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Microplastics are ubiquitous in aquatic ecosystems, but little information is currently available on the dangers and risks to living organisms. In order to assess the ecotoxicity of environmental microplastics (MPs), samples were collected from the beaches of two islands in the Guadeloupe archipelago, Petit-Bourg (PB) located on the main island of Guadeloupe and Marie-Galante (MG) on the second island of the archipelago. These samples have a similar polymer composition with mainly polyethylene (PE) and polypropylene (PP). However, these two samples are very dissimilar with regard to their contamination profile and their toxicity. MPs from MG contain more lead, cadmium and organochlorine compounds while those from PB have higher levels of copper, zinc and hydrocarbons. The leachates of these two samples of MPs induced sublethal effects on the growth of sea urchins and on the pulsation frequency of jellyfish ephyrae but not on the development of zebrafish embryos. The toxic effects are much more marked for samples from the PB site than those from the MG site. This work demonstrates that MPs can contain high levels of potentially bioavailable toxic substances that may represent a significant ecotoxicological risk, particularly for the early life stages of aquatic animals. National Funding Agency | Ref. ANR-15-JOCE-0002-01 Italian Government | Ref. 2017WERYZP Ministerio de Economía | Ref. PCIN-2015-187-C03-03 Ministerio de Economía | Ref. CTM2016-77945-C3 Xunta de Galicia | Ref. ED431C 2017/46

International audience; For several decades, use of nanoparticles (NP) on a global scale has been generating new potential sources of organism disruption. Recent studies have shown that NP can cause modifications on the biochemical macromolecular composition of microalgae and raised questions on the toxicity of plastic particles, which are widespread in the aquatic environment. Polystyrene (PS) particles are among the most widely used plastics in the world. In our experimentation, a combined approach of infrared spectroscopy and molecular biology (real-time PCR) has been applied in order to better apprehend the consequences of interactions between Chlamydomonas reinhardtii, freshwater microalgae and PS NP. Two references have been used, nitrogen deprivation -a well-documented stressor-, and gold nanoparticles (Au-NP). As regards biochemical composition, our experiments show a differing microalga response, according to the NP to which they have been exposed. Results with infrared spectroscopy and gene expression methods are consistent and illustrate variation among several carbohydrates (galactose…). Furthermore, PS-NP seem to react in the same direction as nitrogen limitation, thereby supporting the hypothesis that PS-NP can induce response mechanisms to environmental changes in microalgae. This study highlighted the interest of combining infrared spectroscopy and gene expression as means of monitoring microalgae response to nanoplastics.

International audience; The unicellular photosynthetic organisms known as microalgae are becoming one of the most important models for aquaticsystem studies. Among them, Chlamydomonas reinhardtii is widely used as a bioindicator of pollution or of different changes inthe environment. Numerous pollutants are present in aquatic environments, particularly plastics and nanoplastics. Physiologicalvariations after an environmental change highlight variation in the macromolecular composition of microalgae (proteins, nucleicacids, lipids and carbohydrates). Recently, Fourier transform infrared vibrational spectroscopy has been described as a reliabletool, sensitive and allowing rapid measurement of macromolecular composition of microalgae. Coupled with preprocessing andprincipal component analysis, it is well adapted to monitoring the effect of environmental stress on biochemical composition. Inthis study, infrared spectroscopy, combinedwithmultivariate analysis, has been tested first on known environmental stresses suchas light intensity variation and nitrogen limitation. Then, this technique has been applied to monitor the interaction and potentialimpacts of polystyrene nanoparticles on microalgae. The results showed slight variations on protein and carbohydrates bands inthe presence of nanoplastics, suggesting that their presence led to modifications in the biochemical composition of themicroalgae. To confirm the interaction between microalgae and nanoplastics, visualization by confocal microscopy and cytotoxicitymeasurement has been carried out. Results showed that polystyrene nanoparticles seemed to adsorb on microalgaesurface, leading to a loss of plasma membrane integrity. The resulting chemical modifications, even if moderate, could bedetected by infrared spectroscopy‚ showing that this tool could be very helpful in the understanding of nanoparticlemicroalgaeinteraction mechanisms.

