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Since 20 years, titanium oxide materials, and in particular lithium titanate spinel Li4Ti5O12 (LTO), were considered as promising negative electrode materials for lithium-ion cells. In the case of the TiNb2O7 compound (TNO), which has a larger theoretical lithiation capacity of 388 mAh.g-1, few studies have focused on the outgassing of the material. In this work, we quantified the volume produced as a function of different cycling parameters and then characterize the species. From the obtained results we proposed a reaction mechanism describing the phenomenon as well as solutions to reduce it.

With the advent of high brilliance 4th generation synchrotron sources, the issue of beam damage on the samples cannot be ignored and deserves a wide attention. It is especially true for operando studies in batteries, since the intense photon fluxes are commonly used to probe ever finer effects. Here we report on a quantitative study on the causes and consequences of synchrotron X-ray beam damage in batteries, based on the case study of operando X-ray diffraction. We show that beam damage is caused by the mingled action of dose and dose rate. The after-effects can lie in a broad range, from mild modifications of the crystalline structure to artificial phase transitions, and can thus impede or bias the understanding of the mechanisms at play. From our results, we estimate the doses at which the different effects appear, and provide recommendations for the design of operando synchrotron experiments.

This communication intends to promote an ex-post methodology to systematically document coupled trajectories between environmental sciences and planning. While specific institutional arrangements facilitate collaborative practices in long-term socio-environmental observatories, the collaboration mechanisms are still poorly documented and some framework developments are needed for capitalization studies. To fill this gap, we propose an approach to trace, illustrate and evaluate interactive activities between researchers and managers. We proposed the Systemic Timeline Multistep (STM) methodology on the basis of a typical case-study, the coastal Thau catchment (south of France), where societal challenges emerged from water-related issues.First we propose a conceptual framework of the collaborative process: the system under study is composed of bundles of research and development projects, which forms a given sociotechnical configuration that fulfill specific functions. The trajectory is marked by the succession of relatively stable periods, globally oriented by transitions. Second, we implement this framework on past environmental projects through a diachronic and dialectic approach: the objective is to characterize regimes (driving mechanisms of interactive arrangements) and identify transitions in the trajectory (triggers and impacts of regime shift). The multi-step methodology is divided in: define spatial and temporal system boundaries, list and contextualize all projects, represent the dynamics of projects and events, and analyze the overall pathway (relate projects’ role to context variables).The implementation of the methodology on the Thau case study helps rapidly visualize research activities and their interactions with water management and broader governance and societal events through time. Both research and practice communities were bridged in the frame of specific governance instruments dedicated to lagoon water quality, which ‘sanitary crises’ required interventions across public policies and sustained interactions with knowledge production. It points out the role of technical infrastructures (monitoring and modelling of water fluxes) on water quality and related-activities, and it highlights the importance of boundary works for integrated planning (coastal zone, land and water). Finally, the STM methodology supports the characterization of interdependencies between water fluxes characterization, water management and water uses. Exploring the impacts of information system on collaborative mechanisms may provide place-based reflexive insights on governance approaches in long-term research platforms.

Soil and water salinization is a major threat to agricultural land and biodiversity in natural areas. Coastal areas are highly sensitive to salinization leading to a deterioration of resources (water, soil and biodiversity) and ecosystem services. The Aude lowland is longstanding facing this issue. The main solution is to bring massive amounts of fresh water to the surface of the fields, in the form of anthropic flooding, associated with drainage for the leaching of salts. Understanding system equilibrium is crucial in the context of global change, less fresh water available, sea level rise, strong and fast landuse evolution.To achieve this objective, we propose an integrated approach providing links between high resolution water and soil salinity at lowland scale, lato sensu water management practices and winegrowers perception of the actual state and evolution salinity.Salinity measurement survey consist in three dimensional sampling with more than 1500 samples on the whole study area. Results exhibit high level of salinity, increasing with depth and heterogeneity at short distance and spatially structured at long distance. Closed questions carried out on 27 winegrowers bring an in-depth knowledge on all winegrowing practices related to water management (tillage, weed control practices, irrigation, drainage). Statistical analysis (MCA, HAC) show five groups of practices associated to different salt control strategies. Perception was investigated using open questions and answers were structured in a matrix including six themes (in column) and 27 winegrowers (in row). Main results show three different types for salinity perception.The cross analysis between perception, practices and measured salinity brings an integrated vision of the salinization and its management in the study area. This allows to better understand how viticulture can still partially persist despite high soil and water salinity levels. The reason is inside the strategies promoting the adaptation of the practices to salty pressure and soil functioning and not only based on unique practice.

International audience; Lithium-rich disordered rocksalt Li$_2$TiS$_3$ offers large discharge capacities (>350 mAh.g$^{-1}$) and can be considered a promising cathode material for high-energy lithium-ion battery applications. However, the quick fading of the specific capacity results in a poor cycle life of the system, especially when liquid electrolyte-based batteries are used. Our efforts to solve the cycling stability problem resulted in the discovery of new high-energy selenium-substituted materials (Li$_2$TiSe$_x$S$_{3-x}$), which were prepared using a wet mechanochemistry process. X-ray diffraction analysis confirmed that all compositions were obtained in cation-disordered rocksalt phase and that the lattice parameters were expanded by selenium substitution. Substituted materials delivered large reversible capacities, with smaller average potentials, and their cycling stability was superior compared to Li$_2$TiS$_3$ upon cycling at a rate of C/10 between 3.0 1.6 V vs. Li$^+$/Li.

