Synthesis of Supported Catalysts by Dry Impregnation in Fluidized Bed

The synthesis of catalytic or not composite materials by dry impregnation in fluidized bed is described. This process can be carried out under mild conditions from solutions of organometallic precursors or colloidal solutions of preformed nanoparticles giving rise to reproducible metallic nanoparticles containing composite materials with a high reproducibility. The adequate choice of the reaction conditions makes possible to deposit uniformly the metal precursor within the porous matrix or on the support surface. When the ratio between the drying time and the capillary penetration time (tsec/tcap) is higher than 10, the impregnation under soft drying conditions leads to a homogeneous deposit inside the pores of the particles of support. The efficiency of the metal deposition is close to 100%, and the size of the formed metal nanoparticles is controlled by the pores diameter. Finally, some of the presented composite materials have been tested as catalysts: iron-based materials were used in carbon-nanotubes synthesis, while Pd and Rh composite materials have been investigated in hydrogenation reactions

Dry impregnation in fluidized bed: Drying and calcination effect on nanoparticles dispersion and location in a porous support

The synthesis of metal nanoparticles dispersed inside the grains of a porous inorganic support was carried out by ‘‘dry impregnation’’ in a fluidized bed. The principle of this technique consists in the spraying of a solution containing a metal source into a hot fluidized bed of porous particles. The metal source can be of different nature such as metal salts, organometallic precursors or colloidal solutions. The experimental results obtained from iron oxide deposition on a porous silica gel as support, constitute the core of this article but others results concerning the deposition of rhodium from a colloidal suspension containing preformed rhodium nanoparticles are also described. More precisely, this study aims to understand the effect of the bed temperature during the impregnation step, the initial particle porosity and the calcination operating protocol on the metallic nanoparticles dispersion and location in the silica porous particles. The so-obtained products were characterized by various techniques in order to determine their morphology, their surface properties and the dispersion of the nanoparticles inside the support. The results showed that, under the chosen operating conditions, the deposit efficiency is close to 100% and the competition between the drying rate, depending on the process-related variables, and the capillary penetration rate, depending on the physicochemical-related variables, controls the deposit location. A quasi uniform deposit inside the support particles is observed for soft drying. The metal nanoparticles size is controlled by the pore mean diameter of the support as well as the calcination operating protocol

Frequency and Diversity of Nitrate Reductase Genes among Nitrate-Dissimilating Pseudomonas in the Rhizosphere of Perennial Grasses Grown in Field Conditions

A total of 1246 Pseudomonas strains were isolated from the rhizosphere of two perennial grasses (Lolium perenne and Molinia coerulea) with different nitrogen requirements. The plants were grown in their native soil under ambient and elevated atmospheric CO2 content (pCO2) at the Swiss FACE (Free Air CO2 Enrichment) facility. Root-, rhizosphere-, and non-rhizospheric soil-associated strains were characterized in terms of their ability to reduce nitrate during an in vitro assay and with respect to the genes encoding the membrane-bound (named NAR) and periplasmic (NAP) nitrate reductases so far described in the genus Pseudomonas. The diversity of corresponding genes was assessed by PCR-RFLP on narG and napA genes, which encode the catalytic subunit of nitrate reductases. The frequency of nitrate-dissimilating strains decreased with root proximity for both plants and was enhanced under elevated pCO2 in the rhizosphere of L. perenne. NAR (54% of strains) as well as NAP (49%) forms were present in nitrate-reducing strains, 15.5% of the 439 strains tested harbouring both genes. The relative proportions of narG and napA detected in Pseudomonas strains were different according to root proximity and for both pCO2 treatments: the NAR form was more abundant close to the root surface and for plants grown under elevated pCO2. Putative denitrifiers harbored mainly the membrane-bound (NAR) form of nitrate reductase. Finally, both narG and napA sequences displayed a high level of diversity. Anyway, this diversity was correlated neither with the root proximity nor with the pCO2 treatmen

Compared to conventional, ecological intensive management promotes beneficial proteolytic soil microbial communities for agro-ecosystem functioning under climate change-induced rain regimes