International audience; The aim of the present study was to evaluate the presence and potential toxic effects of plastic fragments (< 400 μm) of polyethylene and polypropylene on the Pacific oyster Crassostrea gigas. Oysters were exposed to environmentally relevant concentrations (0, 0.008, 10, 100 μg of particles/L) during 10 days, followed by a depuration period of 10 days in clean seawater. Effects of microplastics were evaluated on the clearance rate of organisms, tissue alteration, antioxidant defense, immune alteration and DNA damage. Detection and quanti-fication of microplastics in oyster's tissues (digestive gland, gills and other tissues) and biodeposits using infrared microscopy were also conducted. Microplastics were detected in oyster's biodeposits following exposure to all tested concentrations: 0.003, 0.006 and 0.05 particles/mg of biodeposits in oysters exposed to 0.008, 10 and 100 μg of particles/L, respectively. No significant modulation of biological markers was measured in organisms exposed to microplastics in environmentally relevant conditions.

Raman spectroscopy including mapping technique appears as a powerful technique for the characterization of polymer blends like thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs). The Raman spectra of polymers blends such as natural rubber/polypropylene (NR/PP) and 65% hydrogenated natural rubber/polypropylene (65%HNR/PP) were identified and the phase distribution was determined. The study was driven for the same type of blends in TPEs state and TPVs state obtained after to 2 different processes, either peroxide cure or sulfur cure. The morphology of TPEs and TPVs obtained by Raman spectroscopy were compared and confirmed using scanning electronic microscopy. Raman mapping shows that the phase morphology of NR/PP, 65%HNR/PP, were characterized as continuous rubber phase morphology of the thermoplastic elastomers (TPEs) and a fine dispersion of cross-linked rubber phase in a continuous matrix of the thermoplastic vulcanizates (TPVs). Raman spectroscopy is demonstrated to be a reference to determine the content ratio of each component in the TPVs. Moreover, Raman mapping could be used to calculate the phase size of cross-linked rubber phase dispersed in the thermoplastic vulcanizates (TPVs).

Our understanding of the fate and distribution of micro- and nano- plastics in the marine environment is limited by the intrinsic difficulties of the techniques currently used for the detection, quantification, and chemical identification of small particles in liquid (light scattering, vibrational spectroscopies, and optical and electron microscopies). Here we introduce Raman Tweezers (RTs), namely optical tweezers combined with Raman spectroscopy, as an analytical tool for the study of micro- and nanoplastics in seawater. We show optical trapping and chemical identification of sub-20 mu m plastics, down to the 50 nm range. Analysis at the single particle level allows us to unambiguously discriminate plastics from organic matter and mineral sediments, overcoming the capacities of standard Raman spectroscopy in liquid, intrinsically limited to ensemble measurements. Being a microscopy technique, RTs also permits one to assess the size and shapes of particles (beads, fragments, and fibers), with spatial resolution only limited by diffraction. Applications are shown on both model particles and naturally aged environmental samples, made of common plastic pollutants, including polyethylene, polypropylene, nylon, and polystyrene, also in the presence of a thin ecocorona. Coupled to suitable extraction and concentration protocols, RTs have the potential to strongly impact future research on micro and nanoplastics environmental pollution, and enable the understanding of the fragmentation processes on a multiscale level of aged polymers.

The impact of a microplastic (MP) mixture composed of polyethylene (PE) and polypropylene (PP) plastic particles, prepared from commercially available products, was evaluated in blue mussels Mytilus spp. exposed to three environmentally relevant concentrations: 0.008 μg L−1 (low), 10 μg L−1 (medium), and 100 μg L−1 (high). Organisms were exposed for 10 days followed by 10 days of depuration in clean seawater under controlled laboratory conditions. The evaluation of MP effects on mussel clearance rate, tissue structure, antioxidant defenses, immune and digestive parameters, and DNA integrity were investigated while the identification of plastic particles in mussel tissues (gills, digestive gland, and remaining tissues), and biodeposits (feces and pseudofaeces) was performed using infrared microscopy (μFT-IR). Results showed the presence of MPs only in the digestive gland of mussels exposed to the highest tested concentration of MPs with a mean of 0.75 particle/mussel (after the 10 days of exposure). In biodeposits, PE and PP particles were detected following exposure to all tested concentrations confirming the ingestion of MPs by the organisms. A differential response of antioxidant enzyme activities between digestive gland and gills was observed. Significant increases in superoxide dismutase (SOD) and catalase (CAT) activities were measured in the digestive gland of mussels exposed to the low (0.008 μg L−1) and medium (10 μg L−1) concentrations of MPs and in the gills from mussels exposed to the highest concentration (100 μg L−1) of MPs that could be indicative of a change in the redox balance. Moreover, an increase in acid phosphatase activity was measured in hemolymph of mussels exposed to 0.008 and 10 μg L−1 concentrations. No significant difference was observed in the clearance rate, and histopathological parameters between control and exposed mussels. This study brings new insights on the potential sublethal impacts of MPs at environmentally relevant concentrations in marine bivalves.