Promising theoretical capacities and high voltages are offered by Li-rich disordered rocksalt oxyfluoride materials as cathodes in lithium-ion batteries. However, as has been discovered for many other Li-rich materials, the oxyfluorides suffer from extensive surface degradation, leading to severe capacity fading. In the case of Li$_{2}$VO$_{2}$F, we have previously determined this to be a result of detrimental reactions between an unstable surface layer and the organic electrolyte. Herein, we present the protection of Li$_{2}$VO$_{2}$F particles with AlF$_{3}$ surface modification, resulting in a much-enhanced capacity retention over 50 cycles. While the specific capacity for the untreated material drops below 100 mA h g$^{-1}$ after only 50 cycles, the treated materials retain almost 200 mA h g$^{-1}$. Photoelectron spectroscopy depth profiling confirms the stabilization of the active material surface by the surface modification and reveals its suppression of electrolyte decomposition.

Li-rich disordered rock-salt structures have, because of their high theoretical capacity, gained a lot of attention as a promising class of cathode materials for battery applications. However, the ...

Flood mitigation planning requires the proper estimation of the flood risk. When systematic gauging of floods is short or lacking interesting information can be inferred from historical flood records in newspapers. We present the work to locate and evaluate past flood information recorded in newspapers to collate a national flood database for Lebanon and to evaluate the consequent flood risk. Over 700 records of flood events were extracted from newspapers and implemented in a GIS database. The spatial occurrence of these events was studied and linked to a combination of morphological, hydrological, and vulnerability characteristics of the major Lebanese catchments. Accordingly, a flood risk map was developed for the country. In this study, we show that retrieving newspaper information on previous floods was an added value and was beneficial in evaluating flood risk on a national scale.

Salinization is a worldwide issue particularly threatening arid and semi-arid soils. Primary salinization is due to unbalanced flows between upward water and solute flows leading to salts accumulation and downward flows which allow the leaching of salts. Soil salinity affects vegetation by causing osmotic and toxic stress. In return, soil water transfers are impacted since water extraction by plants is limited. Salinity leads also to a decrease of soil hydraulic conductivity.Salinisation is often described as a threat to agriculture, but less as a driver of specific ecosystem functioning, such as salt marshes. These interfaces between land and sea are very present in the Mediterranean deltas and lagoon complexes, and provide several ecosystem services, (e.g. being the natural areas among with the highest carbon storage rate). Salinity in these ecosystems is highly dependent on freshwater inputs from precipitation, natural or anthropic flooding, making them vulnerable to global changes. Nevertheless, the effects of flooding on hydrological dynamics and solute transfers in salt marshes are not well known.We choose a study site in the lowlands of the Aude river (the Castelou site, Narbonne, France) to address the question of the hydrological behavior of a salt marsh managed by different flooding intensities in relation to plant communities. Soil moisture, saturated zone depth, and salinity dynamics are monitored by a set of continuous and point measurements at 12 sites distributed along a flood management gradient and a natural salt pressure gradient. Based on these observations, time continuous data series have been built by a physics-based modeling. The analysis provides a better understanding of the effects of flooding on soil water and solute stocks and fluxes, and relates them to the specific composition of plant communities.We show that flooding has varying effects on water storage in unsaturated and saturated zones. Soil water recharge has a small effect on soil salt content on an annual scale but limits the level of osmotic stress. In the absence of flooding, osmotic stress is more pronounced, altering the specific composition of plant communities, suggesting changes in their functional properties.

Environmental research and management organizations are mutually dependent when it comes to produce and use knowledge in favor of responsible action in an increasingly uncertain world. Still, science and practice interfacing remains a challenge when it comes to implementing and sustaining a collaborative process. In this paper, we develop a descriptive framework to study the coevolution of scientific and planning activities embedded in a territorial system. Scientists and managers dynamically interact through institutional arrangements, operationalization of knowledge and information and communication tools. We propose an approach to systematically document transdisciplinary pathways and characterize the bounding process between organizations on a typical case-study, the coastal Thau territoire (Mediterranean Sea, France). By tracing, illustrating and analyzing coupled trajectories of environmental sciences and planning for the last decades, the Systemic Timeline Multistep methodology tackles cross-fertilization mechanisms. The relational analysis draws on the elaboration of a synchronic timeline to question co-evolution and grasp causal mechanisms of research projects interactions with management pathways. Its application on the Thau territoire shows that scientific activities and public actions shaped each other in a continuous process of interaction. It also gives insights into the contributive roles of long-term place-based research and intermediate organizations for the emergence of new sociotechnical arrangements.

International audience; Heterogeneous potential and lithium distribution inside lithium ion batteries highly affect their performanceand durability. In particular, increased lithium gradients are expected in thick electrodes with high energydensities or cycling at high currents. To optimise electrodes and cells designs, it is thus crucial to predictand probe the local lithium concentration across the depth of the electrode, as a function of theelectrode material properties. Here, we follow the lithium distribution across a 80 mm thick porousgraphite electrode using a 1 mm focused synchrotron X-ray beam during a complete delithiation. Thesequential formation of the individual LixC6 phases is extracted from X-ray diffraction patterns, allowingthe quantification of lithium concentration across the electrode thickness and its heterogeneities. Wereport a striking pattern, with strong heterogeneities at low stoichiometries, even at C/5, and a muchmore homogeneous Li distribution during the stage 1 / 2 transition. A porous electrode model canactually capture the former but fails at predicting the latter. Revisiting the model, we could match theexperimental tendencies by considering that the kinetics of lithium (de)intercalation is reduced duringthe LiC6/LiC12 phase transition compared to the other transitions. By combining modelling and operandoX-rays characterisation, we therefore establish that the main competing forces in graphite are distinctlybalanced depending on the lithiation stage.

