Mass transfer coefficients of styrene into water/silicone oil mixtures: New interpretation using the "equivalent absorption capacity" concept.

International audienceThe physical absorption of styrene into water/silicone oil systems at a constant flow rate for mixtures of different compositions (silicone oil volume fraction ϕ = 0%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, and 10%) was investigated in laboratory-scale bubble reactors using a dynamic absorption method. Experimental results previously analyzed assuming no contact between gas and silicone oil [10] were reconsidered by applying the "equivalent absorption capacity" concept characterized by the value of the styrene partition coefficient between air and the mixture (Hmix). The results indicate that silicone oil addition slightly hinders the styrene mass transfer rate compared to the air/water system. Moreover, a dramatic decrease in KLa values due to silicone oil addition is observed. In comparison with similar measurements available in the literature, it is noted that this decrease in KLa value could be related to the change in the partition coefficient ratio mR = Hwater/Hoil. Two explanations concerning the relationship between the change in a hydrodynamic parameter (KLa) and that in a thermodynamic parameter (mR) are proposed. Finally, it appears questionable to study the change in KLa in terms of silicone oil addition

Effect of aging on decorative and renovation products containing biocides: Assessment of its impact on indoor air quality

To evaluate the impact of the aging (the use of detergent and exposure to light, high relative humidity, and temperature) on the efficiency of biocides present in the renovation plaster after being added to polyester cellulose (combined material) and on VOC and SVOC emissions, an inoculation of innate and aged materials with fungal spores was carried out in this study using a dry aerosolization system. VOCs and SVOCs emitted from these different materials before and after inoculation were characterized using gas (TD-GCMS/ FID) and liquid (HPLC) chromatography.publishedVersio

Novel heating/cooling stage designed for fluid inclusion microthermometry of large stalagmite sections

Liquid–vapour homogenisation temperatures of fluid inclusions in stalagmites are used for quantitative temperature reconstructions in paleoclimate research. Specifically for this application, we have developed a novel heating/cooling stage that can be operated with large stalagmite sections of up to 17 × 35 mm2 to simplify and improve the chronological reconstruction of paleotemperature time-series. The stage is designed for use of an oil immersion objective and a high-NA condenser front lens to obtain high-resolution images for bubble radius measurements. The temperature accuracy of the stage is better than ± 0.1 °C with a precision (reproducibility) of ± 0.02 °C

Mise au point de filtres garnis de matériaux réactifs destinés au traitement des eaux usées au sein de petites installations

