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Compréhension et modélisation de l’emballement thermique des batteries Li-ion
No full textSince the commercialization of Lithium-Ion Battery (LIB) by Sony Inc. in 1991 until today, recurrent incidents involving LIBs have been reported worldwide. During these incidents, the most energetic catastrophic failure of a LIB system is the thermal runaway event. With the emergence of highly reactive Ni-rich LIBs in the market, battery safety is becoming even more critical because these newly introduced LIBs present such high energy density which could lead to more catastrophic events subsequent to the thermal runaway. Therefore, this thesis aims to go deeper into the understanding and modelling of this complex phenomenon at cell scale, taking into account the influence of novel highly reactive technologies and the influence of state of charge (SOC) and aging, in order to understand what the key factors are towards inherently safer design and operation of LIBs. Thanks to the synergism offered by combined experimental and modelling studies of this thesis, knowledge in terms of initiation and evolution of the thermal runaway of Ni-rich Li-ion batteries has been enriched. The modelling study leads to the development of a 3D extended thermal runaway model to predict the behaviours of different Li-ion batteries nearby and during thermal runaway. The experimental study investigates the thermal runaway of LIBs and provides suitable databases for the predictive model calibration and validation. The developed model can be used as a simulation tool to explore more scenarios of cells undergoing thermal runaway in specified conditions for which adequate parameterization can be defined in relation with underpinning physics. This contributes to the future Li-ion battery safety management system in depthAu regard du problème de sécurité récurrent constaté depuis la commercialisation des batteries au lithium-ion (LIBs), associé à un manque de maîtrise du risque d'emballement thermique qui les caractérisent, cette thèse vise à approfondir la compréhension et la modélisation de ce phénomène complexe à l'échelle cellulaire, en prenant en compte l'influence des nouvelles technologies hautement réactives (dopage en Ni) ainsi que les influences de l'état de charge (SOC) et du vieillissement, afin de comprendre le rôle de ces facteurs clés pour une conception et un fonctionnement intrinsèquement plus sûr de telles batteries au lithium-ion. Grâce à la synergie offerte par les études expérimentales et de modélisation combinées de cette thèse, les connaissances en termes d'initiation et d'évolution de l'emballement thermique des batteries Li-ion riches en Ni se sont enrichies. L'étude de modélisation conduit au développement d'un modèle 3D d'emballement thermique étendu pour prédire les comportements de différentes batteries Li-ion en champ temporel proche et pendant le processus d'emballement thermique. L'étude expérimentale examine l'emballement thermique des LIBs et fournit des bases de données suffisantes pour la calibration et la validation du modèle prédictif. Le modèle développé peut être utilisé comme outil de simulation pour explorer plus de scénarios de cellules subissant un emballement thermique dans des conditions spécifiées pour lesquelles un paramétrage adéquat peut être défini en relation avec la physique sous-jacente. Ce travail ouvre de nouvelles perspectives en matière de stratégie de gestion de la sécurité des batteries Li-io
Results of the Pre-Normative Research Project PRESLHY for the Safe Use of Liquid Hydrogen
No full textInternational audienceLiquid hydrogen (LH2) compared to compressed gaseous hydrogen offers advantages for large-scale transport and storage of hydrogen with higher densities. Although the gas industry has good experience with LH2 only little experience is available for the new applications of LH2 as an energy carrier. Therefore, the European FCH JU funded project PRESLHY conducted pre-normative research for the safe use of cryogenic LH2 in non-industrial settings. The central research consisted of a broad experimental program, combined with analytical work, modelling and simulations belonging to the three key phenomena of the accident chain: release and mixing, ignition and combustion. The presented results improve the general understanding of the behavior of LH2 in accidents and provide some design guidelines and engineering tools for safer use of LH2. Recommendations for improvement of current international standards are derived
Comparison of uptake and elimination kinetics of metallic oxide nanomaterials on the freshwater microcrustacean Daphnia magna
