87/T) - 0,44176 log Twhere log T is the common logarithm of the absolute temperature T(K).Using this expression of pKS, the calculated thermodynamic properties of the calcite dissolution reaction at 25 °C are :∆H0 = -2510 cal. mol-1, ∆S0 = -47,2 cal. mol-1. K-1et ∆C∘p = -73,9 cal. mol-1. K-

Élimination des cations métalliques divalents : complexation par l'alginate de sodium et ultrafiltration

Depuis quelques années la pollution par les métaux lourds et devenue un problème important pour la protection de l'environnement et de nombreuses méthodes ont été développées pour éliminer les métaux toxiques présents dans l'eau.Parmi les différents procédés utilisés, la complexation-ultrafiltration est bien connue et de nombreuses études sur ce sujet sont décrites dans la littérature. Cependant, le choix de nouveaux macroligands hydrosolubles demeure important pour développer cette technologie.L'un des objectifs de ce travail était de montrer que dans ce procédé un biopolymère peut remplacer un macroligand de synthèse. Les expériences ont été menées avec de l'alginate de sodium, polysaccharide extrait des algues brunes, et porteur de groupements carboxyliques et hydroxydes capables de complexer les cations.Notre étude se divise en trois parties. Après avoir décrit, dans la première, le matériau et les méthodes utilisées, nous étudions dans la seconde les conditions de l'ultrafiltration (seuil de coupure, pression appliquée, pH, concentration ), avant de discuter dans la troisième les résultats obtenus dans le traitement de solutions contenant Cd2+, Cu2+, Mn2+ and Pb2+.For some years past, pollution by heavy metals has become one of the main problems for environmental protection. A number of methods have been developed to remove toxic metals from water. Among the various processes used, complexation-ultrafiltration is well known and numerous studies on this subject are described in the literature. However, the choice of new water-soluble macroligands remains important for developing this technology.One aim of the present work was to prove that biopolymers can replace synthetic macroligands in the process. The experiments have been conducted with sodium alginate, a polysaccharide extracted from brown seaweeds and containing carboxylic and hydroxyl groups able to complex heavy cations. Filtration experiments were performed with a frontal system, equipped with a polysulfone membrane with a 20000 Daltons cut-off . The solutions studied were prepared by diluting in demineralized water either sodium alginate or "Titrisol Merck" for cations. Before filtration the two solutions were mixed and stirred for 20 min. The pH of the feed solutions was adjusted with HCl (or HNO3 for Pb) or NaOH and determined accurately using a calibrated probe.The molecular weight of sodium alginate was determined by liquid chromatography and the viscosity was measured with either a viscosimeter for low values or a capillary method for concentrated solutions. Cation concentrations were measured by atomic absorption spectrophotometryBoth permeate and retentate macroligands concentrations were estimated from measurements of total organic carbon (TOC). Following each experiment, chemical cleaning was performed by filtration of HCl, NaOH and water. This procedure was followed by demineralized water filtration, to ensure that the initial permeability was restored.In the first part of the work the ultrafiltration of sodium alginate solutions for different concentrations and various pressures was studied. Experimental results for macroligand retention, deduced from the TOC values, show a total rejection. All the curves, permeate flux versus time, present the same profile which indicates a significant concentration polarization. According to the obtained results we chose the value of 5 10-2 g L-1 for the ligand concentration and one bar for the applied pressure.In the second part of the study, the retention of cations (Cd2+, Cu2+, Mn2+ and Pb2+) was investigated. The observed results show that the removal rates are close to 100%. These values depend both on the total concentration of cation and on the pH value. The retention of cations is shown to depend strongly on pH: a variation of pH between 3 and 5 leads to changes in retention efficiency from 0 to 100%. This can be explained by the dissociation of alginic acid as a function of pH. For lower pH values the macroligand is in a molecular form and the metallic cation remains free; for higher values metal complexation is possible, increasing the rejection. If coordination number, rejection rate and pH are known, the various association constants can be determined using a graphical method. It can be seen from the results that the stability of the complexes formed decreases in the sequence Pb>Cu>Mn>Cd.In order to investigate the retention of these cations in a fresh water, the influence of calcium hardness was studied. The results indicate that cation removal decreases when the calcium concentration increases. This observation is an important restriction for fresh water treatment but does not affect the elimination of metals from a solution or an industrial waste containing cations

Nanofiltration de solutions de nitrate d'ammonium. Etude des paramètres influents