International audience; Owing to its specific properties, cobalt is a critical material for catalysis, stainless steel, and of course for Li-Ion batteries. Due to the intensive development of Li-ion batteries for transport applications (All-Electric and Plug-in Hybrid Electric Vehicles), the need for cobalt will dramatically increase. Unfortunately, resource is scarce and more than half of the cobalt production is presently concentrated in only one country (Democratic Republic of the Congo). Recycling and reusing cobalt from used batteries in a closed-loop process in order to limit cobalt imports becomes mandatory. In this paper, we propose a disruptive and very efficient route to selectively precipitate cobalt from a spent batteries solution, which consists in using imidazole linkers.The resulting hybrid material can be directly used as a precursor to produce a new cobalt-cathode based material

This study aims to compare the opportunity cost of illicit financial flows in terms of financing basic social services in CAEMC and WAEMU zone. For this, we use the ICOR simulation method based on the Harrod and Domar model and recently applied by Nkurunziza (2015) and Moulemvo (African Economic Review 28:113–123, 2016). The results of these simulations show that based on the calculated ICOR coefficient, we estimate the loss of GDP in CAEMC at 18 billion USD and that of WAEMU at 13 billion USD. This loss of GDP in the victim countries would make it possible to allocate additional resources for public social spending.

Some scientific studies report that the use of nanosized cathode materials can improve the electrochemical performances of a battery. In fact, these materials can open new and important perspectives for cathode materials such as their use for power applications or for technologies for which an optimized interface with the electrolyte is required (e.g all solid state battery or polymer battery). However, the high scale production and the processing of these powders to obtain dense electrodes are difficult. In this study, submicronic particles of LiNi1/3Mn1/3Co1/3O2 are synthesized using an easy and scalable coprecipitation synthesis protocol. Isolated particles of 200 nm are obtained and are fully characterized. The non-agglomerated morphology of this material improves the accessibility of the lithium insertion planes, and consequently, the high C-rate behavior is clearly improved as compared to classic agglomerate materials. The difficult processing of submicronic particles is overcome thanks to an environmentally-friendly water-based formulation. Proof-of-concept Li-ion cells have been realized. Although submicronic particles are used, the cell is manufactured with a cathode loading of 18.8 mg cm−2 which is relevant for commercial application.

International audience; The dissolution, migration and deposition (DMD process) of transition metal ions during cycling is a well-known phenomenon reported in literature especially concerning high manganese spinel cathode0246810121416182001020304050Pouch capacity (mAh)Cycle index12SuddendeatheffectManganesedetectionat the anode sidePoint 1Point 22material. The main approach to solve this issue consists in coating or doping the particles surface with electrochemically inert cations and/or anions. In this study, we describe a DMD process mechanism which happens in the silicon-graphite/lithium rich layered oxide (Si-Gr/Li1.2Ni0.2Mn0.6O2) systems. This phenomenon leads to a sudden death effect of the cell after 20 cycles. AlF3 coating is envisaged to limit the cation dissolution from the positive electrode: we highlight that our synthesis finally results in improving the electrochemical performances of lithium rich layered oxides by offering an Al/F doped surface. Despite this improvement, the coating fails, on the other hand, to stop the transition metal cations dissolution, especially in Li-ion cells (Si-Gr as anode).

We re-examine the charge transfer mechanism in the Chevrel phase Mo6S8 upon Mg intercalation and deintercalation by the mean of X-ray photoemission spectroscopy. We highlighted a two-step reversible charge transfer process involving successively axial sulfurs and Mo6 cluster redox center. In parallel, the Mg 2p and Mg KLL Auger transition evolution evidenced two insertion sites having different polarizations in accordance with previous studies. The nonconventional metal transition redox reaction, involved during Mg intercalation in Chevrel phase, might be at the origin of its excellent reversibility and intercalation kinetics.

Although intravenous dexamethasone prolongs the analgesic duration of interscalene brachial plexus block, it is uncertain whether this effect can be observed using lower doses of dexamethasone. This study evaluated the impact of intravenous dexamethasone (4 mg and 10 mg) on the analgesic duration of single-shot interscalene block after arthroscopic shoulder surgery. We hypothesized that both doses would prolong the analgesic duration compared with placebo. This was a prospective double-blind randomized placebo-controlled study in patients undergoing elective arthroscopic shoulder surgery under regional anesthesia with a single-shot interscalene block (0.5% ropivacaine 20 mL). Patients received dexamethasone 4 mg (D4), dexamethasone 10 mg (D10), or a placebo (normal saline [NS]) intravenously at the time of block completion. The primary outcome was the duration of analgesia, defined as the time from the onset of sensory blockade to the first analgesic request. The primary outcome was first analyzed with a Kruskal-Wallis test and then with a Mann-Whitney test for pairwise between-group comparison. Sixty-nine patients completed the study. The median [interquartile range] duration of analgesia was significantly different between the three groups (D4, 19.7 [16.9-23.3] hr; D10, 19.1 [11.5-22.8] hr; and NS, 11.8 [9.3-14.0] hr; P = 0.001). This difference was statistically significant for D4 and D10 compared with placebo (median difference [MD], 7.8 hr; 95% confidence interval [CI], 4.6 to 11.1 hr; P < 0.001; and MD, 7.4 hr; 95% CI, 4.2 to 10.5 hr; P = 0.001, respectively) but not for D4 compared with D10 (MD, 0.5 hr; 95% CI, −2.8 to 3.7 hr; P = 0.38). Low doses of intravenous dexamethasone (4 mg and 10 mg) significantly prolong the analgesic duration of interscalene block. This trial was registered at ClinicalTrials.gov (NCT02412657).

