Le péroxyde d'hydrogène en désodorisation physico-chimique : Rôle de la composition de la solution de lavage dans le mécanisme d'action

La désodorisation physico-chimique en stations d'épuration s'effectue généralement par lavage basique oxydant pour piéger les espèces soufrées réduites telles que H2 S ou CH3 SH. L'utilisation du peroxyde d'hydrogène n'est pas encore répandue en comparaison de celle du chlore. Cette étude a été menée afin de déterminer le comportement de H2O2 en fonction de la composition de l'eau de lavage. L'influence des paramètres : concentration en métaux (fer, manganèse, cuivre et zinc), pH, [H2O2], [CO32-], [HS-] a été étudiée en utilisant un plan d'expériences. La décomposition de H2O2 et la concentration de radicaux libres ont été mesurées pour chaque expérience. En présence de métaux, un pH élevé et une forte concentration en peroxyde sont les deux paramètres principalement responsables d'une forte décomposition. Cette décomposition serait accompagnée d'une production de radicaux avec [HO°]max =10-13 M. Cette valeur mesurée de radicaux dans le milieu n'explique qu'une petite part de la décomposition de peroxyde observée. Par conséquent, la majorité de la décomposition est due à des réactions soit à la surface des oxydes, soit en solution avec les cations dissous. Le mélange de métaux et de carbonates à pH 10,5 présente un effet de synergie sur la décomposition de H2O2. Ces résultats démontrent que malgré le pouvoir oxydant des radicaux HO° formés, l'utilisation de H2O2 en désodorisation ne sera possible qu'avec l'ajout de stabilisant.Deodorization of wastewater treatment plants involves the elimination of molecules such as NH3, amines and sulphur compounds like H2 S and mercaptans. In classical physico-chemical processes, NH3 and amines are trapped in acid solution by washing air in a scrubbing tower, while sulphides are eliminated in basic oxidising solutions. The oxidant usually used is sodium hypochlorite. Elimination of sulphides and organosulphides generally demands two scrubbers: one at pH 9 and the other at pH 11. Because chlorine in deodorization generates the formation of organochlorinated species, it should soon become necessary to replace this oxidant in order to avoid the formation of such compounds. The present study follows the behaviour in wash conditions not of chlorine, but hydrogen peroxide, in order to discover the deodorization capacity of this molecule.The kinetics of H2 S oxidation by H2O2 are well known; the constant is given by log k = 12.04 - (2641/T) - 0.186 x pH (Millero et al., 1989). Unfortunately H2O2 shows strong decomposition in alkaline medium, due to the presence of metals and carbonates in the solution. Initiating a homolytic reaction results in the decomposition of peroxide. However, increasing the concentration of free radicals may improve H2 S oxidation and consequently, the efficiency of the process.To better understand the behaviour of H2O2 in wash conditions, various parameters were studied, namely pH (9 and 10.5), [H2O2] (1 and 5 g L-1), metal concentrations (iron, manganese, copper and zinc) (20 and 200 µg L-1), [CO32-] (0 and 100 mg L-1) and [HS-] (0 and 2 mg L-1). Four experimental designs, one for each metal, were employed to reduce the number of experiments and benefit from statistical laws. H2O2 decomposition and HO° concentration were measured and empirical equations established. All experiments were performed in closed-batch reactors with ultra-pure reactants and water. Measurements of HO° concentrations necessitated the addition of atrazine to the solution. The oxidation of this pesticide by HO° is well known. Using atrazine concentrations measured through time, the HO° concentrations were calculated according to the equationln ([Atz]0/[Atz]) = k[HO∘]twith k=2.1 × 109 M-1 s-1 (De Laat et al., 1997). Oxidation of atrazine was halted by extraction onto a Ct18 Sep-Pack resin and samples were analysed by liquid chromatography.The results showed that in the presence of metals H2O2 decomposition was maximal at high pH and with high peroxide concentrations. The decomposition was accompanied by HO° production. However, the presence of metals generated the decomposition of H2O2 with a reduced production of free radicals compared with ultra-pure water, which indicates that metal oxides were not only decomposition catalysts, but also radical inhibitors. Comparison of simplified radical decomposition, calculated according to the equation([H2O2]/[H2O2]0)=e-k[HO∘]t,and observed decomposition showed that under these conditions H2O2 consumption was mainly due to metal reactivity. Nonetheless, increasing iron and copper concentrations from 20 to 200 µg L-1 did not modify the decomposition rate of H2O2. For this reason we postulate a Fenton-like reaction between H2O2 and dissolved metals in which concentrations are determined by solubility products. It follows that the kinetics of H2O2 decomposition can be summarised by r=-k1 [oxide][H2O2] - k2[ Mn+][H2O2] - k3 [HO°][H2O2], with [metal]Tot =[Mn+] + [oxide] and, in the case of Cu and Fe, k1 [oxide][H2O2] << k2[ Mn+][H2O2].To conclude, the addition of four metals with [CO32-]=1 g L-1 at pH 10.5 produces a synergetic effect, resulting in a much faster decomposition. These conditions, unfortunately, resemble deodorization conditions. The use of a stabiliser that inhibits not only free radicals but also decomposition catalysts is therefore necessary for deodorization