Projected climate change and rainfall variability will affect soil microbial communities, biogeochemical cycling and agriculture. Nitrogen (N) is the most limiting nutrient in agroecosystems and its cycling and availability is highly dependent on microbial driven processes. In agroecosystems, hydrolysis of organic nitrogen (N) is an important step in controlling soil N availability. We analyzed the effect of management (ecological intensive vs. conventional intensive) on N-cycling processes and involved microbial communities under climate change-induced rain regimes. Terrestrial model ecosystems originating from agroecosystems across Europe were subjected to four different rain regimes for 263 days. Using structural equation modelling we identified direct impacts of rain regimes on N-cycling processes, whereas N-related microbial communities were more resistant. In addition to rain regimes, management indirectly affected N-cycling processes via modifications of N-related microbial community composition. Ecological intensive management promoted a beneficial N-related microbial community composition involved in N-cycling processes under climate change-induced rain regimes. Exploratory analyses identified phosphorus-associated litter properties as possible drivers for the observed management effects on N-related microbial community composition. This work provides novel insights into mechanisms controlling agro-ecosystem functioning under climate change

General palaeontology (Palaeobiochemistry) Biological activity and the Earth's surface evolution: Insights from carbon, sulfur, nitrogen and iron stable isotopes in the rock record

Abstract The search for early Earth biological activity is hindered by the scarcity of the rock record. The very few exposed sedimentary rocks have all been affected by secondary processes such as metamorphism and weathering, which might have distorted morphological microfossils and biogenic minerals beyond recognition and have altered organic matter to kerogen. The search for biological activity in such rocks therefore relies entirely on chemical, molecular or isotopic indicators. A powerful tool used for this purpose is the stable isotope signature of elements related to life (C, N, S, Fe). It provides key informations not only on the metabolic pathways operating at the time of the sediment deposition, but more globally on the biogeochemical cycling of these elements and thus on the Earth's surface evolution. Here, we review the basis of stable isotope biogeochemistry for these isotopic systems. Rather than an exhaustive approach, we address some examples to illustrate how they can be used as biosignatures of early life and as proxies for its environment, while keeping in mind what their limitations are. We then focus on the covariations among these isotopic systems during the Archean time period to show that they convey important information both on the evolution of the redox state of the terrestrial surface reservoirs and on co-occurring ecosystems in the Archean. Résumé Apport des isotopes stables (C, N, S, Fe) à l'étude des interrelations entre activités biologiques et conditions physicochimiques de surface de la terre primitive. La recherche et la caractérisation des écosystèmes à la surface de la Terre primitive sont un défi, étant donné le faible degré de préservation des roches archéennes. Les quelques formations sédimentaires disponibles ont, en effet, été modifiées par de nombreux processus secondaires (métamorphisme, altération) qui excluent toute diagnose morphologique robuste des microfossiles et des minéraux associés. La recherche de traces de vie fossile et la caractérisation des environnements contemporains du dépôt reposent ainsi sur des indices chimiques dont les plus robustes sont les isotopes stables. Dans ce manuscrit, nous tenterons de résumer les bases de la biogéochimie des isotopes stables et nous illustrerons comment cette discipline peut permettre d'apporter des contraintes sur la vie primitive et son environnement. Quelques exemples choisis dans différents systèmes isotopiques pertinents pour l'étude de la vie (C, N, S, Fe) et pour l'étude des conditions d'oxydation de surface de la Terre primitiv

General palaeontology (Palaeobiochemistry) Biological activity and the Earth's surface evolution: Insights from carbon, sulfur, nitrogen and iron stable isotopes in the rock record

