The chemical diversity of comets

A fundamental question in cometary science is whether the different dynamical classes of comets have different chemical compositions, which would reflect different initial conditions. From the ground or Earth orbit, radio and infrared spectroscopic observations of a now significant sample of comets indeed reveal deep differences in the relative abundances of cometary ices. However, no obvious correlation with dynamical classes is found. Further results come, or are expected, from space exploration. Such investigations, by nature limited to a small number of objects, are unfortunately focussed on short-period comets (mainly Jupiter-family). But these in situ studies provide "ground truth" for remote sensing. We discuss the chemical differences in comets from our database of spectroscopic radio observations, which has been recently enriched by several Jupiter-family and Halley-type comets.Comment: In press in Earth, Moon and Planets (proceedings of the workshop "Future Ground-based Solar System Research: Synergies with Space Probes and Space Telescopes", Portoferraio, Isola d'Elba, Livorno (Italy), 8-12 September 2008). 6 pages with 2 figure

Bayesian calibration of the nitrous oxide emission module of an agro-ecosystem model

Nitrous oxide (N2O) is the main biogenic greenhouse gas contributing to the global warming potential (GWP) of agro-ecosystems. Evaluating the impact of agriculture on climate therefore requires a capacity to predict N2O emissions in relation to environmental conditions and crop management. Biophysical models simulating the dynamics of carbon and nitrogen in agro-ecosystems have a unique potential to explore these relationships, but are fraught with high uncertainties in their parameters due to their variations over time and space. Here, we used a Bayesian approach to calibrate the parameters of the N2O submodel of the agro-ecosystem model CERES-EGC. The submodel simulates N2O emissions from the nitrification and denitrification processes, which are modelled as the product of a potential rate with three dimensionless factors related to soil water content, nitrogen content and temperature. These equations involve a total set of 15 parameters, four of which are site-specific and should be measured on site, while the other 11 are considered global, i.e. invariant over time and space. We first gathered prior information on the model parameters based on the literature review, and assigned them uniform probability distributions. A Bayesian method based on the Metropolis–Hastings algorithm was subsequently developed to update the parameter distributions against a database of seven different field-sites in France. Three parallel Markov chains were run to ensure a convergence of the algorithm. This site-specific calibration significantly reduced the spread in parameter distribution, and the uncertainty in the N2O simulations. The model’s root mean square error (RMSE) was also abated by 73% across the field sites compared to the prior parameterization. The Bayesian calibration was subsequently applied simultaneously to all data sets, to obtain better global estimates for the parameters initially deemed universal. This made it possible to reduce the RMSE by 33% on average, compared to the uncalibrated model. These global parameter values may be used to obtain more realistic estimates of N2O emissions from arable soils at regional or continental scales

Sélection participative et adaptation locale

The use of organic seeds has been compulsory since 2005 for practicing organic farming. Despite the efforts made by seed companies, applications are not yet fully satisfied in quantity and diversity. Producers of Bio Loire Ocean made the bet to develop a research program on this issue. How to set up and select specific varieties for their territories and production systems? Choice was made to work with varieties populations because of their plasticity and diversity. With the help of INRA SAD, a local participatory breeding work was initiated on many vegetable crops including leading species in the region (carrot, salad) and other species for diversification (parsnips, tomatoes,...). The results are encouraging and the producers wish to pursue and develop specific selection on their farms in order to have organic varieties adapted to their pedoclimatic and socio-economic environments. Like the partnership established with AGROCAMPUS OUEST and the network Carotte et autres Daucus, we wish to promote the genetic diversity of crop varieties and meet the needs of producers and consumers. Our program will grow in the coming years, involving and combining the skills and expertise of researchers, producers and multipliers for an overall, coherent and sustainable organic vegetable seed industry in the region of Pays de Loire

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

Nitrogen isotopic ratios in Barnard 1: a consistent study of the N2H+, NH3, CN, HCN and HNC isotopologues

The 15N isotopologue abundance ratio measured today in different bodies of the solar system is thought to be connected to 15N-fractionation effects that would have occured in the protosolar nebula. The present study aims at putting constraints on the degree of 15N-fractionation that occurs during the prestellar phase, through observations of D, 13C and 15N-substituted isotopologues towards B1b. Both molecules from the nitrogen hydride family, i.e. N2H+ and NH3, and from the nitrile family, i.e. HCN, HNC and CN, are considered in the analysis. As a first step, we model the continuum emission in order to derive the physical structure of the cloud, i.e. gas temperature and H2 density. These parameters are subsequently used as an input in a non-local radiative transfer model to infer the radial abundances profiles of the various molecules. Our modeling shows that all the molecules are affected by depletion onto dust grains, in the region that encompasses the B1-bS and B1-bN cores. While high levels of deuterium fractionation are derived, we conclude that no fractionation occurs in the case of the nitrogen chemistry. Independently of the chemical family, the molecular abundances are consistent with 14N/15N~300, a value representative of the elemental atomic abundances of the parental gas. The inefficiency of the 15N-fractionation effects in the B1b region can be linked to the relatively high gas temperature ~17K which is representative of the innermost part of the cloud. Since this region shows signs of depletion onto dust grains, we can not exclude the possibility that the molecules were previously enriched in 15N, earlier in the B1b history, and that such an enrichment could have been incorporated into the ice mantles. It is thus necessary to repeat this kind of study in colder sources to test such a possibility.Comment: accepted in A&

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