International audience; Microplastics are ubiquitous in the aquatic environment and polyethylene (PE) fragments are commonly identified in field samples. Studies are needed to evaluate the toxicity of microplastics, especially for the smallest ones that can be ingested by a wide range of organisms. However, due to a lack of preparation methods, small PE microplastics are not often used in laboratory studies. Here, a simple method was developed for the preparation of PE microparticles using dissolution of PE in toluene followed by emulsification in water. After complete evaporation of water and toluene, a powder of PE microparticles was obtained with radii between 0.2 to 0.80 μm. The protocol could be optimized by adding surfactants like Tween 60 or Tween 80, and the possible use of a solution of microalgae exudates as a biosurfactant was also demonstrated. Planktonic crustaceans were exposed to different types of microparticles to evaluate their bioavailability depending on the surfactant.

International audience; Plastic pollution is a source of chemical to the environment and wildlife. Despite the ubiquity of plastic pollution and thus plastic additive in the environment, plastic additives have been studied to a limited extend. As a prerequisite to a study aiming to evaluate the leaching of a common additive used as an antioxidant (Irgafos® 168) from polyethylene microparticles, an inventory of the potential background contamination of the laboratory workplace was done. In this study, Irgafos® 168 (tris(2,4-ditert-butylphenyl) phosphite) and its oxidized form (tris (2,4-ditert-butylphenyl) phosphate) were quantified in different laboratory reagents, including the plastic packaging and the powders, using Pyrolysis-GC/MS. At least one form of Irgafos® 168 was detected in all tested laboratory reagents with higher concentrations in caps and bottles as compared to the powders. Additionally, oxidized Irgafos® 168 was also found in the reverse osmosed and deionized water container used in the laboratory. The same profile of contamination, i.e. higher concentration of the oxidized form and higher concentrations in acidic reagents, was observed when comparing the reagent and their respective containers suggesting that the additive is leaching from the container into the powder. Overall, this study demonstrates that the antioxidant additive Irgafos® 168 is ubiquitous in the laboratory workplace. Plastic additives such as Irgafos® 168 can therefore largely interfere and biased ecotoxicological and toxicological studies especially using environmentally relevant concentrations of microplastics. The source, fate and effects of plastic additive from plastic debris should be carefully considered in future studies that require setting up methods to overcome these contaminations

International audience; New methods for pathogens identification are of growing interest in clinical and food sectors. The challenge remains to develop rapid methods that are more simple, reliable, and specific. Surface-enhanced Raman spectroscopy (SERS) appears to be a promising tool to compete with current untargeted identification methods. This article presents the intensive research devoted to the use of SERS for bacterial identification, from the first to the very recent published results. Compared to normal Raman spectroscopy, the introduction of nanoparticles for SERS acquisition introduces a new degree of complexity. Bacterial Raman fingerprints, which are already subject to high spectral variability for a given strain, become then very dependent on numerous experimental parameters. To overcome these limitations, several approaches have been proposed to prepare the sample, from the microbiological culture conditions to the analysis of the spectrum including the coupling of nanoparticles on the bacterial membrane. Main strategies proposed over the last 20 years are examined here and discussed in the perspective of a protocol transfer towards industry.