L objectif de ce travail est la mise au point de filtres garnis de laitiers d aciéries destinés au traitement du phosphore (P) des eaux usées au sein de petites installations. Deux types de laitiers on été testés: laitiers de four à arc électrique (EAF), et laitiers d'aciérie de conversion (BOF). Une approche intégrée a été suivie, avec investigations à différentes échelles: (i) Des expériences en flacons ont été réalisées pour établir les capacités de rétention du P de laitiers produits en Europe, et ainsi sélectionner les échantillons les plus adaptés pour l élimination du P; (ii)Des expériences en colonnes ont été menées pour étudier l'effet de divers paramètres, notamment la taille et la composition du laitier, sur les performances hydrauliques et épuratoires des filtres; (iii) Enfin, des expériences sur terrain ont été conduites afin d évaluer les performances hydrauliques et épuratoires de deux unités démonstration conçues pour le traitement du P au sein d un marais artificiel. Les résultats expérimentaux ont indiqué que le principal mécanisme d'élimination du P est lié à la dissolution du CaO des laitiers, suivie de la précipitation de phosphate de Ca et recristallisation en hydroxyapatite (HAP). Après 100 semaines d'alimentation avec une solution de P (concentration moyenne de P totale 10,2 mgP/L), les colonnes remplies de laitiers de petite taille (BOF6-12 mm et EAF 5-16 mm) ont retenu >98% du P total en entrée, tandis que les colonnes remplies de laitiers de grande taille (BOF 20-50 mm et EAF 20-40) ont retenu 56et 86% du P total en entrée, respectivement. Il apparaît que, plus la taille des laitiers est petite, plus la surface spécifique disponible pour la dissolution du CaO et pour l adsorption des phosphates de Ca est grande. Les expériences sur terrain ont confirmé que les laitiers sont efficaces pour le traitement du P de l'effluent d'un marais artificiel (concentration moyenne du P totale 8,3 mg P/L). Sur une période de 85 semaines d'opération, de laitiers EAF ont retenu le 36% du P total en entrée, tandis que les laitiers BOF ont retenu le 59% du P total en entrée.L efficacité de rétention du P apparaît augmenter avec la température et le temps de rétention hydraulique (HRT),très probablement parce que l'augmentation de la température et du HRT a favorisé la dissolution de la CaO et la précipitation de phosphate de Ca. Toutefois, il a été constaté que HRT >3 jours peuvent produire des pH élevés (>9), à la suite d une excessive dissolution de CaO.Cependant, les résultats des unités démonstration ont montré que, à HRT de 1-2 jours, les filtres produisent des pH élevés seulement pendant les 5 premières semaines de fonctionnement, puis les pH se stabilisent en dessous de 9. Enfin, une équation de dimensionnement sur la base des résultats expérimentaux a été proposée.This thesis aimed at developing the use of electric arc furnace steel slag (EAF-slag) and basic oxygen furnace steel slag (BOF-slag) in filters designed to upgrade phosphorus (P) removal in small wastewater treatment plants. An integrated approach was followed, with investigation at different scales: (i) Batch experiments were performed to establish an overview of the P removal capacities of steel slag produced in Europe, and then to select the most suitable samples for P removal; (ii)Continuous flow column experiments were performed to investigate the effect of various parameters including slag size and composition, and column design on treatment and hydraulic performances of lab-scale slag filters; (iii)Finally, field experiments were performed to investigate hydraulic and treatment performances of demonstration scale slag filters designed to remove P from the effluent of a constructed wetland. The experimental results indicated that the major mechanism of P removal was related toCaO-slag dissolution followed by precipitation of Caphosphate and recrystallisation into hydroxyapatite (HAP).Over 100 weeks of continuous feeding of a synthetic Psolution (mean inlet total P 10.2 mg P/L), columns filled with small-size slag (6-12 mm BOF-slag; 5-16 mm EAFslag)removed >98% of inlet total P, whereas columnsfilled with big-size slag (20-50 mm BOF-slag and 20-40mm EAF-slag) removed 56 and 86% of inlet total P,respectively. Most probably, the smaller was the size ofslag, the greater was the specific surface for CaO-slagdissolution and adsorption of Ca phosphate precipitates.Field experiments confirmed that EAF-slag and BOF-slagare efficient substrate for P removal from the effluent of aconstructed wetland (mean inlet total P 8.3 mg P/L). Overa period of 85 weeks of operation, EAF-slag removed 36%of inlet total P, whereas BOF-slag removed 59% of inlettotal P. P removal efficiencies increased with increasing temperature and void hydraulic retention time (HRTv),most probably because the increase in temperature and HRTv affected the rate of CaO dissolution and Caphosphate precipitation. However, it was found that longHRTv (>3 days) may produce high pH of the effluents(>9), as the result of excessive CaO-slag dissolution. However, the results of field experiments demonstrated that at shorter HRTv (1-2 days), slag filters produced pH that were elevated only during the first 5 weeks of operation, and then stabilized below a pH of 9. Finally, a dimensioning equation based on the experimental results was proposed.NANTES-ENS Mines (441092314) / SudocSudocFranceF

Optimisation du traitement de l'azote et du phosphore des eaux usées domestiques adapté aux filtres plantés de roseaux

