Biodeterioration of cementitious materials in biogas digester

In biogas production plants, concrete structures suffer chemical and biological attacks during the anaerobic digestion process. The attack on concrete may be linked to the effects of (i) organic acids; (ii) ammonium and CO2 co-produced by the microorganisms’ metabolisms; and (iii) the bacteria’s ability to form biofilms on the concrete surface. In a context of biogas industry expansion, the mechanisms of concrete deterioration need to be better understood in order to propose innovative, efficient solutions. This study aims, firstly, to characterise the evolution of the biochemical composition of the biodegradable wastes during digestion so as to identify the compounds that are aggressive for concrete. Secondly, it aims to evaluate the mechanisms of concrete deterioration in anaerobic digesters. CEM I paste specimens were immersed in synthetic inoculated biowaste in anaerobic digestion conditions. The liquid fractions were analysed chemically. The alteration mechanisms of the cementitious matrices were investigated using XRD and SEM analyses. The maximal total concentration of organic acids was 65 mmol/L in the liquid fraction during the digestion process. The pH evolution showed two phases: acidification in the first few days and then a slow increase to pH 7–8. In only 4 weeks, an abundant biofilm developed on the cement paste surface. Biodeterioration leads to calcium leaching and carbonation of the cement past

Impact BIochimique des effluents agricoles et agroindustriels sur les structures/ouvrages en BEtOn dans la filière de valorisation par Méthanisation (ou codigestion anaérobie)

La digestion anaérobie est une succession d’étapes de dégradation de la matière organique, par l’intermédiaire de microorganismes, opérée industriellement dans des digesteurs en béton. Des métabolites microbiens (acides gras volatils (AGV), NH4+, CO2) produits au cours du processus de digestion attaquent la matrice cimentaire du béton. Afin d’assurer un développement pérenne de la filière de méthanisation, il est donc nécessaire de comprendre d’abord tous ces phénomènes d’altération pour ensuite proposer des solutions durables pour les matériaux de construction des digesteurs. Les objectifs de la thèse visaient à identifier et quantifier les agents agressifs pour le béton présents dans les milieux de la méthanisation, puis à comprendre leurs rôles dans les mécanismes d’altération des matrices cimentaires. Enfin, l’action de ces milieux a pu être comparée sur un panel de matériaux cimentaires réalisées à partir de différents liants : ciment Portland ordinaire, ciment de haut-fourneau, ciment d’aluminate de calcium et liant alcali activé. Dans des digesteurs de laboratoire, les concentrations maximales des agents chimiques agressifs mesurées pendant la digestion anaérobie d’un biodéchet modèle étaient de 3000 mg.L-1 d’AGV, de 800 mg.L-1 de NH4+, et de 140 mg.L-1 de CO2 dissous. La prolifération de microorganismes capables de métaboliser ces composés chimiques agressifs a été observée à la surface des matériaux cimentaires exposés dans le biodéchet au cours de sa digestion. La zone dégradée des matériaux cimentaires exposés est partiellement décalcifiée, vraisemblablement du fait de l’action des AGV et de l’ammonium NH4+, et carbonatée en raison de la présence de CO2 dissous. Des essais in situ, c’est à dire en conditions réelles, réalisées sur une plateforme expérimentale de méthanisation, ont permis de confirmer les phénomènes d’altération observés en laboratoire. En termes de durabilité, le ciment alumineux présente la meilleure résistance face aux attaques biochimiques lorsqu’on le compare au ciment ordinaire ou aux ciments composés de laitier de haut-fourneau au sein de systèmes de méthanisation en laboratoire ou in situ

Atomic Force Microscopy Study of Human Tooth Enamel Surfaces

Human enamel features from individual crystals up to prisms were observed by atomic force microscopy (AFM). Low magnification images of vestibular tooth surfaces show the existence of enamel prisms appearing as deep holes. Individual, parallel enamel crystals show lateral faces elongated and formed by the (100) planes of hydroxyapatite (HA). Height differences between (001) faces create the roughness of enamel surface. Individual (001) crystal faces can be observed clearly at higher magnification and show the characteristic hexagonal shape with 60° angles between (100) faces. This study confirms the applicability of AFM for studying biological hydroxyapatite crystals

