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One of the industrial ecology fulfillments is the concept of eco-industrial park (EIP). This cooperative approach leads to a more resources-efficient production system at the park scale, namely a more sustainable industrial system. Eco-industrial parks are generally growing on existing industrial area. Existing methodological and technical tools could support such development in this context but this work aims to support initiative for the preliminary design and layout of industrial ecosystem in a new area. If the management of area allows to fulfill the technical and economic factors for many eco-industrial synergies, this is unsatisfactory concerning the relationships issues. The study of the life cycle of the park underlines importance of the layout and commercialization phases. It makes it possible to select the best technical and economical compromise for synergies and to plan and ease future information exchange, collaborative context and trust. The experimental field is a 200ha park in Occitanie region namely “Les Portes du Tarn”, 20 km far from Toulouse (south of France). SPLA81 urban planning agency started the ecosystem development process in 2012 and needs for a formal methodology and a toolbox for layout and commercialization process and its related decisions. The scientific proposal targets the development of a simple and operational group-based decision-making methodology for industrial ecology, especially to prospect and approve a company to join the park and its territory, to identify the “optimal” synergies and to select the appropriate slot within the park area. The first applicant, a wine production industrial unit, applies this approach to join the industrial park.

We propose a dedicated tool that permits the evaluation of food production process sustainability, in particular virgin olive oil process. It is based on an integrated process-product-enterprise (P²E) approach that allows systematically taking into account sustainable issues within food production process design. The domain specific tool “&cOlive” is implemented as an Excel application. This CAPE based tool assesses sustainability of a future or an existing system of virgin olive oil production. In the first case, 28 configurations of the system may be chosen based on 7 agricultural scenarios and 4 industrial scenarios (extraction).These scenarios were built with field data directly collected through questionnaires and visits of olive oil producers in France, in the context of the European OiLCA project. Complementary data were provided by French experts from the Centre Technique de l’Olivier. They completed and reinforced the relevance and the quality of the model. Finally, commercial databases such as Ecoinvent for environmental LCA were used. The tool offers the opportunity to simulate a lot of scenarios and to study the influence of different extraction technologies and different operating parameters on sustainability.

With the rise of global warming issues due to the increase of the greenhouse gas emission and more generally with growing importance granted to sustainable development, process system engineering (PSE) has turned to think more and more environmentally. Indeed, the chemical engineer has now taken into account not only the economic criteria of the process, but also its environmental and social performances. To evaluate such non-economic performances is challenging and arduous. For this purpose, many approaches could be taken into consideration like environmental impact assessment, environmental impact indices, environmental risk assessment, cost-benefit analysis, life cycle assessment (LCA) and Social LCA. Among these approaches, the coupling of PSE and LCA will be investigated here because it is viewed as a good instrument to evaluate the environmental performance of different unitary processes and whole process. The coupling can be of different nature depending on the focus of the study. Either the study is focused on PSE with an associated LCA study (LCA applied to PSE), or LCA study including mass balance and energy balance (PSE applied to LCA). PSE mainly focuses on design, operation, control and optimization of process with the help of computer based methods i.e. Computer Aided Process Engineering (CAPE). In this study we proceed to an environmental analysis of a non-food agro-process (i.e. biodiesel production from Jatropha) applying our CAPE based LCA proposal. To complement the experimental data the highly impactful unitary processes (i.e. transesterification) is selected for further analysis via simulation. A modelling tool on Microsoft Excel is developed to link LCA and process simulation. For results validation we also implement LCA in a dedicated tool (SIMAPRO) and simulation in a CAPE simulator (ProSim Plus). Furthermore this development of simulation based LCA framework can serve as a step forward for determination of sustainability and eco-efficient designing.

Quoique l'utilisation agricole des déchets ou produits organiques (déjections animales, boues, composts) apparaisse intuitivement comme une pratique bénéfique pour l'environnement, la démonstration objective du bien-fondé environnemental des filières de gestion biologique se révèle difficile, tant sur le choix des critères à prendre en compte que sur l'évaluation de ces critères. Le travail présenté ici visait à rassembler les connaissances de base nécessaires à la réalisation d'évaluations environnementales globales du type " analyse de cycle de vie " de ces filières. Autant que possible, toutes les catégories d'impact potentiel, ainsi que toutes les étapes de traitement ont été considérées, y compris la phase suivant le retour au sol des produits. L'étude a comporté deux phases : la collecte des données disponibles dans la littérature sur les rejets et consommations de substances et d'énergie associés à ces différentes étapes, puis la mise en cohérence des valeurs retenues pour chaque facteur d'impact dans un format directement utilisable par les outils d'évaluation environnementale. Globalement, au regard de la grande sensibilité des facteurs d'impact à la nature des produits ainsi qu'aux conditions de traitement et de milieu (température, type de sol), les connaissances disponibles s'avèrent souvent beaucoup trop partielles en termes, à la fois, d'acquisition de données en conditions réelles et de compréhension des phénomènes mis en jeu.