Le rejet des nutriments (phosphates et nitrates) issues des eaux usées domestiques entraînent la dégradation des écosystèmes (74 % du territoire français concerné en 2006). Compte tenu de la situation, l Etat français a promulgué la Loi sur l Eau et les Milieux Aquatiques le 30décembre 2006 qui vise à atteindre le bon état écologique des eaux et des milieux aquatiques d ici 2015. Cette notion bien que difficilement intégrable a généré des normes plus strictes pour les stations d épuration en termes de rejet de nutriments vers le milieu récepteur (jusque 15 mg NTOT.L-1 et 2 mg PTOT.L-1). Depuis la fin des années 1990, la technologie des filtres plantés de roseaux (FPR) est de plus en plus employée(> 2500 unités en 2012) pour le traitement des eaux usées domestiques des petites collectivités inférieures à 2000 Equivalent-Habitants. Cependant, des limites de traitement existent sur les concentrations résiduelles en azote (rejet de 70-80 mg NTOT.L-1) et en phosphore (rejet> 10 mg PTOT.L-1), en vue de répondre à la réglementation future. Ce travail a eu pour objectif de mettre en oeuvre des améliorations telles que la recirculation sur un étage de traitement pour le traitement de l azote d une part et l emploi de matériaux réactifs pour piéger le phosphore d autre part. La démarche scientifique expérimentale déployée a consisté à suivre des pilotes sur site réel et en laboratoire pendant 2 années. Le suivi des performances épuratoires et hydrauliques a été réalisé au cours du temps. Pour l azote, 2 FPR (2,5 m ) garnis de schiste expansé (Mayennite®) ont été alimentés en effluent brut. L effet de la hauteur de saturation en eau dans la partie drainante ainsi que l effet de la recirculation ont été étudiés. Les résultats obtenus ont montré : une couche saturée à 38 % (rapporté à la hauteur totale) et un ratio de recirculation de 100 % permettent une meilleure élimination de la matière particulaire-carbonée (Arrêté du22 juin 2007) et de l azote ( 15 C) et/ou du temps de séjour (48h et plus) améliore la cinétique d élimination du phosphore à échelle pilote et (iii) l implantation d un filtre réactif garni de laitier de four à arc électrique est limité par le degré de traitement souhaité et la distance du futur chantier (coût du transport).Nutrient (phosphorus and nitrogen) discharges from wastewater lead to water quality degradation (74 % of the total French territory in 2006). According to the actual situation, the French government has adopted a Water Framework on December 30, 2006 to achieve a good ecological status of water in 2015. Therefore,more stringent standards on nutrients removal for raw wastewater treatment plants are expected (down to 15mg TN.L-1 and 2 mg TP.L-1). However, standards actually remain under the responsibility of departmental authorities according to the water quality of the receiving environment. Since 1990s, Vertical Flow Constructed Wetlands(VFCWs) have been more and more popular in treating raw domestic wastewater for small collectivities of less than 2000 person equivalent (> 2500 units in 2012). However, nitrogen and phosphorus removal are limited in VFCWs (70-80 mg TN.L-1; > 10 mg TP.L-1) according to the new legislation. The aim of this work was on the one hand to implement a recirculation of treated effluent on a VFCW for better nitrogen removal and on the other to use reactive materials to improve phosphorus removal. The experimental scientific approach consisted in monitoring both laboratory and field pilot scale systems under process conditions during 2 years. Treatment and hydraulic performances were monitored over time. Two VFCWs (2,5 m ) filled with expanded schist (Mayennite®) were fed with raw domestic wastewater. The effect of a saturated layer and of the recirculation of treated effluent were studied. Results showed that 38 % of a saturated layer and 100 % of recirculation enabled to improve nitrogen treatment performances ( 15C) and/or hydraulic retention time (more than 2 days) improved the kinetics of phosphorus removal at pilot scale, (iii) the active filter implementing is limited by the discharge standard required (> 3 mg PTOT.L-1) and the distance to the steel factory (transport costs).NANTES-ENS Mines (441092314) / SudocSudocFranceF

Devenir de polluants émergents lors d'un traitement photochimique ou photocatylitique sous irradiation solaire