Simultaneous quantification of steroid hormones and endocannabinoids (ECs) in human hair using an automated supported liquid extraction (SLE) and LC-MS/MS – Insights into EC baseline values and correlation to steroid concentrations

Endogenous steroid hormones and endocannabinoids (ECs) are important regulators in the stress response of the human body. For the measurement of chronic stress, hair analysis has been established as method of choice for long-term and retrospective determination of endogenous stress markers. A sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the quantification of five steroid hormones (cortisone, cortisol, androstenedione, testosterone, progesterone) and four endocannabinoids (anandamide, palmitoylethanolamide, 2-arachidonylglycerol, oleoylethanolamide) in hair was developed and validated. The hair samples were extracted with methanol and cleaned up with a fully automated supported liquid extraction (SLE) before analysis. Special attention was paid to the difficulties accompanying the quantification of endogenous analytes in hair. Five different strategies for endogenous compound quantification in hair (surrogate analyte, standard addition, background correction, stripped matrix and solvent calibration) were tested and compared. As a result, the approach of the surrogate analyte was used for the quantification of steroid hormones whereas background correction was used for endocannabinoids. The measurement of 58 samples from healthy young adults allowed insights into endocannabinoid ranges in hair and the correlation to steroid hormones. No significant differences in steroid and EC concentration levels of male and female in hair were found, except for testosterone (p < 0.001) and androstenedione (p < 0.0001). Cortisol to cortisone and testosterone to androstenedione concentrations were significantly and positively correlated. There were significant intercorrelations between endocannabinoids

Spray-assisted polyelectrolyte multilayer buildup: from step-by-step to single-step polyelectrolyte film constructions.

The alternate deposition of polyanions and polycations on a solid substrate leads to the formation of nanometer to micrometer films called Polyelectrolyte Multilayers. This step-by-step construction of organic films constitutes a method of choice to functionalize surfaces with applications ranging from optical to bioactive coatings. The method was originally developed by dipping the substrate in the different polyelectrolyte solutions. Recent advances show that spraying the polyelectrolyte solutions onto the substrate represents an appealing alternative to dipping because it is much faster and easier to adapt at an industrial level. Multilayer deposition by spraying is thus greatly gaining in interest. Here we review the current literature on this deposition method. After a brief history of polyelectrolyte multilayers to place the spraying method in its context, we review the fundamental issues that have been addresses so far. We then give an overview the different fields where the method has been applied.journal articlereview2012 Feb 212012 01 26importe

Mechanisms of cementitious material deterioration in biogas digester

Digesters produce biogas from organic wastes through anaerobic digestion processes. These digesters, often made of concrete, suffer severe premature deterioration caused mainly by the presence of fermentative microorganisms producing metabolites that are aggressive towards cementitious materials. To clarify the degradation mechanisms in an anaerobic digestion medium, ordinary Portland cement paste specimens were immersed in the liquid fraction of a running, lab-scale digester for 4 weeks. The anaerobic digestion medium was a mixture of a biowaste substrate and sludge from municipal wastewater treatment plant used as a source of anaerobic bacteria. The chemical characteristics of the anaerobic digestion liquid phase were monitored over time using a pH metre, high performance liquid chromatography (HPLC) and ion chromatography (HPIC). An initial critical period of low pH in the bioreactors was observed before the pH stabilized around 8. Acetic, propionic and butyric acids were produced during the digestion with a maximum total organic acid concentration of 50 mmol L− 1. The maximum ammonium content of the liquid phase was 40 mmol L− 1, which was about seven times the upper limit of the highly aggressive chemical environment class (XA3) as defined by the European standard for the specification of concrete design in chemically aggressive environments (EN 206). The changes in the mineralogical, microstructural and chemical characteristics of the cement pastes exposed to the solid and liquid phase of the digesters were analysed at the end of the immersion period by X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometry (EDS) and electron-probe micro-analysis (EPMA). A 700-μm thick altered layer was identified in the cement paste specimens. The main biodeterioration patterns in the bioreactors' solid/liquid phase were calcium leaching and carbonation of the cement matrix