Cet article propose une étude de la rétention du nitrate d'ammonium par une membrane commerciale de nanofiltration (Nanomax 50). Les effets de la pression, de la concentration et de la vitesse d'écoulement tangentiel ont été étudiés avec le souci d'une meilleure compréhension du mécanisme de transport des ions nitrate et en vue d'une optimisation de la rétention. Le taux de rétention des ions nitrate augmente dans un premier temps avec la pression, atteint un maximum puis diminue. La rétention, pour des pressions élevées, peut cependant être améliorée en augmentant la vitesse d'écoulement tangentiel. La séparation résulterait d'un rapport de différentes forces : une force d'entraînement radial dans le pore (illustrée par l'effet de la pression transmembranaire), une force d'entraînement tangentiel vers le rétentat (illustrée par l'effet de la vitesse d'écoulement tangentiel) et une force de surface traduisant les interactions membrane-soluté (illustrée par l'effet de la concentration). L'équation de Spiegler et Kedem est proposée en première approche de modélisation pour une valeur limite de pression.Many water sources deal with the problem of increasing nitrate concentrations above authorised levels for drinking water. In order to minimise this amount of pollution and to achieve high quality of water and reused water in the distribution system, membrane processes are becoming a promising technology. Indeed, they present the major advantages of a small land area requirement, low temperature operation, continuous separation, better effluent quality, little or no sludge production and a large reduction in the quantities of chemical additives. Reverse osmosis has already been used to remove most of the nitrates together with the other solutes, but the disadvantage is that this technique induces a total demineralisation of the treated water. Another possible filtration process, nanofiltration, has been investigated in this study while no extensive research has been carried out on its nitrate removal potential. Theories cannot adequately predict the influence of operating parameters on membrane performance. Consequently, new membranes and modules must be experimentally evaluated for each new application. The main objective of this study was to provide fundamental data for designing an operation of nanofiltration under various operating conditions such as transmembrane pressure, cross-flow velocity and initial feed concentration for drinking water and water reuse purposes.The retention rate rises with an increase of the applied pressure, reaches a maximum and then decreases. Such a result is quite different from those usually mentioned in the literature where the retention increases and reaches a plateau when the pressure grows. The singular decrease of the retention rate observed in this study could be explained in terms of a concentration polarization phenomenon. However, since the volumetric flux increased linearly with the pressure and remained close to the pure water flux, it might be thought that such an assumption is not valid in the case of this work. Therefore, another hypothesis has to be provided to explain the variation of the retention with transmembrane pressure. As the size of NH4+ ion (ionic radius=0.148 nm) is lower than that of the pore of membrane (diameter=1 nm), cations can enter the pores where they are partially retained due to surface forces (electrostatic and friction forces). When the pressure increases, these forces remain constant while drag forces increase due to the flux in the pore. At low pressure (∆P < 5 bars), the surface forces are stronger than the drag forces. Therefore, the solute flux remains low while the solvent flux increases with the pressure, leading to an increase in the solute retention. Above a given pressure (≅ 5 bars), the drag forces become higher than the surface forces. Consequently, the retention rate decreases.As can be observed in the obtained results, the retention rate decreased when the feed concentration was increased regardless of the operating pressure. This effect is mainly attributed to the cation shielding of the effective charge of the membrane. This characteristic can be explained by the fact that the electric repulsion becomes less efficient at higher concentration. It has been recognized that the effective charge density of the membrane decreases with an increase in the feed concentration of an ionic solution. Consequently, the retention rate of the co-ion due to charge effect is reduced. It follows that a greater amount of nitrate ions could permeate when feed solutions of higher concentration are applied.The effect of cross-flow velocity on the fluxes is insignificant since the permeate flux depends only on transmembrane pressure. However, the retention performance increases with velocity. The lower the cross-flow velocity, the higher the interaction between the solute and the membrane. Therefore, at low cross-flow rate, the solute amount that enters the membrane pores is high. When the drag forces become stronger than the surface forces, as explained above, the retention sharply decreases. At high cross-flow velocity, the feed circulation transports a large solute amount and therefore, the solute amount that enters the pores is reduced and is less sensitive to operating pressure. In consequence, the sensitivity of the retention to transmembrane pressure is not so marked. It might be thought that for a very high cross-flow velocity, the retention increases and then remains constant.It was demonstrated in this work that nanofiltration can be successfully used to remove nitrates from water. The retention was shown to depend strongly on operating parameters such as feed solution concentration, applied pressure and circulation cross-flow rate. In fact, the retention is mainly determined by the intensity of the solute / membrane interaction. This interaction comes from two main forces: a tangential one due to the feed solute flow (illustrated by the cross-flow velocity effect) and a radial one in the pores due to drag forces (illustrated by the transmembrane pressure effect). Moreover, it was observed that the valence of the associated ions is an important factor that can affect nitrate retention. It can be expected that the optimization of the separation performance will result of the best combination of all these parameters. Therefore, with a view to a future industrial application, it will be necessary to take into consideration the chemical composition of the resource and to adapt the operating conditions to the desired objectives