Inter-tropical regions are nowadays faced to major land-use changes in data-sparse context leading to difficulties to assess hydrological signatures and their evolution. This work is part of the theme Panta Rhei of the IAHS, and aims to develop a combined approach of data acquisition and a new semi-distributed model taking into account land-use changes to reconstruct and predict annual runoff on an urban catchment. Applications were conducted on the Mefou catchment at Nsimalen (421 km2; Yaoundé, Cameroon) under rapid increase in urbanization since 1960. The data acquisition step combines an historical data processing and a short-term spatially-dense dedicated instrumentation (2017–2018), leading to 12 donor catchments, 6 from historical studies and 6 from the instrumentation presenting various topographic, soil and land-use characteristics. We developed an annual rainfall-runoff model based on mathematical relationships similar to the SCS model. The model needs the definition of a hydrological index I which is time variable and enables to take into account land-use changes and non-stationary relationships between rainfall and runoff. The index I is an empirical indicator defined as a combination of several components such as topography, soil, and land-use. The rules for the construction of I are obtained from data analysis on donor catchments. Then, the model was calibrated on donor catchments. Finally, two applications were conducted on eight target catchments composing the Mefou in order: (i) to study the spatial hydrological functioning and calculate the water balance during the short instrumentation period; (ii) to reconstruct the hydrograph at the Mefou and to simulate the impact of future scenarios of land-use and urbanization. Results show that that the Mfoundi catchment, integrating the three more urbanized sub-catchments, contributes near to 40 % of the Mefou despite covering only 23 % of the basin. The most urbanized sub-catchments present annual runoff coefficient about 0.86 against 0.24 for the most natural sub-catchments. The second result is the reconstruction of historical annual runoff from 1930–2017 with r2 = 0.68, RMSE = 99 mm and a mean absolute normalized error Ē = 14.5 % over the 29 observed years. The reconstruction of the annual runoff at Nsimalen confirms the moderate impact of urbanization on annual runoff before 1980. However, a decrease of about 50 % of the forest cover and an increase from 10 % to 35 % of the urban area between 1980 and 2017 are associated with an increase of 53 % of annual runoff coefficient for the Mefou at Nsimalen (0.44 against 0.29). Application for a fictive plausible scenario of urbanization in 2030 leads to an increase of more than 85 % of the annual runoff in comparison of the values observed in 1980. The coupled experimental-modelling approach proposed herein opens promising perspectives regarding the evaluation of the annual runoff in catchments under changes.

Due to the increase in energy storage for consumer electronics, stationary application and above all for electrical vehicles, the manufacturing of Li-ion batteries has dramatically increased in the past few years. Unfortunately, cathode materials still often use cobalt, and consequently, an increase of 10% per year of the world’s cobalt consumption has been observed. Li-ion batteries represent 60% of the use of extracted cobalt today (more than 80% expected in 2030), which is classified as a critical material since 2011 by the European Commission. Battery grade cobalt is produced by only few countries. 60% is provided by the Democratic Republic of Congo. In order to avoid reliance on cobalt supplying, European industry should have to develop alternative solution. We present here a new way to extract cobalt from a solution of battery-waste materials. Through a one-step process, it is possible to recover the cobalt, selectively, in a solution composed in majority of cobalt, nickel and manganese. The goal of the process is to form a cobalt-based Metal Organic Framework compounds (MOF) from a multi-metals based solution. The contact of a well-designed ligand with model multi-metallic solution of nickel, manganese and cobalt, under specific conditions, creates a precipitate, which is recovered by centrifugation or filtration. The XRD analysis of the resulting material demonstrates a crystalline structure, and its ICP analysis shows up to 99% of cobalt composition of the metallic nodes of the material. The same process with a real battery waste solution enables the formation of a precipitate made of 94% of cobalt (among the metallic centers). The resulting MOF can be used as a precursor for synthetizing cathode materials. In order to complete the described closed-loop concept, it is indeed possible to assemble a coin-cell from those products. The well define crystalline structure of the MOF makes them suitable for other industrial application, such as separation or catalysis (open-loop concept). We are focusing on better understanding of this selectivity process. Density Functional Theory (DFT) calculations are performed, as a tool to evaluate the energy of the different complexes in solution at all states of the nucleation and growth of the MOF. Moreover, the ligand used can form a MOF with each of the metals present in solution. Some nickel and manganese phases (more or less soluble) are involved during the process as a function of the reaction conditions. Identifying their nature and formation is another axis for the understanding of the presented work. Modelling these phenomena could help to determine the reaction that occurs, how the selectivity happens, and why the growing material is made of cobalt only (no other metal).

A solvothermal synthesis is developed to build a 3D network of nanoparticles, enhancing the electrochemical performances of both TiNb2O7 and Ti2Nb10O29, especially at high current densities, with up to 190 mA h g−1 at 10C. A set of 11 mA h pouch cells combining the nanosized TiNb2O7 with LiMn1.5Ni0.5O4 is tested and is the first to be reported for this material. Soft shell cells are used, not only to evaluate the electrochemical performances of this oxide in a larger scale battery, but also to assess its gassing behavior, a well-known limitation for application of Li4Ti5O12 in hybrid electric vehicles. In order to evaluate the sole contribution of TiNb2O7 to the swelling, an additional set of soft shell TiNb2O7/Li(Ni1/3Mn1/3Co1/3)O2 cells is assembled and stored at 45 °C in a charged state. A higher swelling behavior is observed for TiNb2O7 in comparison to Li4Ti5O12; a clear trend also appears between the surface area of the oxide and the amount of gassing. The swelling of TiNb2O7 or Ti2Nb10O29 based pouch cells should be addressed before further industrial development of the two oxides can be considered.