In this work, the artificial photodegradation of polyethylene films was studied in laboratory to compare the fragmentation pathways of this polymer at air and in water. Oxidation, surface mechanical properties, crystallinity and crack propagation were monitored to investigate their influence on fragmentation. Without any external stress, fragmentation only occurred in water despite a higher level of oxidation for films weathered at air. The cracking of the films did not appear correlated with the oxidation level and the presence of water appeared as a promoter of cracking propagation. The results also showed that the mechanical properties at the surface play a major role in the fragmentation pathway whereas the fabrication process may influence the propagation direction of the cracks. Consequently, the distribution in size of plastic fragments in the aquatic environment may be linked to the nature of the polymer but also to its manufacturing process. In this study, after 25 weeks of weathering in water, 90% of the fragments were1 mm with very similar shapes showing that micrometric fragments were not yet abundant. These results suggest that long times of weathering in water and many steps of fragmentation appear necessary from macroplastics to reach sizes1 mm in the aquatic environment. These results constitute a first attempt to understand the pathways leading from macroplastics to microplastics in water. They have to be confirmed for other polymers and the long-term behavior of the fragments needs to be studied to predict their decrease in size among time.

International audience; Marine plastic pollution is a major environmental issue. Given their ubiquitous nature and small dimensions, ingestion of microplastic (MP) and nanoplastic (NP) particles and their subsequent impact on marine life are a growing concern worldwide. Transfers along the trophic chain, including possible translocation, for which the hazards are less understood, are also a major preoccupation. Effects of MP ingestion have been studied on animals through laboratory exposure, showing impacts on feeding activity, reserve depletion and inflammatory responses, with consequences for fitness, notably reproduction. However, most experimental studies have used doses of manufactured virgin microspheres that may not be environmentally realistic. As for most ecotoxicological issues, the environmental relevance of laboratory exposure experiments has recently been debated. Here we review constraints and priorities for conducting experimental exposures of marine wildlife to microplastics based on the literature, feedback from peer reviewers and knowledge gained from our experience. Priorities are suggested taking into account the complexity of microplastics in terms of (i) aggregation status, surface properties and interactions with organic and inorganic materials, (ii) diversity of encountered particles types and concentrations, (iii) particle bioavailability and distribution in experimental tanks to achieve reproducibility and repeatability in estimating effects, and (iv) strict experimental procedures to verify the existence of genuine translocation. Relevant integrative approaches encompass a wide spectrum of methods from -omics to ecophysiological approaches, includingmodeling, are discussed to provide novel insights on the impacts of MP/NP on marine ecosystems from a long-term perspective. Knowledge obtained in this way would inform stakeholders in such a way as to help them mitigate impacts of the micro- and nano-plastic legacy.

The ubiquitous presence of microplastics (MPs) has been demonstrated in all environmental compartments in the recent years. They are detected in air, freshwater, soil, organisms and particularly in marine ecosystems. Since sediments are known to be the major sink of many organic and inorganic pollutants, the aim of this study was to develop and validate a fast and cheap methodology to assess the MP contamination in intertidal sediments from the Gulf of Biscay (Pays de la Loire region, France). Sediments were sampled at three locations (Pays de la Loire region, France) and during two seasons: October 2015 and March 2016. The analytical protocol involved MP extraction from dried sediments using milliQ water and a centrifugation technique. After a filtration step of supernatants, MPs were detected and directly identified on the membrane filters using μFTIR spectroscopy in reflection mode. For the first time, the number of replicates allowing to obtain a satisfying representativeness of the whole sampled sediment was also evaluated at 10 replicates of 25 g each. The average number of MPs in sediments was 67 (±76) MPs/kg dw (N = 60) with no significant difference between sites and seasons. Ten different compositions of MPs were defined by μFT-IR with a high proportion of polypropylene (PP) and polyethylene (PE), 38 and 24%, respectively. Among MPs, mainly fragments (84%) were observed with main size classes corresponding to [100 μm] and [50-100 μm] but no particles 1 mm could be found suggesting that mainly small microplastics (1 mm) were subject to vertical transport.

Monitoring the presence of microplastics (MP) in marine organisms is currently of high importance. This paper presents the qualitative and quantitative MP contamination of two bivalves from the French Atlantic coasts: the blue mussel (Mytilus edulis) and the Pacific oyster (Crassostrea gigas). Three factors potentially influencing the contamination were investigated by collecting at different sampling sites and different seasons, organisms both wild and cultivated. Inter- and intra-species comparisons were also achieved. MP quantity in organisms was evaluated at 0.61±0.56 and 2.1±1.7MP per individual respectively for mussels and oysters. Eight different polymers were identified. Most of the MPs were fragments; about a half of MPs were grey colored and a half with a size ranging from 50 to 100μm for both studied species. Some inter-specific differences were found but no evidence for sampling site, season or mode of life effect was highlighted.