A survey of volatile species in Oort cloud comets C/2001 Q4 (NEAT) and C/2002 T7 (LINEAR) at millimeter wavelengths

The line emission in the coma was measured in the comets C/2001 Q4 (NEAT) and C/2002 T7 (LINEAR), that were observed on five consecutive nights, 7-11 May 2004, at heliocentric distances of 1.0 and 0.7 AU, respectively, by means of high-resolution spectroscopy using the 10-m Submillimeter Telescope (SMT). We present a search for six parent- and product-volatile species (HCN, H2CO, CO, CS, CH3OH, and HNC) in both comets. Multiline observations of the CH3OH J = 5-4 series allow us to estimate the rotational temperature using the rotation diagram technique. We derive rotational temperatures of 54(9) K for C/2001 Q4 (NEAT) and 119(34) K for C/2002 T7 (LINEAR) that are roughly consistent with observations of other comets at similar distances from the Sun. The gas production rates of material are computed using a spherically symmetric molecular excitation code that includes collisions between neutrals and electrons. We find an HCN production rate of 2.96(5)e26 molec.s-1 for comet C/2001 Q4 (NEAT), corresponding to a mixing ratio with respect to H2O of 1.12(2)e-3. The mean HCN production rate during the observing period is 4.54(10)e26 molec.s-1 for comet C/2002 T7 (LINEAR), which gives a Q_HCN/Q_H2O mixing ratio of 1.51(3)e-3. With systematically lower mixing ratios in comet C/2001 Q4 (NEAT), production rate ratios of the observed species with respect to H2O lie within the typical ranges of dynamically new comets in both objects. We find a relative low abundance of CO in C/2001 Q4 (NEAT) compared to the observed range in other comets based on millimeter/submillimeter observations, and a significant upper limit on the CO production in C/2002 T7 (LINEAR) is derived. Depletion of CO suggests partial evaporation from the surface layers during previous visits to the outer Solar System and agrees with previous measurements of dynamically new comets.Comment: 20 pages, 18 figures. Minor changes to match the published versio

Millimetre continuum observations of comet C/2009 P1 (Garradd)

Little is known about the physical properties of the nuclei of Oort cloud comets. Measuring the thermal emission of a nucleus is one of the few means for deriving its size and constraining some of its thermal properties. We attempted to measure the nucleus size of the Oort cloud comet C/2009 P1 (Garradd). We used the Plateau de Bure Interferometer to measure the millimetric thermal emission of this comet at 157 GHz (1.9 mm) and 266 GHz (1.1 mm). Whereas the observations at 266 GHz were not usable due to bad atmospheric conditions, we derived a 3-sigma upper limit on the comet continuum emission of 0.41 mJy at 157 GHz. Using a thermal model for a spherical nucleus with standard thermal parameters, we found an upper limit of 5.6 km for the radius. The dust contribution to our signal is estimated to be negligible. Given the water production rates measured for this comet and our upper limit, we estimated that Garradd was very active, with an active fraction of its nucleus larger than 50%.Comment: Accepted for publication in Astronomy & Astrophysics. 5 pages, 2 figure