Most of the current Li-Ion cathodes use cobalt/nickel-based layered oxides as active materials. Due to the increasing demand of these critical and scarce elements in the coming years, it becomes urgent to develop new materials based on abundant elements. In 2014, Sakuda et al. introduce new sulphide rocksalt materials which can deliver a capacity higher than 400 mAh/g at 2.2 Volts.1 In 2019, a project named Spider funded by the European Union's Horizon 2020 research and innovation programme started with the objective to develop and use these materials in Li-Ion batteries. Several synthesis methods have been evaluated to produce Li2TiS3 materials. High capacities are obtained with these materials but they suffer from a poor cycle life. Several characterizations and experiments have been performed in order to obtain a better understanding of the material evolution during cycling. Ex-situ XRD are in good agreement with previous results reported by Sakuda et al. and we completed the investigation thanks to Ex-situ SEM and XPS characterizations.2 We highlight that the material is partially oxidized during the cathode manufacturing process which lead to a loss of the lithium content in the materials structure. Our conclusions will be helpful to overcome these issues. References (1) Sakuda, A.; Takeuchi, T.; Okamura, K.; Kobayashi, H.; Sakaebe, H.; Tatsumi, K.; Ogumi, Z. Rock-Salt-Type Lithium Metal Sulphides as Novel Positive-Electrode Materials. Sci. Rep. 2014, 4, 4883. https://doi.org/10.1038/srep04883. (2) Sakuda, A.; Ohara, K.; Kawaguchi, T.; Fukuda, K.; Nakanishi, K.; Arai, H.; Uchimoto, Y.; Ohta, T.; Matsubara, E.; Ogumi, Z.; et al. A Reversible Rocksalt to Amorphous Phase Transition Involving Anion Redox. Sci. Rep. 2018, 8 (1), 1–6. https://doi.org/10.1038/s41598-018-33518-4. Figure 1

Cobalt is a critical material used in many applications such as steel alloys, catalysis and of course Li-Ion batteries. The massive market diffusion of electrified passenger vehicles expected in the next decades will most probably induce a considerable need of this scarce and expensive metal.1 The small number of locations where cobalt is produced may lead to several drawbacks such as geopolitical dependence, material shortage and also production capability. Consequently, it is necessary to identify new and efficient solutions to trap and reuse cobalt out of from various sources. Cobalt could be of course obtained by mining but it is also possible to recycle it from used batteries. Here, we propose a disruptive and very efficient way to selectively precipitate cobalt from a solution by using Metal-Organic Frameworks (MOFs). MOFs belong to a particular class of porous hybrid materials.2 These hybrid materials are intensively studied for adsorption and catalysis applications. Recently, we discovered an organic ligand which is able to selectively precipitate cobalt based-MOFs from a mixture of nickel, manganese and cobalt.3–5 When a well-selected linker is put in contact with an equimolar solution of nickel, manganese and cobalt, at room temperature, a precipitate appears. The powder is recovered by filtration and characterized. In specific experimental conditions, we show that a hybrid material, belonging to the MOFs family, is synthesized. ICP-AES of the resulting material shows that the resulting compound contains up to 99% cobalt (molar percentage as a function of the metal contained in the MOF). This result may pave the way to the reuse of cobalt in many applications fields but the battery recycling field could reveal a critical case study. We introduce here the experimental results achieved when this new type of synthesis is used with a real, spent Li-ion battery leach solution. The resulting material has a cobalt content of 94.4 % (vs other metals) and contains a large part of the initial amount of cobalt initially present in the solution (figure 1). The resulting material could be directly reused and implemented as positive electrode active material in a new Li-Ion battery. One other interesting aspect of this synthesis is the high value product obtained: the resulting MOF can indeed have many other uses such as catalyst or adsorbent The results presented during the conference have been recently patented but have never been published and introduced before. References (1) Bloch, D.; Lefebvre, G.; Les matériaux requis par les batteries Li-ion. REE 2019-4 2019, 2019 (4). (2) Férey, G. Hybrid Porous Solids: Past, Present, Future. Chem. Soc. Rev. 2007, 37 (1), 191–214. https://doi.org/10.1039/B618320B. (3) Peralta, D.; Chaplais, G.; Simon-Masseron, A.; Barthelet, K.; Chizallet, C.; Quoineaud, A.-A.; Pirngruber, G. D. Comparison of the Behavior of Metal–Organic Frameworks and Zeolites for Hydrocarbon Separations. J. Am. Chem. Soc. 2012, 134 (19), 8115–8126. https://doi.org/10.1021/ja211864w. (4) Peralta, D.; Chaplais, G.; Simon-Masseron, A.; Barthelet, K.; Pirngruber, G. D. Metal–Organic Framework Materials for Desulfurization by Adsorption. Energy Fuels 2012, 26 (8), 4953–4960. https://doi.org/10.1021/ef300762z. (5) Chevalier, V.; Martin, J.; Peralta, D.; Roussey, A.; Tardif, F. Performance of HKUST-1 Metal-Organic Framework for a VOCs Mixture Adsorption at Realistic Concentrations Ranging from 0.5 to 2.5 Ppmv under Different Humidity Conditions. J. Environ. Chem. Eng. 2019, 7 (3), 103131. https://doi.org/10.1016/j.jece.2019.103131. Figure 1

Purpose: In a context of flourishing eco-labelling programs and environment policy for food products, LCA application to agricultural systems faces the challenges of being operational, accurate and exhaustive. This is particularly challenging for the newly developing LCA and ISO-compliant water footprinting, with many LCIA methods only recently developed, but no dedicated inventory method. To support the inventory of elementary water flows, LCA practitioners have a variety of tools available, ranging from databases (e.g. World Food LCA Database) to complex agro-hydrological models. To allow all LCA practitioners to fulfil their diverse agri-food LCA objectives, a review of available inventory tools for field water flows and recommendations are needed. Methods: The selection of the appropriate method and tool for the inventory of field water flows in agri-food LCA studies depends on the objectives of the LCA study, data and resources available (time and skills). We analysed water inventory and agri-food LCA databases by evaluating the models on which they rely and their input data. Then, we explored the use of agro-hydrological models for LCA aiming at discriminating between different cropping system practices (LCA-based eco-design). Results and discussion: Water inventory and agri-food LCA databases provide estimates of theoretical water consumed by a crop and rely on data and methods that have limitations, making them suitable only for background agricultural LCAs. In addition, databases do not support the application of water availability footprint indicators (assessing quantitative water use and water quality alteration). For the LCA-based eco-design of cropping systems, the inventory of water flows should be based on a model simulating evapotranspiration, deep percolation and runoff accounting for crop specificities, pedo-climatic conditions and agricultural management. In particular, the model should account for possible water, salinity and nutrient stresses; assess evaporation and transpiration separately; and estimate runoff and drainage according to the system specificities. Yield should not be estimated with a model but with primary data. Recommended and default data sources are provided for each input parameter. Conclusions: The FAO AquaCrop model represents a good trade-off between accuracy, simplicity and robustness for LCA-based eco-design of cropping systems. However, this model is not yet applicable for perennial crops. Beyond a single model selection, this is a modelling approach that we characterised in this work.