Microplastics (MPs) constitute a main environmental issue due to their threat to marine organisms and so far to humans. The lack of a fast standard protocol in MP isolation and identification from living organisms bring to challenge for the science. In this paper, an optimized protocol using potassium hydroxide 10% (KOH 10%; m/v) for digestion of mussel soft tissues (Mytilus edulis) and multi-steps of sedimentation has been developed. Efficiency higher than 99.9% of organic and mineral matter elimination was shown by application on mussels sampled on the French Atlantic coast. The identification of MPs was performed by FTIR microscopy straight on the filter and the whole analysis can be compatible with a routine goal. Fourteen MPs of four different chemical natures were found and identified in 5 pools of 3 sampled mussels. Their size ranged from 30 to 200 μm. Further investigations are now needed to evaluate the potential risk of such particles within this marine bivalve species and other filter feeders.

The ozone stability of partially hydrogenated natural rubbers (HNRs) was evaluated. HNRs with the hydrogenation levels of 14, 33 and 65 mol% including with vulcanization systems of peroxide and sulfur on ozone stability comparing with natural rubber (NR) and ethylene-propylene-diene-rubber (EPDM) vulcanizates were studied. The chemical structures of rubber vulcanizates were characterized by Raman spectroscopy. The surface cracks were observed by Raman optical microscopy. The results clearly exhibited that the ozone stability of HNRs vulcanizates was much greater than that of the NR vulcanizates. The difference between the integral intensities of C=C bonds of isoprene units in rubber chains by Raman spectroscopy before and after ozone exposed was minimized with the degree of hydrogenation. The depth of cracking observed by three-dimensional (3D) modes clearly decreased with an increase in the degree of hydrogenation, while no cracks on the surface of EPDM were found. These findings indicated that ozone stability increased with the degree of hydrogenation. Regarding the effect of vulcanizing systems, sulfur cure showed greater resistance to ozone degradation than peroxide cure.

Baztan, Juan ... et al.-- MICRO 2016, 25-27 May 2016, Lanzarote, Spain.-- 5 pages

In this work, two sets of samples were considered: field samples collected from local waste wood and synthetic samples made by mixing clean wood (including oak, beech, poplar) with typical organic pollutants: creosote, polychlorinated byphenils (PCBs), pentachlorophenol (PCP), cypermethrin, dodecyl dimethyl ammonium chloride (DDAC). Vibrational spectroscopy techniques were tested to detect organic pollutants in wood items. Raman and infrared spectroscopies were showed as fast, non-destructive and non-invasive fingerprint techniques for detection of organic molecules. Associated with principal component analysis, we have shown the evidence of quick detection of and discrimination of polluted wood items by kinds and versus concentration.

In this work, we present a new complete method using Surface Enhanced Raman Spectroscopy (SERS) and chemometrics for the qualitative and quantitative detection of pesticides by measuring the acetylcholinesterase (ACHE) activity. The Raman SERS is not only used for measuring the ACHE activity, but also for the direct detection of pesticides individually and for their identification. Gold nanoparticles (AuNPs) were used as dynamic SERS substrates for sensitive monitoring of ACHE activity in the presence of very low levels of organophosphate and carbamate pesticides, chemical warfare agents that are known to be ACHE inhibitors. The lowest detectable level for paraoxon was determined at 4.0 x 10(-14)M and 1.9 x 10(-9)M for carbaryl. The use of the enzyme allowed limits of detection for both pesticides that were much lower than the limits obtained by direct SERS analysis of the pesticides. The system shows a linear relationship between the intensity band at 639 cm(-1) and pesticide concentration. These results suggest that this biosensor could be used in the future for the non-selective detection of all ACHE inhibitors at very low concentrations with possible identification of the inhibitor. (C) 2016 Elsevier B.V. All rights reserved.