Abstract The search for early Earth biological activity is hindered by the scarcity of the rock record. The very few exposed sedimentary rocks have all been affected by secondary processes such as metamorphism and weathering, which might have distorted morphological microfossils and biogenic minerals beyond recognition and have altered organic matter to kerogen. The search for biological activity in such rocks therefore relies entirely on chemical, molecular or isotopic indicators. A powerful tool used for this purpose is the stable isotope signature of elements related to life (C, N, S, Fe). It provides key informations not only on the metabolic pathways operating at the time of the sediment deposition, but more globally on the biogeochemical cycling of these elements and thus on the Earth's surface evolution. Here, we review the basis of stable isotope biogeochemistry for these isotopic systems. Rather than an exhaustive approach, we address some examples to illustrate how they can be used as biosignatures of early life and as proxies for its environment, while keeping in mind what their limitations are. We then focus on the covariations among these isotopic systems during the Archean time period to show that they convey important information both on the evolution of the redox state of the terrestrial surface reservoirs and on co-occurring ecosystems in the Archean. Résumé Apport des isotopes stables (C, N, S, Fe) à l'étude des interrelations entre activités biologiques et conditions physicochimiques de surface de la terre primitive. La recherche et la caractérisation des écosystèmes à la surface de la Terre primitive sont un défi, étant donné le faible degré de préservation des roches archéennes. Les quelques formations sédimentaires disponibles ont, en effet, été modifiées par de nombreux processus secondaires (métamorphisme, altération) qui excluent toute diagnose morphologique robuste des microfossiles et des minéraux associés. La recherche de traces de vie fossile et la caractérisation des environnements contemporains du dépôt reposent ainsi sur des indices chimiques dont les plus robustes sont les isotopes stables. Dans ce manuscrit, nous tenterons de résumer les bases de la biogéochimie des isotopes stables et nous illustrerons comment cette discipline peut permettre d'apporter des contraintes sur la vie primitive et son environnement. Quelques exemples choisis dans différents systèmes isotopiques pertinents pour l'étude de la vie (C, N, S, Fe) et pour l'étude des conditions d'oxydation de surface de la Terre primitiv

Polymer versus phosphine stabilized Rh nanoparticles as components of supported catalysts : implication in the hydrogenation of cyclohexene model molecule

The solution synthesis of rhodium nanoparticles (Rh NPs) was achieved from the organometallic complex [Rh(η³-C₃H₅)₃] under mild reaction conditions in the presence of a polymer (PVP), a monophosphine (PPh₃) and a diphosphine (dppb) as a stabilizer, leading to very small Rh NPs of 2.2, 1.3 and 1.7 nm mean size, with PVP, PPh3 and dppb, respectively. The surface properties of these nanoparticles were compared using a model catalysis reaction namely, hydrogenation of cyclohexene, first under colloidal conditions and then under supported conditions after their immobilization onto an amino functionalized silica-coated magnetite support. PVP-stabilized Rh NPs were the most active catalyst whatever the catalytic conditions as a result of a strong coordination of the phosphine ligands at the metal surface that blocks some surface atoms even after several recycles of the supported nanocatalysts and limit the reactivity of the metallic surface

Metabolic flexibility as a major predictor of spatial distribution in microbial communities

A better understand the ecology of microbes and their role in the global ecosystem could be achieved if traditional ecological theories can be applied to microbes. In ecology organisms are defined as specialists or generalists according to the breadth of their niche. Spatial distribution is often used as a proxy measure of niche breadth; generalists have broad niches and a wide spatial distribution and specialists a narrow niche and spatial distribution. Previous studies suggest that microbial distribution patterns are contrary to this idea; a microbial generalist genus (Desulfobulbus) has a limited spatial distribution while a specialist genus (Methanosaeta) has a cosmopolitan distribution. Therefore, we hypothesise that this counter-intuitive distribution within generalist and specialist microbial genera is a common microbial characteristic. Using molecular fingerprinting the distribution of four microbial genera, two generalists, Desulfobulbus and the methanogenic archaea Methanosarcina, and two specialists, Methanosaeta and the sulfate-reducing bacteria Desulfobacter were analysed in sediment samples from along a UK estuary. Detected genotypes of both generalist genera showed a distinct spatial distribution, significantly correlated with geographic distance between sites. Genotypes of both specialist genera showed no significant differential spatial distribution. These data support the hypothesis that the spatial distribution of specialist and generalist microbes does not match that seen with specialist and generalist large organisms. It may be that generalist microbes, while having a wider potential niche, are constrained, possibly by intrageneric competition, to exploit only a small part of that potential niche while specialists, with far fewer constraints to their niche, are more capable of filling their potential niche more effectively, perhaps by avoiding intrageneric competition. We suggest that these counter-intuitive distribution patterns may be a common feature of microbes in general and represent a distinct microbial principle in ecology, which is a real challenge if we are to develop a truly inclusive ecology