An elevated level of TSH might be predictive of differentiated thyroid cancer

Suppression therapy of thyreostimulin (TSH) using thyroid hormones improves survival of subjects operated for differentiated thyroid cancer. The TSH level might be different depending on the type of nodule. The objective of this study was to compare retrospectively the TSH level between two groups of subjects who underwent total thyroidectomy for a nodule, matched on sex, ethnicity, age and biological method of TSH measurement, one whose final histology was benign and one malignant. There was no significant difference between the two groups in terms of age, sex, family history of thyroid disease or thyroid autoimmunity. The subjects, whose final histology was malignant, had a mean TSH level significantly higher than subjects with benign disease (1.55 mU/l versus 0.96 mU/l, P=0.003). Cancer risk was greater when the TSH was in the upper tertile of normal range. There was no correlation between the risk of thyroid cancer and age, sex, family history of thyroid disease, or menopausal status. The relative risk of having thyroid carcinoma was higher when the margins of nodules were blurred or in the presence of microcalcifications. These data confirm a trend toward baseline values of TSH higher in subjects with a thyroid-differentiated cancer. However, we could not define a preoperative threshold that would reliably determine the malignant or benign nature of the nodule

Reusability of filtering facepiece respirators after decontamination through drying and germicidal UV irradiation.

During pandemics, such as the SARS-CoV-2, filtering facepiece respirators plays an essential role in protecting healthcare personnel. The recycling of respirators is possible in case of critical shortage, but it raises the question of the effectiveness of decontamination as well as the performance of the reused respirators. Disposable respirators were subjected to ultraviolet germicidal irradiation (UVGI) treatment at single or successive doses of 60 mJ/cm &lt;sup&gt;2&lt;/sup&gt; after a short drying cycle (30 min, 70°C). The germicidal efficacy of this treatment was tested by spiking respirators with two staphylococcal bacteriophages (vB_HSa_2002 and P66 phages). The respirator performance was investigated by the following parameters: particle penetration (NaCl aerosol, 10-300 nm), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry and mechanical tensile tests. No viable phage particles were recovered from any of the respirators after decontamination (log reduction in virus titre &gt;3), and no reduction in chemical or physical properties (SEM, particle penetrations &lt;5%-6%) were observed. Increasing the UVGI dose 10-fold led to chemical alterations of the respirator filtration media (FTIR) but did not affect the physical properties (particle penetration), which was unaltered even at 3000 mJ/cm &lt;sup&gt;2&lt;/sup&gt; (50 cycles). When respirators had been used by healthcare workers and undergone decontamination, they had particle penetration significantly greater than never donned respirators. This decontamination procedure is an attractive method for respirators in case of shortages during a SARS pandemic. A successful implementation requires a careful design and particle penetration performance control tests over the successive reuse cycles

CheckMate-032 study: efficacy and safety of nivolumab and nivolumab plus ipilimumab in patients with metastatic esophagogastric cancer

Purpose: Metastatic esophagogastric cancer treatments after failure of second-line chemotherapy are limited. Nivolumab demonstrated superior overall survival (OS) versus placebo in Asian patients with advanced gastric or gastroesophageal junction cancers. We assessed the safety and efficacy of nivolumab and nivolumab plus ipilimumab in Western patients with chemotherapy-refractory esophagogastric cancers. Patients and Methods: Patients with locally advanced or metastatic chemotherapy–refractory gastric, esophageal, or gastroesophageal junction cancer from centers in the United States and Europe received nivolumab or nivolumab plus ipilimumab. The primary end point was objective response rate. The association of tumor programmed death-ligand 1 status with response and survival was also evaluated. Results: Of 160 treated patients (59 with nivolumab 3 mg/kg, 49 with nivolumab 1 mg/kg plus ipilimumab 3 mg/kg, 52 with nivolumab 3 mg/kg plus ipilimumab 1 mg/kg), 79% had received two or more prior therapies. At the data cutoff, investigator-assessed objective response rates were 12% (95% CI, 5% to 23%), 24% (95% CI, 13% to 39%), and 8% (95% CI, 2% to 19%) in the three groups, respectively. Responses were observed regardless of tumor programmed death-ligand 1 status. With a median follow-up of 28, 24, and 22 months across the three groups, 12-month progression-free survival rates were 8%, 17%, and 10%, respectively; 12-month OS rates were 39%, 35%, and 24%, respectively. Treatment-related grade 3/4 adverse events were reported in 17%, 47%, and 27% of patients in the three groups, respectively. Conclusion: Nivolumab and nivolumab plus ipilimumab demonstrated clinically meaningful antitumor activity, durable responses, encouraging long-term OS, and a manageable safety profile in patients with chemotherapy-refractory esophagogastric cancer. Phase III studies evaluating nivolumab or nivolumab plus ipilimumab in earlier lines of therapy for esophagogastric cancers are underway