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Phytomanagement of a Trace Element-Contaminated Site to Produce a Natural Dye: First Screening of an Emerging Biomass Valorization Chain
No full textInternational audienceThe study of different possible biomass valorization routes is crucial in order to diversify phytomanagement options, allowing the landowner/stakeholder to choose the best option based on site characteristics and the benefits of local value chains. In the current study, field and laboratory experiments were conducted to assess the suitabilitity of Malva sylvestris L. for the phytoattenuation of a dredged sediment disposal site contaminated with trace elements (trace element (Cd, Cu, Pb, and Zn). The selected crop was Malva sylvestris, a flowering plant from which a colourant can be extracted to be used in dying of textiles as a way to valorize the produced biomass grown on this contaminated land. Under the conditions of the investigated site, the analysis of TE in the sediment and the biomass matrix showed no effect of M. sylvestris on the sediment TE contamination mobility with an excluder phenotype (Bioconcentration factor < 1). Metal concentrations were found to be the highest in the leaves followed by in the stem and flower. The dye extract obtained from the flower part of M. sylvestris permitted the silk alum-pretreated fabric to be dyed yellow, and the TE concentration in the dyed textile fabrics respected the threshold values set by OEKO-Tex standard 100
Nanopharmaceuticals (Au-NPs) after use: Experiences with a complex higher tier test design simulating environmental fate and effect
No full textInternational audienceThe current environmental hazard assessment is based on the testing of the pristine substance. However, it cannot be excluded that (nano)pharmaceuticals are excreted into sewage during the use phase followed by entry into wastewater treatment plants (WWTPs). Sorption to sewage sludge or release via effluent can result in modified ecotoxicological effects which possibly can only be detected with a modified test approach. The objective of our study was to investigate a realistic exposure scenario for metallic nanoparticles (NPs) in pharmaceutical products, excreted into effluent, and released into the environment after treatment in WWTPs. The test approach was illustrated by using gold (Au) NPs. Effluent from model WWTPs were investigated in aquatic tests (Daphnia magna, fish cell lines). Sewage sludge was used as a sole food source (Eisenia fetida) or mixed with soil and used as test medium (soil microorganisms, Folsomia candida, Enchytraeus crypticus). To cover the aspect of regulation, the test systems described in OECD-test guidelines (OECD TG 201, 211, 220, 232, 249, 317) were applied. Modifications and additional test approaches were included to meet the needs arising out of the testing of nanomaterials and of the exposure scenarios. The results were assessed regarding the suitability of the test design and the toxicity of Au-NPs. Except for activated sludge as a sole food source for E.fetida, the selected test approach is suitable for the testing of nanomaterials. Additional information can be gained when compared to the common testing of the pristine nanomaterials in the standardized test systems. Effects of Au-NPs were observed in concentrations exceeding the modeled environmental
Indicateur de la pression de pollution chimique sur le bassin de la Seine
No full textCe travail s'inscrit dans l'objectif de développer des indicateurs permettant de connaître la pression de pollution chimique s'exerçant sur le bassin de la Seine. En effet, malgré les efforts et les progrès considérables réalisés par le programme dans la connaissance de la contamination chimique, le nombre de produits chimiques présents de longue date et actuellement utilisés sur le bassin de la Seine est certainement de l'ordre de grandeur de la dizaine de milliers au moins. De plus leur nombre et les quantités utilisées sont vraisemblablement en augmentation. Le but de ces travaux est d'essayer de mieux appréhender cette réalité de la « chimiodiversité » et ses conséquences, pour ce qui est de l'évolution passée, et future de cette pression, même si seule une partie très minoritaire en est accessible à la connaissance. Dans un second temps, des scénarios prospectifs permettront d'essayer de dessiner des moyens de réduire les impacts futurs, tenant compte des approches règlementaires (sur les produits chimiques, le recyclage, les matériaux...), mais cherchant à intégrer également des innovations territoriales sur le bassin. Ce rapport porte sur la première phase de ce programme, à savoir l'identification des données pour la construction d'un univers initial des substances chimiques incluant