International audience; Soil salinization is a major threat to agricultural lands. Among salt-affected lands, coastal areas could be considered as highly complex systems, where salinization degradation due to anthropogenic pressure and climate-induced changes could significantly alter system functioning. For such complex systems, conceptual models can be used as evaluation tools in a preliminary step to identify the main evolutionary processes responsible for soil and water salinization. This study aimed to propose a conceptual model for water fluxes in a coastal area affected by salinity, which can help to identify the relationships between agricultural landscape evolution and actual salinity. First, we conducted field investigations from 2012 to 2016, mainly based on both soil (EC1/5) and water (ECw) electrical conductivity survey. This allowed us to characterize spatial structures for EC1/5 and ECw and to identify the river as a preponderant factor in land salinization. Subsequently, we proposed and used a conceptual model for water fluxes and conducted a time analysis (1962-2012) for three of its main constitutive elements, namely climate, river, and land systems. When integrated within the conceptual model framework, it appeared that the evolution of all constitutive elements since 1962 was responsible for the disruption of system equilibrium, favoring overall salt accumulation in the soil root zone.

Recently, rechargeable aluminum batteries have received much attention due to their low cost, easy operation, and high safety. As the research into rechargeable aluminum batteries with a room-temperature ionic liquid electrolyte is relatively new, research efforts have focused on finding suitable electrode materials. An understanding of the environmental aspects of electrode materials is essential to make informed and conscious decisions in aluminum battery development. The purpose of this study was to evaluate and compare the relative environmental performance of electrode material candidates for rechargeable aluminum batteries with an AlCl3/EMIMCl (1-ethyl-3-methylimidazolium chloride) room-temperature ionic liquid electrolyte. To this end, we used a lifecycle environmental screening framework to evaluate 12 candidate electrode materials. We found that all of the studied materials are associated with one or more drawbacks and therefore do not represent a “silver bullet” for the aluminum battery. Even so, some materials appeared more promising than others did. We also found that aluminum battery technology is likely to face some of the same environmental challenges as Li-ion technology but also offers an opportunity to avoid others. The insights provided here can aid aluminum battery development in an environmentally sustainable direction.

Flood modelling in data-sparse regions have been always limited to empirical, statistical or geomorphic approaches that are suitable to produce regional hazard maps. Such coarse resolution maps are not adapted for basin-scale applications, small to medium sized basins (< 1000 km(2)), especially when detailed estimates of flows and water levels of a particular event is required and hence cannot replace the hydrological/hydraulic modelling. The latter is a challenging task in data-sparse regions characterized by floods of typical duration times of a few hours which offer little opportunity for real-time recording by traditional rain-gauge networks, remote sensing or satellite imaging. Such data sparseness is not always compatible with the resolution, in both space and time, of the hydrological and hydraulic models. We propose a framework for flood modelling using sparse data from a coupled hydrological-hydraulic model constrained by past storm events and post-event measurements in space. The approach is applied to the Awali river basin (301 km(2)), in Lebanon, particularly to simulate the investigated early January 2013 extreme flood event, which is considered one of the largest events in the last three decades. The hydrological model was calibrated and evaluated with 12 past storm events aiming at defining narrow parameter ranges and uncertainty was performed with Monte Carlo simulations for these parameter ranges. The hydraulic model, based on a fine resolution DEM, was simulated using hydrological outflows and validated with 27 post-event measurements in space of high water marks. The resulting outflow values were satisfactory, and uncertainty was reduced when compared with arbitrarily wide parameter ranges. The hydrological model performance was highly variable but for the hydraulic model, 93% of the observed water levels fall within the simulated uncertainty bounds with an RMSE error of 0.26 m. The proposed framework allows mapping the possible inundation and can be compared to other approaches dealing with model complexity and associated performances.

Lithium-rich layered oxide is known to be one of the most promising positive electrode materials for high energy Li-ion batteries. Some publications report specific capacities higher than 250 mAh/g but the fade of the average potential during electrochemical cycling is an important drawback for commercial use of this material. The objective of this work is to study the origin of this potential decay during cycling of lithium-rich compounds. For this purpose, the electrochemical behavior of xLi 2 MnO 3 ·(1−x)LiNi 0.5 Mn 0.5 O 2 (with x = 1, 0.7, 0.5, 0.27) materials synthesized using coprecipitation route have been compared. For this study, complete or partial charge and discharge cycles have been performed in the 2.5 V–4.8 V voltage range. The results can be briefly summarized as follows: the potential decay is mainly provoked by several phenomena occurring at low potential, this growth being induced by the charging of lithium-rich at high voltage (>4.15 V). Whatever the compositions, same phenomena are involved, only the kinetics is modified.

International audience; We report the lithium insertion into a copper iron oxyborate, i.e. Cu2FeBO5. Four electrons are involved in the course of the first discharge, which is ascribed to the Cu2+/Cu redox couple. The reaction is associated with a collapse of the structure but this material shows a reversible and stable capacity of 180 mAh/g at 2.35 V vs. Li+/Li.