The aim of this article is to compare two different sets of optimal conditions for twin-screw extraction of xylans and define their influence on the purification steps, combining ultrafiltration and industrial chromatography. Two xylan extracts were obtained by twin-screw extrusion of straw and bran. Condition 1 used a high straw/bran ratio (equal to 6) and high sodium hydroxide content, and condition 2 used a lower straw/bran ratio (equal to 2) and low sodium hydroxide content. Arabinoxylan extraction yields are slightly higher for conditions with low straw content (5.1% versus 4.4%). Nevertheless, these recovery yields remain between 9% and 10%. Ultrafiltration is as efficient as evaporation for polysaccharide concentration, with lower energy consumption, but also demineralizes the solution. The combination of ultrafiltration and chromatography gives partial purification of the extract with a final arabinoxylan purity ranging from 16% to 26%. This is slightly higher than by direct precipitation, but limited because all the large molecules such as proteins and lignins were retained by ultrafiltration., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

After closure of a waste disposal cell in a repository for radioactive waste, resaturation is likely to cause the release of soluble species contained in cement and bituminous matrices, such as ionic species (nitrates, sulfates, calcium and alkaline ions, etc.), organic matter (mainly organic acids), or gases (from steel containers and reinforced concrete structures as well as from radiolysis within the waste packages). However, in the presence of nitrates in the near-field of waste, the waste cell can initiate oxidative conditions leading to enhanced mobility of redox-sensitive radionuclides (RN). In biotic conditions and in the presence of organic matter and/or hydrogen as electron donors, nitrates may be microbiologically reduced, allowing a return to reducing conditions that promote the safety of storage. Our work aims to analyze the possible microbial reactivity of nitrates at the bitumen - concrete interface in conditions as close as possible to radioactive waste storage conditions in order (i) to evaluate the nitrate reaction kinetics; (ii) to identify the by-products (NO2(-), NH4(+), N2, N2O, etc.); and (iii) to discriminate between the roles of planktonic bacteria and those adhering as a biofilm structure in the denitrifying activity. Leaching experiments on solid matrices (bitumen and cement pastes) were first implemented to define the physicochemical conditions that microorganisms are likely to meet at the bitumen-concrete interface, e.g. highly alkaline pH conditions (10 < pH < 11) imposed by the cement matrix. The screening of a range of anaerobic denitrifying bacterial strains led us to select Halomonas desiderata as a model bacterium capable of catalyzing the reaction of nitrate reduction in these particular conditions of pH. The denitrifying activity of H. desiderata was quantified in a batch bioreactor in the presence of solid matrices and/or leachate from bitumen and cement matrices. Denitrification was relatively fast in the presence of cement matrix (<100 h) and 2-3 times slower in the presence of bituminous matrix (pH 9.7). The maximal rate of denitrification was approximately 0.063 mM h(-1) and some traces of nitrite were detected for a few hours (<2%). Overall, the presence of solid cement promoted the kinetics of denitrification. The inspection of the solid surfaces at the end of the experiment revealed the presence of a biofilm of H. desiderata on the cement paste surface. These attached bacteria showed a comparable denitrifying activity to planktonic bacterial culture. However, no colonization of bitumen was observed either by SEM or by epifluorescence microscopy., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The quality of stored roof runoff in terms of pesticide pollution was assessed over a one-year period. Two tanks, located at a rural and suburban site, respectively, were sampled monthly. The two studied collection surface were respectively a tile slope roof and a bituminous flat roof. Four hundred and five compounds and metabolites were screened using liquid and gas chromatography coupled with various detection systems. Principal Component Analysis was applied to the data sets to elucidate patterns. At the rural site, two groups of compounds associated with two different types of agriculture, vineyard and crops, were distinguished. The most frequently detected compound was glyphosate (83%) which is the most commonly used herbicide in French vineyards. At the suburban site, quantified compounds were linked to agriculture rather than urban practices. In addition, all samples were contaminated with mecoprop which is a roof-protecting agent. Its presence was attributed to the nature of roofing material used for rainwater collection. For both sites, the highest number and concentrations of compounds and metabolites were recorded at the end of spring and through summer. These results are consistent with treatment periods and higher temperatures., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The city of Toulouse with its separate sewer system is ideal for studying stormwater. However, during dry weather, the storm sewer also discharges water into the environment, and it is the impact of these discharges on annual pollution from storm sewer that is the object of this study. Samples have been taken from the outlets of two storm drains located in heavily and moderately urbanized areas. Sampling has been undertaken during wet weather and during dry weather between January 2010 and February 2011. Three dry weather and two wet weather samples have been taken every three months and from each outlet. The overall pollution parameters have been analyzed (chemical oxygen demand, biological oxygen demand, total nitrogen, ammonium, nitrate, total phosphorus, suspended solid matter, volatile suspended matter, pH, conductivity, turbidity). Characterization has been completed by analysis of trace organic compounds: polycyclic aromatic hydrocarbons, total hydrocarbons, methyl tert-butyl ether, diethylhexylphthalate, nonylphenols, hormones (estradiol, ethinylestradiol). For