L industrialisation et l utilisation dans la vie courante d un nombre croissant de produits chimiques et médicamenteux sont responsables de la dissémination dans l environnement de substances variées nommées polluants émergents . Les traitements des eaux usées existants ne sont pas conçus pour éliminer cette catégorie de pollution et les polluants émergents sont alors rejetés dans le milieu récepteur. Une possible solution pour limiter le rejet de ces composés par les effluents de station d épuration serait l utilisation de procédés de traitement additionnels tels que les procédés d oxydation avancés. C est dans ce contexte qu a démarré le projet Européen Clean Water en 2009 associant 7 entités dont le GEPEA-Ecole des Mines de Nantes. Le concept du projet est de développer des procédés photocatalytiques mettant en œuvre des nanomatériaux actifs sous la lumière solaire. Ces procédés visent à éliminer les polluants émergents tels que les perturbateurs endocriniens ou les produits pharmaceutiques. Dans ce programme, le laboratoire GEPEA est concerné par l évaluation de l efficacité des matériaux vis-à-vis de l élimination des polluants émergents sous irradiations UV et visibles. Pour cela, une méthodologie expérimentale a été établie de façon à exprimer les performances des catalyseurs testés en termes de constantes cinétiques de dégradation, de taux de conversion et de minéralisation des molécules étudiées mais aussi en fonction de la formation de produits intermédiaires. Ces performances sont également évaluées en termes de biodégradabilité, d effet de toxicité et de perturbation endocrinienne des produits intermédiaires. Dans un premier temps, la méthodologie expérimentale établie a été testée sur la dégradation de la tétracycline en utilisant un catalyseur de référence puis, elle a été appliquée sur la dégradation respective du bisphénol A et de la 17b-oestradiol en utilisant un catalyseur de référence et les catalyseurs élaborés dans le cadre du projet Clean Water. Les résultats sur la dégradation de la tétracycline ont montré que i) les intermédiaires réactionnels sont moins toxiques que la tétracycline, ii) la structure des intermédiaires réactionnelles est semblable à celle de la tétracycline ce qui explique la faible biodégradabilité de ces intermédiaires. Concernant la dégradation du bisphénol A et de la 17b-oestradiol, les résultats ont montré que i) les catalyseurs sont efficaces sous irradiation solaire simulée. Cependant, l efficacité photocatalytique du catalyseur dépend du composé à dégrader, ii) la nature des intermédiaires réactionnels identifiés du bisphénol A dépend du catalyseur utilisé, iii) l effet œstrogénique de la solution d oestradiol persiste au cours du traitement photocatalytique.Industrialisation, the use of numerous chemical products in domestic activities and the use of medicine drugs have led to the release in the environment of various substances named "emerging pollutants . The existing wastewater treatments are not designed to eliminate this kind of pollution and then these pollutants are released into the natural aquatic media. To limit the release of these compounds by waste water treatment plant effluent, a solution could be the use of additional treatment processes such as advanced oxidation processes. In this context, the European project Clean Water has started in 2009. Clean Water involves 7 entities including the GEPEA laboratory-Ecole des Mines de Nantes. The aim of the Clean Water project is to develop sustainable and cost effective water treatment and detoxification processes using TiO2 nanomaterials with UV-visible light response under solar light. These processes act to remove emerging contaminants such as endocrine disruptors and pharmaceuticals. In this program, theGEPEA laboratory is concerned with the evaluation of the efficiency of novel photocatalysts under UV and visible irradiations for the elimination of emerging pollutants. For this purpose, an experimental methodology was established to express the efficiency of the tested catalysts in terms of degradation kinetic constants, pollutants conversion and mineralisation and also in terms of the intermediate products formed. The efficiency of photocatalysts is also evaluated in terms of intermediates biodegradability, toxicity and endocrine disruption effects. First, the experimental methodology was tested on the degradation of tetracycline with a reference catalyst. Then, it was applied to the degradation of bisphenol A and estradiol respectively with the reference catalyst and the catalysts developed within the Clean Water Project. The results obtained on the tetracycline degradation have showed that: i) tetracycline intermediate products are less toxic than tetracycline ii) the intermediates structure is similar to that of tetracycline, this can explain the low biodegradability observed for these intermediates. For the degradation of bisphenol A and estradiol, the results showed that: i) the photocatalysts are efficient under simulated solar irradiation. However, the catalyst photocatalytic efficiency depends on the compound to be degraded ii) the nature of the bisphenol A reaction intermediates identified depends on the catalyst used iii)the estrogenic effect of the estradiol treated solution persists during the photocatalytic treatment.NANTES-ENS Mines (441092314) / SudocSudocFranceF

Sustainable Conversion of Agriculture and Food Waste into Activated Carbons Devoted to Fluoride Removal from Drinking Water in Senegal