Determination of structural parameters characterizing thin films by optical methods: A comparison between scanning angle reflectometry and optical waveguide lightmode spectroscopy

International audienceWe present a comparative study of the structural parameters characterizing thin macromolecular adsorbed films that are obtained from two optical techniques: optical waveguide lightmode spectroscopy ͑OWLS͒ and scanning angle reflectometry ͑SAR͒. We use polyelectrolyte multilayers and polyelectrolyte multilayers/protein films to perform this study. The comparison between the information obtained with the two methods is possible because the buildup of the polyelectrolyte multilayers is known to become substrate independent after the deposition of the first few polyelectrolyte layers. The analysis of the optical data requires usually to postulate a refractive index profile for the interface. Two profiles have been used: the homogeneous and isotropic monolayer and the bilayer profiles. When the refractive index profile of an adsorbed film is well approximated by a homogeneous and isotropic monolayer, as shown by using an analysis of the deposited films in terms of optical invariants, the two optical techniques lead to similar values for the film thickness and the optical mass. The situation is more complex in the case of the multilayers/protein films for which the calculated parameters can strongly depend upon the refractive index profile that is postulated to analyze the optical data. Whereas the optical mass and, to a lesser extent, the thickness seem fairly model independent for OWLS, they appear to be extremely sensitive to the model for SAR. For proteins deposited on top of the polyelectrolyte film, optical mass and protein thickness were found to be comparable when determined by OWLS and by SAR using the bilayer model. The data analysis of the SAR curves with the monolayer model leads to much larger and even physically unreasonable film thicknesses and optical masses. This was particularly noticeable for proteins having a large size ͑human serum albumin and fibrinogen͒, whereas both models lead to similar results for small sized proteins. By means of the different refractive index profiles, we show that great care must be taken in the physicochemical interpretation of the structural parameters determined by these optical techniques

Assemblage de films polymères par réaction click électrocontrôlée

Les multicouches de polyélectrolytes, systèmes auto-assemblés par adsorptions successives de polycations et polyanions, peinent à trouver des applications concrètes en raison de leur fragilité mécanique et du temps nécessaire à leur assemblage. Pour améliorer leur tenue mécanique, nous avons développé une méthode d'assemblage couche-par-couche par liaisons covalentes de films polymères. Des films formés de polymères portant des groupements alcynes et azides ont ainsi été réticulés par une réaction click catalysée par les ions Cu+ obtenus par voie électrochimique. Pour améliorer le mode d'assemblage, l'auto-construction en une seule étape de films par approche morphogénique, a été développée. Cette approche, confinée à la surface et caractérisée par la présence en solution de l'ensemble des constituants, marque une rupture. Elle permet ainsi un contrôle spatial de l'assemblage des films et la combinaison de plusieurs modes d'interactions pendant leur assemblage. Des films dont la cohésion repose sur des interactions covalentes, hôtes-invités et supramoléculaires, ont ainsi été assemblés. L'introduction de nanoparticules métalliques dans les films (multicouches et auto-construits) a également été effectuée dans le but de développer des électrodes de grande surface spécifique.Polyelectrolyte multilayer films, built by alternated adsorption of polycations and polyanions, face two main challenges: their construction process is tedious and their mechanical stability is poor. We developped a layer-by-layer strategy to improve the film stability by covalent reticulation of the polymers chains by click chemistry. Polymers bearing alkyne and azide functions were reticulated by triggering electrochemically the production of Cu+ catalyst ions. A one pot morphogen driven self-construction strategy was also developped to improve the buildup process of the films.In this case, all the constituants are simultaneously present in solution while the film grows up only at the electrode. Films based on covalent, host-guest and supramolecular interactions were obtained and the possibility of combining different interactions was also demonstrated. Nanoparticles were also included in layer-by-layer and self-constructed films in order to improve the electrode specific area.STRASBOURG-Bib.electronique 063 (674829902) / SudocSudocFranceF