certain parameters, the results obtained did not conform to legislative requirements concerning discharge into the natural environment. Correlations between these parameters have been studied, and identified between several of them using principal component analysis. The most important correlation observed was between conductivity and concentration in total phosphorus for one of the outlet. Results showed that dry weather had an impact on annual pollution load from separate storm sewer and that level of urbanization was also a factor. The effect of season has been studied but no significant impact was found., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The present paper describes an analytical method for the determination of 2 widely administered anticancer drugs, ifosfamide and cyclophosphamide, contained in sewage sludge. The method relies on the extraction from the solid matrix by pressurized liquid extraction, sample purification by solid-phase extraction and analysis by ultra high performance liquid chromatography coupled with tandem mass spectrometry. The different parameters affecting the extraction efficiency were optimized using an experimental design. Solvent nature was the most decisive factor for the extraction but interactions between some parameters also appeared very influent. The method was applied to seven different types of sludge for validation. The performances of the analytical method displayed high variability between sludges with limits of detection spanning more than one order of magnitude and confirming the relevance of multi-sample validation. Matrix effect has been determined as the most limiting analytical step for quantification with different extent depending on analyte and sludge nature. For each analyte, the use of deuterated standard spiked at the very beginning ensured the complete compensation of losses regardless of the sample nature. The suitability of the method between freshly spiked and aged samples has also been verified. The optimized method was applied to different sludge samples to determine the environmental levels of anticancer drugs. The compounds were detected in some samples reaching 42.5μg/kgDM in ifosfamide for the most contaminated sample., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The quality of harvested rainwater used for toilet flushing in a private house in the south-west of France was assessed over a one-year period. Temperature, pH, conductivity, colour, turbidity, anions, cations, alkalinity, total hardness and total organic carbon were screened using standard analytical techniques. Total flora at 22 °C and 36 °C, total coliforms, Escherichia coli and enterococci were analysed. Overall, the collected rainwater had good physicochemical quality but did not meet the requirements for drinking water. The stored rainwater is characterised by low conductivity, hardness and alkalinity compared to mains water. Three widely used bacterial indicators - total coliforms, E. coli and enterococci - were detected in the majority of samples, indicating microbiological contamination of the water. To elucidate factors affecting the rainwater composition, principal component analysis and cluster analysis were applied to the complete data set of 50 observations. Chemical and microbiological parameters fluctuated during the course of the study, with the highest levels of microbiological contamination observed in roof runoffs collected during the summer. E. coli and enterococci occurred simultaneously, and their presence was linked to precipitation. Runoff quality is also unpredictable because it is sensitive to the weather. Cluster analysis differentiated three clusters: ionic composition, parameters linked with the microbiological load and indicators of faecal contamination. In future surveys, parameters from these three groups will be simultaneously monitored to more accurately characterise roof-collected rainwater., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Application of the European Water Framework Directive requires Member States to have better understanding of the quality of surface waters in order to improve knowledge of priority pollutants. Xenobiotics in urban receiving waters are an emerging concern. This study proposes a screening campaign of nine molecular species of xenobiotics in a separated sewer system. Five sites were investigated over one year in Toulouse (France) using quantitative monitoring. For each sample, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, nonylphenols, diethelhexylphthalate, linear alkylbenzene sulphonates, methyl tert-butylether, total hydrocarbons, estradiol and ethinylestradiol were analysed. Ground, rain and roof collected water concentrations are similar to treated wastewater levels. Run-off water was the most polluted of the five types investigated, discharged into the aquatic environment. The wastewater treatment plant reduced xenobiotic concentrations by 66% before discharge into the environment. Regarding environmental quality standards, observed concentrations in waters were in compliance with standards. The results show that xenobiotic concentrations are variable over time and space in all urban water compartments.

The contribution of discharge from carwashes to pollutant levels in stormwater was evaluated. Five carwashes and two outlets in the city of Toulouse (France) were selected. Water samples were collected from December 2006 to December 2007. Concentrations and loadings of classical water quality parameters (conductivity, pH, turbidity, chemical oxygen demand, nitrogen, phosphorus, ammonium, nitrate, suspended solid and volatile suspended solid) and five groups of organic compounds (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, lauryl alkyl benzene sulphonates, methyl tert-butyl ether and total hydrocarbons) were determined. The results suggest that the wastewater derived from carwashes was negligible compared to the volume and flow rates within the stormwater network. However, high concentrations of polycyclic aromatic hydrocarbons, phosphorus and lauryl alkyl benzene sulphonates in liquid waste from carwashes, and the impact of these pollutants on stormwater quality could not be neglected.