Submillimetric spectroscopic observations of volatiles in comet C/2004 Q2 (Machholz)

We aim to determine the production rates of several parent and product volatiles and the 12C/13C isotopic carbon ratio in the long-period comet C/2004 Q2 (Machholz), which is likely to originate from the Oort Cloud. The line emission from several molecules in the coma was measured with high signal-to-noise ratio in January 2005 at heliocentric distance of 1.2 AU by means of high-resolution spectroscopic observations using the Submillimeter Telescope (SMT). We have obtained production rates of several volatiles (CH3OH, HCN, H13CN, HNC, H2CO, CO and CS) by comparing the observed and simulated line-integrated intensities. Furthermore, multiline observations of the CH3OH (7-6) series allow us to estimate the rotational temperature using the rotation diagram technique. We find that the CH3OH population distribution of the levels sampled by these lines can be described by a rotational temperature of 40 \pm 3 K. Derived mixing ratios relative to hydrogen cyanide are CO/CH3OH/H2CO/CS/HNC/H13CN/HCN = 30.9/24.6/4.8/0.57/0.031/0.013/1 assuming a pointing offset of 8" due to the uncertain ephemeris at the time of the observations and the telescope pointing error. The measured relative molecular abundances in C/2004 Q2 (Machholz) are between low- to typical values of those obtained in Oort Cloud comets, suggesting that it has visited the inner solar system previously and undergone thermal processing. The HNC/HCN abundance ratio of ~3.1% is comparable to that found in other comets, accounting for the dependence on the heliocentric distance, and could possibly be explained by ion-molecule chemical processes in the low-temperature atmosphere. From a tentative H13CN detection, the measured value of 97 \pm 30 for the H12CN/H13CN isotopologue pair is consistent with a telluric value.Comment: 14 pages with 11 figures, abridged abstrac

Measuring shell resonances of spherical acoustic resonators

International audienceCoupling between gas and shell is a concern in the experiment used at LNE-CNAM to determine the Boltzmann constant kB by an acoustic method. As the walls of real resonators are not perfectly ridig, some perturbations occur in the frequency range of the acoustic resonances measured within helium gas contained in the caivity. As a contribution for a better understanding of the phenomenon, we have built an experiment to measure the shell modes of the spherical resonators in use in our laboratory. We report here a work in progress to assess these modes using a hammer blow method together with modal analysis. The study is carried out with air-filled, copper-walled, half-litre quasi-spherical resonator in the frequency range from 1 Hz to 20 kHz. Our results show that the shell modes expand into multiple resonances of similar modal shape, including the "breathing" mode. We confirm the observations reported in other works [4,6] of shell perturbations at other frequencies than the breathing frequency

NK cells and cancer: you can teach innate cells new tricks

Abstract | Natural killer (NK) cells are the prototype innate lymphoid cells endowed with potent cytolytic function that provide host defence against microbial infection and tumours. Here, we review evidence for the role of NK cells in immune surveillance against cancer and highlight new therapeutic approaches for targeting NK cells in the treatment of cancer

Cometary water expansion velocity from OH line shapes

We retrieve the H_2O expansion velocity in a number of comets, using the 18-cm line shapes of the OH radical observed with the Nan\c{c}ay radio telescope. The H_2O velocity is derived from the large base of a trapezium fitted to the observed spectra. This method, which was previously applied to 9 comets, is now extended to 30 further comets. This allows us to study the evolution of their water molecule outflow velocity over a large range of heliocentric distances and gas production rates. Our analysis confirms and extends previous analyses. The retrieved expansion velocities increases with increasing gas production rates and decreasing heliocentric distances. Heuristic laws are proposed, which could be used for the interpretation of observations of cometary molecules and as a touchstone for hydrodynamical models. The expansion velocities retrieved from 18 cm line shapes are larger than those obtained from millimetric observations of parent molecules with smaller fields of view, which demonstrates the acceleration of the gas with cometocentric distance. Our results are in reasonable quantitative agreement with current hydrodynamical models of cometary atmospheres.Comment: Accepted for publication in Astronomy & Astrophysic