International audience; Soil is a key component of the terroir concept for wine production. Indeed, the soil provides water and nutrients to the vine plants depending on its properties and environmental conditions. A part of the complexity in the pro- duction of high-quality wines is the adaptation of the winegrowing practices to soil conditions variability in space and time. Then, a deep understanding of the environmental conditions that modulate soil-plant system function- ing and control the production of quality wine is crucial for future global change adaptation. This study aimed to identify environmental factors controlling red wine quality by merging both winemaker and scientist knowledge. This work was performed on a vineyard in Saint-Emilion Grand Cru appellation, France. First, we conducted field investigations for micro-terroir scale soil mapping in 2017, based on pedological prospections (pits and auger borings) and both water table levels and main meteorological parameters monitoring (from November 2017 to November 2018). Additionally, we collected for each vineyard plot the corresponding wine quality rank established each year since 2012 and based on wine tasting sessions supervised by the winemakers. Subse- quently we investigated both nutrients and water availability for the vine. This was achieved through correlative analysis using soil description, roots observation and water table level, stratified according to both soil functional units and wine quality ranks maps. Results show that the water table dynamic and the soil texture have a major impact on the root pattern of vines. Our study suggests that explanatory factors for wine quality are interactions between soil-water and roots during vine crop season. Here, best soils for fine wines could be observed for both non-severe water deficit and no-limited nutrient conditions.

Rock salt materials are experiencing a comeback and being reconsidered as promising positive materials for lithium ion batteries due to recent advancements. This reappraisal has been accelerated by the latest studies1 which have shown that the overlithiated compositions could provide much higher capacities (> 250 mAh/g) than the stoichiometric compositions. As the material becomes richer in lithium, the probability for Li+ ions finding an available space in the lattice increases due to the percolating network that is formed through the lithium diffusion channels2. Thus, greater material capacities can be achieved. Lithium titanium sulfide (Li2TiS3), which has been reported by Sakuda et al., demonstrated excellent capacity owing to the multi electron redox reactions3. By utilizing both sulfur and titanium redox, more than two lithium ions were reversibly intercalated through the structure and the capacity reached 425 mAh/g upon cycling between 3 V and 1.5 V vs Li+/Li. Although Li2TiS3 possesses such a large reversible capacity, its cycling stability is rather poor. Therefore, new approaches are necessary to enhance its cyclability. Partial substitution mechanisms are promising solutions in this issue. Here, we propose Se-substituted lithium titanium sulfide materials (Li2TiSexS3-x), which have recently been patented. By applying our patented synthesis process, Se substituted materials showed better cycling stability. For comparison, we will provide a comprehensive study of pure and substituted materials through fine characterization tools (XRD, SEM, EDX, ex situ and in situ XRD) in order to examine electrochemical and structural properties as well as the capacity degradation mechanism. References: [1] N. Yabuuchi, Proc. Natl. Acad. Sci., 112 (25), 7650–7655 (2015) [2] J. Lee, Science, 343 (6170), 519-521 (2014) [3] A. Sakuda, Sci. Rep, 4 (1), 4883 (2015) Figure 1

Lithium-rich manganese-based layered oxides Li[Li(x)Mn(y)TM(1-x-y)]O2 with TM standing for Ni, Co, or Fe are of great interest as cathode materials for lithium ion batteries. Indeed, among all of the materials, they offer the highest rechargeable capacity and energy density. However, when used, they suffer from complex evolutions that need to be understood before their practical use. Here we report on such evolutions studied using advanced transmission electron microscopy. Structural modifications are directly observed at the atomic scale using Cs corrected STEM HAADF imaging technique, and the chemical modifications are probed by the means of STEM EELS experiments. For the first time, segregation between nickel and manganese close the particle surface is pointed out. Finally, observed evolutions are correlated within a proposed mechanism that leads to the densification of the material. Our results allow understanding the link between the decrease of electrochemical performance and these evolutions occurring into the material upon cycling.

The aim of this study was to identify primary flow paths involved in the chlordecone (CLD) river contamination and quantify the CLD fluxes to assess CLD pollution levels and duration according to a typical catchment of the banana cropping area in the French Indies (Guadeloupe): the Perou Catchment (12 km(2)) characterized by heavy rainfall (5686 mm year(-1)). Three sub-catchments (SC1, SC2 and SC3) were studied during the hydrological year 2009-2010: a pedological survey combined with a spatialized hydrochemical approach was conducted. The average soil concentration is higher in the Perou Catchment (3400 mu g kg(-1)) than in the entire banana cropping area in Guadeloupe (2100 mu g kg(-1)). The results showed that CLD stocks in soils vary largely among soil types and farming systems: the weakest stocks are located upstream in SC1 (5 kg ha(-1)), where a majority of the area is non-cultivated; medium stocks are located in Nitisols downstream in SC3 (9 kg ha(-1)); and the greatest stocks are observed in SC2 on Andosols (12 kg ha(-1)) characterized by large farms. The annual water balance and the hydro-chemical analysis revealed that the three sub-catchments exhibited different behaviors. Perou River contamination was high during low flows, which highlighted that contamination primarily originated from groundwater contributions. The results showed that only a small part of the catchment (SC2), contributing little to the water flow, comprises a major CLD contribution, which is in agreement with the highly contaminated andosol soils observed there. Another significant result considers that at least 50 years would be required to export the totality of the actual CLD soil stocks retained in the topsoil layer. The actual time for soil remediation will however be much longer considering (i) the necessary time for the chlordecone to percolate and be stored in the shallow aquifers and (ii) its travel time to reach the river.rights reserved.