International audienceThe objective of this study was to investigate the production of activated carbons (AC) from cashew shells, and millet stalks and their efficiency in fluoride retention. These agricultural residues are collected from Senegal. It is known that some regions of Sénégal, commonly called the groundnut basin, are affected by a public health problem caused by an excess of fluoride in drinking water used by these populations. The activated carbons were produced by a combined pyrolysis and activation with water steam; no other chemical compounds were added. Then, activated carbonaceous materials obtained from cashew shells and millet stalks were called CS-H2O and MS-H2O respectively. CS-H2O and MS-H2O show very good adsorbent features, and present carbon content ranges between 71 % and 86 %. The BET surface areas are 942 m² g-1 and 1234 m².g-1 for CS-H2O and MS-H2O respectively. A third activated carbon produced from food wastes and coagulation-flocculation sludge (FW/CFS-H2O) was produced in the same conditions. Carbon and calcium content of FW/CFS-H2O are 32.6 and 39.3 % respectively. The kinetics sorption were performed with all these activated carbons, then the pseudo-first equation was used to describe the kinetics sorption. Fluoride adsorption isotherms were performed with synthetic and natural water with the best activated carbon from kinetics sorption, Langmuir and Freundlich models were used to describe the experimental data. The results showed that carbonaceous materials obtained from CS-H2O and MS-H2O were weakly efficient for fluoride removal. With FW/CFS-H2O, the adsorption capacity is 28.48 mg.g-1 with r² = 0.99 with synthetic water

Activated char produced from chontaduro seeds: a new potential precursor

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Hydrophobic VOC absorption in two-phase partitioning bioreactors; influence of silicone oil volume fraction on absorber diameter.

International audienceA methodology to determine the diameter of an absorber contacting a gas phase and two immiscible liquid phases (water/silicone oil mixture) is presented. The methodology is applied to a countercurrent gas/liquid randomly packed column for the absorption of three VOCs (toluene, dimethyl sulfide, or dimethyl disulfide). Whatever the silicone oil volume fraction, Eckert's generalized pressure drop correlation was used. The results present the change in the column diameter through the change in the dimensionless ratio D(ϕ)/D(ϕ=1) versus the silicone oil volume fraction for the same operating conditions. For toluene and dimethyl disulfide, characterized by Hvoc,silicone oil values equal to 2.3 and 3.4 Pa m3 mol−1, respectively, it is highlighted that it is unwise to use water/silicone oil mixtures for mass transfer. In these cases, the contact between the polluted air and pure silicone oil requires roughly the same amount of silicone oil as for a (90/10 v/v) water/silicone oil mixture, but enables a 2-fold decrease in the column diameter. For dimethyl sulfide, which is characterized by a larger partition coefficient value (Hvoc,silicone oil=17.7 Pa m3 mol−1), the mass transfer operation should not be considered because large amounts of silicone oil are required (whatever the silicone oil volume fraction), which is not acceptable from an economic point of view. The feasibility of using a bioscrubber for the treatment of hydrophobic pollutants depends mainly on the partition coefficient Hvoc,silicone oil. VOC absorption in TPPB should therefore be restricted to pollutants characterized by a Hvoc,silicone oil value of around 3 to 4 Pa m3 mol−1 or less. In this case, absorption can be efficiently carried out in a biphasic air/silicone oil system

Volumetric mass transfer coefficients characterising VOC absorption in water/silicone oil mixtures

International audienceThe physical absorption of three Volatile Organic Compounds (dimethyldisulphide (DMDS), dimethylsulphide (DMS) and toluene) in "water/silicone oil" systems at a constant flow rate for mixtures of different compositions (f = 0, 5, 10, 15, 20 and 100%) was investigated using a dynamic absorption method. The results indicate that silicone oil addition leads to a dramatic decrease in KLa which can be related to the change in the partition coefficient (Hmix). They confirm the results obtained for styrene absorption using another measurement technique [15]. The interpretation of the results using dimensionless ratios KLa(f)/KLa(f=0%) and KLa(f)/KLa(f=100%) versus f also confirms the importance of the partition coefficient ratio mR = Hwater/Hoil in the KLa change. Moreover, the results obtained for toluene absorption in "air/water/silicone oil" systems (f = 10, 15 and 20%) suggest that the mass transfer pathway is in the order gas→water→oil for these operating conditions