Surfactants are widely used in household and industrial products. The risk of incorporation of linear alkylbenzene sulfonates (LAS) from biosolids, wastewater, and fertilizers land application to the food chain is being assessed at present by the European Union. In the present work, a complete analytical method for LAS trace determination has been developed and successfully applied to LAS (C10-C13) uptake in carrot plants used as model. These carrots were grown in soil with the trace organics compounds added directly into the plant containers in pure substances form. LAS trace determination (mug kg(-1) dry matter) in carrots samples was achieved by Soxtec apparatus and high-performance liquid chromatography-fluorescence detection. The methodology developed provides LAS determination at low detection limits (5 mug kg(-1) dry matter) for carrot sample (2 g dry matter) with good recoveries rate (>90%). Transfer of LAS has been followed into the various parts of the carrot plant. LAS are generally found in the carrot leaves and percentage transfer remains very low (0.02%).

A routine method which is simple, quick and precise has been set up and validated for phthalate analysis in environmental samples (tomato plants and sewage sludges). Six phthalates have been studied simultaneously: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethyl-hexyl phthalate (DEHP) and di-n-octylphthalate. Optimization of sample, solvent extraction uses a Soxtec apparatus and extract purification with an a solid-phase extraction cartridge allows between 90 and 110% recovery of phthalates. Precise, sensitive and selective identification and quantifying of analytes is by GC-MS in the single ion monitoring mode. This protocol allows analytes with concentrations as low as 10 microg/kg dry matter (DM) to be determined from small (1-2 g DM) samples. This analytical method has been applied to the phthalate transfer study for agricultural recycling of sludges, where phthalate bioavailability has been studied in aquiculture using two types of experiments. Tomatoes have been grown in containers where the trace organics have been directly introduced as pure substances, and in a second experiment under the same growth conditions, sewage sludge has replaced the pure substances. Transfer of these trace organics has been followed into the various parts of the tomato plant and in general only the DEHP is worthy of note although its percentage transfer remains very low even in an experiment designed to maximize this.

Theophylline still occupies a dominant place in asthma therapy. Unfortunately its adverse central nervous system (CNS) stimulant effects can dramatically limit its use, and adjustments in the dosage are often needed. We have synthesized a new series of imidazo[1,2-alpha]pyrazine derivatives which are much more potent bronchodilators than theophylline in vivo and do not exhibit the CNS stimulatory profile. In vitro studies on isolated rat uterus and guinea pig trachea confirm the high potentialities of these derivatives. 6-Bromo-8-(methylamino)imidazo[1,2-alpha]-pyrazine-3-carbonitrile (23) is identified as the most potent compound of the series. As in the case of theophylline, phosphodiesterase inhibition appears unlikely to be the unique mechanism of action of this series of heterocycles.

Theophylline and other methylxanthines display a large number of biological effects, some of which are clinically important. The effects of these compounds are commonly ascribed to an inhibition of cyclic AMP breakdown. However, it becomes actually evident that another mechanism, namely adenosine receptor antagonism, could be responsible for certain methylxanthine effects. It could be of interest to find new compounds displaying only one of these mechanisms, either phosphodiesterase inhibition or adenosine receptor antagonism. We have studied several synthetic imidazol[1,2a]pyrazines, some of which display theophylline-like pharmacological properties at lower doses than theophylline. We showed that some of these compounds inhibited mitogen-induced [3H]-thymidine uptake by human lymphocytes, which is consistent with increases in cyclic AMP levels: the most efficient compounds were those which were better phosphodiesterase inhibitors than theophylline and poorer adenosine receptor antagonists.

A series of imidazo[1,2-alpha]pyrazine derivatives was synthesized by condensation of alpha-halogenocarbonyl compounds and aminopyrazines. Various compounds resulted from competitive reactions or reagent isomerization and demonstrated in vitro uterine-relaxing and in vivo antibronchospastic activities. On isolated atria, 5-bromoimidazo-[1,2-alpha]pyrazine showed positive chronotropic and inotropic properties; the latter was associated with an increase in the cyclic AMP tissue concentration. Potentiation of the isoproterenol positive inotropic effect of 5-bromoimidazo[1,2-alpha]pyrazine and the lack of blockade of the 5-bromoimidazo[1,2-alpha]pyrazine positive inotropic effect by propranolol suggested phosphodiesterase-inhibiting properties.