In this study, the interactions between microplastics, chosen among the most widely used in industry such as polypropylene (PP) and high-density polyethylene (HDPE), and a model freshwater microalgae, Chlamydomas reinhardtii, were investigated. It was shown that the presence of high concentrations of microplastics with size >400 μm did not directly impact the growth of microalgae in the first days of contact and that the expression of three genes involved in the stress response was not modified after 78 days. In parallel, a similar colonization was observed for the two polymers. However, after 20 days of contact, in the case of PP only, hetero-aggregates constituted of microalgae, microplastics and exopolysaccharides were formed. An estimation of the hetero-aggregates composition was approximately 50% of PP fragments and 50% of microalgae, which led to a final density close to 1.2. Such hetero-aggregates appear as an important pathway for the vertical transport of PP microplastics from the water surface to sediment. Moreover, after more than 70 days of contact with microplastics, the microalgae genes involved in the sugar biosynthesis pathways were strongly over-expressed compared to control conditions. The levels of over-expression were higher in the case of HDPE than in PP condition. This work presents the first evidence that depending on their chemical nature, microplastics will follow different fates in the environment.

The ubiquitous presence and persistency of microplastics (MPs) in aquatic environments are of particular concern since they represent an increasing threat to marine organisms and ecosystems. Great differences of concentrations and/or quantities in field samples have been observed depending on geographical location around the world. The main types reported have been polyethylene, polypropylene, and polystyrene. The presence of MPs in marine wildlife has been shown in many studies focusing on ingestion and accumulation in different tissues, whereas studies of the biological effects of MPs in the field are scarce. If the nature and abundance/concentrations of MPs have not been systematically determined in field samples, this is due to the fact that the identification of MPs from environmental samples requires mastery and execution of several steps and techniques. For this reason and due to differences in sampling techniques and sample preparation, it remains difficult to compare the published studies. Most laboratory experiments have been performed with MP concentrations of a higher order of magnitude than those found in the field. Consequently, the ingestion and associated effects observed in exposed organisms have corresponded to great contaminant stress, which does not mimic the natural environment. Medium contaminations are produced with only one type of polymer of a precise sizes and homogenous shape whereas the MPs present in the field are known to be a mix of many types, sizes and shapes of plastic. Moreover, MPs originating in marine environments can be colonized by organisms and constitute the sorption support for many organic compounds present in environment that are not easily reproducible in laboratory. Determination of the mechanical and chemical effects of MPs on organisms is still a challenging area of research. Among the potential chemical effects it is necessary to differentiate those related to polymer properties from those due to the sorption/desorption of organic compounds.

Bayram, Cem/0000-0001-8717-4668; Cetin, Demet/0000-0003-1186-4229; SULUDERE, ZEKIYE/0000-0002-1207-5814; Tamer, Ugur/0000-0001-9989-6123; Greneche, Jean-Marc/0000-0001-7309-8633; Lagarde, Fabienne/0000-0002-4015-4376 WOS: 000341752200001 The high product yield of multi-branched core-shell Fe3-x O-4@Au magnetic nanoparticles was synthesized used as magnetic separation platform and surface-enhanced Raman scattering (SERS) substrates. The multi-branched magnetic nanoparticles were prepared by a seed-mediated growth approach using magnetic gold nanospheres as the seeds and subsequent reduction of metal salt with ascorbic acid in the presence of a stabilizing agent chitosan biopolymer and silver ions. The anisotropic growth of nanoparticles was observed in the presence of chitosan polymer matrix resulting in multi-branched nanoparticles with a diameter over 100 nm, and silver ions also play a crucial role on the growth of multi-branched nanoparticles. We propose the mechanism of the formation of multi-branched nanoparticles while the properties of nanoparticles embedded in chitosan matrix are discussed. The surface morphology of nanoparticles was characterized with transmission electron microscopy, scanning electron microscopy, ultraviolet visible spectroscopy (UV-Vis), X-ray diffraction, and fourier transform infrared spectroscopy and Fe-57 Mossbauer spectrometry. Additionally, the magnetic properties of the nanoparticles were also examined. We also demonstrated that the synthesized Fe3-x O-4@Au multi-branched nanoparticle is capable of targeted separation of pathogens from matrix and sensing as SERS substrates. Scientific and Technological Research Council (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [108T794, 111T983]; Gazi BAPGazi University [05/2004-03, 05/2011-69] This work was supported by the Scientific and Technological Research Council (TUBITAK) grant numbers 108T794 and 111T983. We also acknowledge support from Gazi BAP, project number 05/2004-03 and 05/2011-69. We would like to thank Gokhan Demirel and Mehmet Yilmaz for 3D simulation. We also thank to Dr Saime Sebnem Cetin and Prof.Dr. Suleyman Ozcelik for XRD measurements.