[Departement_IRSTEA]Territoires [TR1_IRSTEA]SYNERGIE [Axe_IRSTEA]TETIS-ATTOS; National audience; This work examines 140 hydrological studies conducted in the Mediterranean region. It identifies key characteristics of the hydrological responses of Mediterranean catchments at various time scales and compares different methods and modelling approaches used for individual-catchment studies. The study area is divided into the northwestern (NWM), eastern (EM) and southern (SM) Mediterranean. The analysis indicates regional discrepancies in which the NWM shows the most extreme rainfall regime. A tendency for reduced water resources driven by both anthropogenic and climatic pressures and a more extreme rainfall regime are also noticeable. Catchments show very heterogeneous responses over time and space, resulting in limitations in hydrological modelling and large uncertainties in predictions. However, few models have been developed to address these issues. Additional studies are necessary to improve the knowledge of Mediterranean hydrological features and to account for regional specificities.

The evolutions of the structure occurring into the lithium rich cobalt free layered cathode material Li1.2Mn0.61Ni0.18Mg0.01O2 upon the first electrochemical cycle were investigated by the means of high angle annular dark field (HAADF) imaging in a scanning transmission electron microscope and electron diffraction in a transmission electron microscope. They are coupled with electron energy loss spectroscopy (EELS) experiments in order to probe the chemical evolutions occurring during the first charge/discharge cycle. In the pristine material, the analysis of the HAADF images and electron diffraction patterns confirmed the ordering between the cations (Li or Ni with Mn) and the existence of disoriented domains stacked along the c axis. Moreover, the partial solid solution of Ni into Li2MnO3 leading to a composite material is evidenced. Upon the first charge, a loss of material is shown to have occurred, and the presence of a defect spinel phase due to the transfer of transition metal cations to the intersl...

Aim: Altmeier's procedure (perineal rectosigmoidectomy) is the operation of choice for rectal prolapse in the elderly. The aims of this prospective observational study were to evaluate its long-term actuarial recurrence risk and the influence of the length of rectosigmoid resection and associated levatorplasty on recurrence rate and continence. Method: The perioperative and long-term data of all patients undergoing Altemeier's procedure since 1992 were analyzed with regard to mortality, morbidity, continence, anorectal function and recurrence rate. Results: Sixty patients (median age: 77 years [35-98]) underwent rectosigmoid resection (median length of bowel 14 [6-60] cm) with associated levatorplasty in 21 (35%). Overall mortality and morbidity were 1.6% and 11.6% respectively. Manometry showed increased anal sphincter basal pressure and maximal squeeze pressure. We observed a decrease in postoperative rectal compliance (p=0.002). Age, gender, prolapse duration before surgery, levatorplasty and length of resection had no statistically significant relationship to recurrence. Continence improved in 62% and was stable over a median follow-up of 48 [1-186] months). Continence was positively related to a short length of bowel resection, but not to decreased rectal compliance. Actuarial recurrence was 14% at 4 years. Conclusion: The long-term recurrence rate after Altemeier procedure was low and not linked to resection length or to levatorplasty. Improvement in continence was stable over time.

The study of runoff is a crucial issue because it is closely related to flooding, water quality and erosion. In cultivated catchments, agricultural ditch drainage networks are known to influence runoff. As anthropogenic elements, agricultural ditch drainage networks can therefore be altered to better manage surface runoff in cultivated catchments. However, the relationship between the spatial configuration, i.e., the density and the topology, of agricultural ditch drainage networks and surface runoff in cultivated catchments is not understood. We studied this relationship by using a random network simulator that was coupled to a distributed hydrological model. The simulations explored a large variety of spatial configurations corresponding to a thousand stochastic agricultural ditch drainage networks on a 6.4 km2 Mediterranean cultivated catchment. Next, several distributed hydrological functions were used to compute water flow-paths and runoff for each simulation. The results showed that (i) denser networks increased the drained volume and the peak discharge and decreased hillslopes runoff, (ii) greater network density did not affect the surface runoff any further above a given network density, (iii) the correlation between network density and runoff was weaker for small subcatchments (< 2 km2) where the variability in the drained area that resulted from changes in agricultural ditch drainage networks increased the variability of runoff and (iv) the actual agricultural ditch drainage network appeared to be well optimized for managing runoff as compared with the simulated networks. Finally, our results highlighted the role of agricultural ditch drainage networks in intercepting and decreasing overland flow on hillslopes and increasing runoff in drainage networks.

This study aimed to review the authors' 16-year experience with transanal endoscopic microsurgery (TEM). Mortality, morbidity, recurrence rate, and functional outcome were assessed. New indications and technical improvements are presented.From November 1991 to August 2008, 123 patients (72 men and 51 women; median age, 68 years; range, 21-91 years) underwent TEM for excision of 105 adenomas with low- or high-grade dysplasia, 9 invasive adenocarcinomas (5 curative and 4 palliative resections), 2 neuroendocrine tumors, and 2 extramucosal lesions. Five additional patients had excisional biopsies, allowing staging after previous endoscopic resection. Most of the resections were full-thickness rectal resections using electrocautery or, more recently, the Harmonic scalpel. The latest mucosectomies were performed using the endoscopic submucosal dissection (ESD) technique. In addition, nontumoral indications included pelvic abscess (7 patients) and rectal strictures, which were either anastomotic or chemical. Pelvic abscesses were drained transrectally, whereas rectal stenoses were treated by strictureplasty. Foreign object retrieval and collagen plug placement for anal fistulas were performed using TEM in three patients.No mortality occurred. One intraoperative rectal perforation required conversion to laparotomy. The postoperative complications included one pneumoperitoneum, which was treated medically, and one rectal perforation requiring Hartmann's procedure. In the polyp subgroup, six patients (6/91, 7%) experienced local recurrence. Pelvic abscesses were successfully treated, and stenosis did not recur after strictureplasty. Anorectal manometry showed functional alterations without significant clinical impact.The findings showed TEM to be a safe and effective procedure for local excision of rectal lesions with a low recurrence rate and minimal consequences in terms of anorectal function. In addition, TEM proved to be feasible and effective for pelvic abscess drainage and rectal stenosis treatment. New technologies such as the Harmonic scalpel and ESD increase the precision already offered by this approach.