Natural rubber/styrene-butadiene rubber (NR/SBR) blends, with and without silica, were prepared by co-coagulating the mixture of rubber latices and various amounts of well-dispersed silica suspension. An attempt to predict blend compositions was made using Raman spectroscopy in association with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It was found that the intensity of each Raman characteristic peak was strongly dependent on the blend composition, but there was no significant evolution with the presence of silica. Also, TGA results revealed an improvement in thermal stability of NR/SBR blends with increasing both SBR and silica contents due to the dilution effect. Two distinct glass transition temperatures (Tg) were observed in DSC thermograms of all blends, and their Tg values were independent on both blend composition and silica content. This indicated a physical blend formation, which agreed well with no shifts in Raman peaks of the blends in comparison with those of the individual rubbers. Linear regression with R2 quality factor close to 0.99 was achieved when plotting intensity ratio at 1371/1302 cm−1 versus blend ratios. On the other hand, the peak height ratio and heat capacity ratio from TGA and DSC analysis, respectively, yielded quadratic equations as a function of blend ratios.

International audience; Un polymère de type polythiophène comportant des groupements chlorure de parabenzenesulfonile a été synthétisé par voie électrochimique afin d'obtenir une surface destinée à ` l'immobilisation rapide et efficiente de biomolécules. Graceà une liaison sulfonamide, une protéine A a ainsi été fixée pour permettre l'accroche et l'orientation d'un anticorps spécifique. Le dispositif a pu être testé pour piéger une bactérie pathogène ''Salmonella enterica paratyphi''. La présence de la bactérie sur la surface a e ´té vérifiée conjointement par microbalance a ` quartz et par spectroscopie Raman. Les résultats obtenus ont e ´té comparés a ` ceux obtenus sur une surface d'or fonctionnalisée selon le même procédé et ils témoignent de la très grande réactivité de la surface polymère. Ce procédé de fonctionnalisation de surface, facile a ` mettre en oeuvre, spécifique et peu coûteux, constitue, par couplage avec la technique de diffusion Raman, une méthode alternative potentielle de détection et identification rapide de micro-organismes pathogènes.; A simple electrochemical procedure was used for the synthesis of a polythiophene containing para-ben-zenesulfonyl chloride groups. The obtained polymer was shown to be very reactive and directly able to covalently bind nucleophile biomolecules. Protein A and a specific antibody were then successively immobilized on the conductive polymer through a covalent bonding of Protein A with the as-prepared linker for bacteria trapping purpose. All reactions were controlled in situ by cyclic voltammetry, quartz crystal microbalance and Raman spectroscopy. The results were compared to those previously obtained on gold surface modified with the same chemical linker. The conductive polymer led to a very high rate of antibody recognition compared to the gold surface and to literature, probably due to a large available surface obtained after polymerization. One example of pathogenic bacteria ''Salmonella enterica paratyphi'' detection was successfully tested on the substrates. The presented results are promising for the future design of simple and inexpensive immunocapture-based sensors

Interaction and surface binding characteristics of staphylococcal protein A (SpA) and an anti-Escherichia coli immunoglobulin G (IgG) were studied using the Raman spectroscopy. The tyrosine amino acid residues present in the α-helix structure of SpA were found to be involved in interaction with IgG. In bulk interaction condition the native structure of proteins was almost preserved where interaction-related changes were observed in the overall secondary structure (α-helix) of SpA. In the adsorbed state, the protein structure was largely modified, which allowed the identification of tyrosine amino acids involved in SpA and IgG interaction. This study constitutes a direct Raman spectroscopic investigation of SpA and IgG (receptor-antibody) interaction mechanism in the goal of a future biosensor application for detection of pathogenic microorganisms.

We present a new and advanced methodology, developed for surface functionalisation of gold and to study immobilisation of an immuno-specific system of proteins. A combination of electrochemical quartz crystal microbalance and Raman spectroscopy techniques allowed a complete understanding of the system starting from surface functionalisation and progressing to the functional structure analysis of immobilised proteins. A simple electrochemical procedure was formulated to prepare sulphonyl chloride terminated gold surfaces that form a strong sulphonamide bond with the receptor protein staphylococcal protein A (SpA). On the SpA grafted surfaces, the immobilisation of a human IgG and consecutive binding of an immuno-specific anti-human IgG was observed. The surface functional groups form a strong interaction with SpA without disturbing its functional properties. The native functional structure of SpA and also the IgGs was found to be retained in their immobilised state.

This paper provides a detailed investigation of the mass transfers involved in chemical oxygen demand (COD) and N removal in an intermittent aeration activated sludge plant, as described by the widely used ASM1 model. The model was calibrated and validated on a data set obtained during three intensive sampling campaigns. The mass transfers of COD and nitrogen were calculated with the calibrated model for every biodegradable variable of the model in each tank of the biological treatment. Only by making this balance can evaluation of the contribution of each reactor (anaerobic, anoxic and intermittently aerated) to carbon and nitrogen removal be done. It was pointed out that in such a plant (activated sludge under very low organic mass loading (F/M)ratios, sludge retention time of 30 days) operating at 20, Cet article fournit une analyse détaillée des tansferts de masse simulés par le modèle ASM1 lors de la dégradation de la DCO et de l'azote ndas une station d'épuration boues activées en aération prolongée. Le modèle a été calibré et validé sur une ensemble de données obtenues pendant trois campagnes de mesures. Les tranferts de masse ont été calculés avec le modèle calibré, pour chaque variable biodégradable du modèle, dans chacun des bassins du traitement biologique. C'est seulement en faisant de tels bilans de masse que l'on peut évaluer la contribution de chaque bassin (anaéorbique, anoxique et aération) à la dégradation du carbone et de l'azote. Dans une telle station (boues activées en aération prolongée, SRT 30 jours), à 20°C, la contribution de la zone anoxique à la dénitrification est très faible (seulement 17%)/ Le transfert d'oxygène dans ce nasso, a également été estimé et est probablement responsable de cette faible efficacité.

International audience; This paper presents a methodology for assessing the variability of biodegradable chemical oxygen demand (COD) fractions in urban wastewaters. Thirteen raw wastewater samples from combined and separate sewers feeding the same plant were characterised, and two optimisation procedures were applied in order to evaluate the variability in biodegradable fractions and related kinetic parameters. Through an overall optimisation on all the samples, a unique kinetic parameter set was obtained with a three-substrate model including an adsorption stage. This method required powerful numerical treatment, but improved the identifiability problem compared to the usual sample-to-sample optimisation. The results showed that the fractionation of samples collected in the combined sewer was much more variable (standard deviation of 70% of the mean values) than the fractionation of the separate sewer samples, and the slowly biodegradable COD fraction was the most significant fraction (45% of the total COD on average). Because these samples were collected under various rain conditions, the standard deviations obtained here on the combined sewer biodegradable fractions could be used as a first estimation of the variability of this type of sewer system.

International audience; Two different re-oxygenation techniques (aeration and peroxide addition) were compared in respirometric experiments. As similar results were obtained in both cases, it was concluded that the addition of peroxide did not modify the respirations under either endogenous or feeding conditions. The respiration rates obtained with the aeration were often more scattered due to the adhesion of fine bubbles to the probes after the switch off of the aeration. Moreover, the transfer rate of oxygen to the solution is faster in the case of H2O2 addition.; Deux techniques différentes de réoxygénation (aération et eau oxygénée) ont été comparées au cours d'expériences de respirométrie. Des résultats similaires étant obtenus dans les deux cas, on a conclu que l'addition d'eau oxygénée ne modifiait ni la biodégradabilité du substrat, ni les taux de croissance de la biomasse hétérotrophe, en conditions endogènes ou alimentées. Les respirations obtenues avec l'aération sont plus dispersées à cause de l'adhésion de fines bulles sur les sondes. De plus, le transfert de l'oxygène dissous est plus rapide dans le cas d'addition d'eau oxygénée.