les substances historiquement étudiées par le programme PIREN-Seine et d'autres molécules d'intérêt, concernant potentiellement le bassin, l'identification des sources de données à mobiliser et la construction de l'indicateur. L'indicateur proposé est basé sur : (i) le nombre de produits chimiques pris en compte pour chaque période temporelle, (ii) les quantités de produit chimique mises sur le marché, (iii) un score de persistance dans des matériaux et articles présents sur le bassin, (iv) la demi-vie dans les milieux environnementaux, (v) un facteur de bioconcentration/bioaccumulation, (vi) un indicateur de la toxicité pour les milieux aquatiques (PNEC), et (vii) un indicateur de la toxicité pour la santé humaine (VTR) pouvant être affecté d'un facteur aggravant lorsque les produits chimiques sont suspectés ou confirmés en tant que perturbateur endocrinien et/ou Cancérigènes Mutagènes Reprotoxiques (CMR). Cet indicateur sera calculé pour des périodes temporelles passées et futures afin de reconstruire l'évolution passée et étudier des scénarios prospectifs. Les paramètres pouvant évoluer dans le temps sont le nombre, l'identité et les quantités des produits chimiques. En raison de limitations concernant la disponibilité des données sur les usages, notamment des données spécifiques au bassin de la Seine, il sera pertinent de travailler par plages temporelles d'au moins une dizaine d'années. Des hypothèses seront nécessaires pour relier les usages à l'évolution de données connues (par exemple, l'évolution des quantités de matériaux de base dans lesquels les produits chimiques sont employés, ou interpolations avec des variables macroéconomiques pour les périodes non documentées)
Emission factors and chemical characterization of particulate emissions from garden green waste burning
No full textInternational audienceThis work provides an evaluation of the emission factors (EFs) of typical garden waste burning (fallen leaves and hedge trimming) in terms of particulate matter (PM), elemental and organic carbon (EC-OC) together with a detailed chemical characterization of 88 particle-bound organic species including polycyclic aromatic hydrocarbons (PAHs), levoglucosan and its isomers, lignin breakdown products (methoxyphenols), cholesterol, alkanes, polyols and sugars. Furthermore, wood-log based burning experiments have been performed to highlight key indicators or chemical patterns of both, green waste and wood burning (residential heating) sources, that may be used for PM source apportionment purposes. Two residential log wood combustion appliances, wood stove (RWS) and fireplace, under different output conditions (nominal and reduced) and wood log moisture content (mix of beech, oak and hornbeam), have been tested. Open wood burning experiments using wood logs were also performed. Green waste burning EFs obtained were comparable to the available literature data for open-air biomass burning. For PM and for most of the organic species studied, they were about 2 to 30 times higher than those observed for wood log combustion experiments. Though, poor performance wood combustions (open-air wood log burning, fireplace and RWS in reduced output) showed comparable EFs for levoglucosan and its isomers, methoxyphenols, polyols, PAHs and sugars. Toxic PAH equivalent benzo[a]pyrene EFs were even 3–10 times higher for the fireplace and open-air wood log burning. These results highlighted the impact of the nature of the fuel burnt and the combustion performances on the emissions. Different chemical fingerprints between both biomass burning sources were highlighted with notably a predominance of odd high-molecular weight n-alkanes (higher carbon preference index, CPI), lower levoglucosan/mannosan ratio and lower sinapylaldehyde abundance for green waste burning. However, the use of such indicators seems limited, especially if applied alone, for a clear discrimination of both sources in ambient air
Living Labs and other participatory approaches applied to research on multiple environnemental exposures and chronic risks
No full textInternational audienceParticipatory research in environmental health is still rare in France. The objectives of environmental health research, in general, can be very diverse (e.g.: identifying situations associated with risks estimating exposures and effects, testing the effectiveness of preventive actions) and related methods are diverse as well. Opportunities for greater implication of the civil society and related challenges differ at each step of research activities. These aspects need to be better known and shared collectively. The LILAS project aimed to 1) co-construct, among institutional researchers, academics and civil society representatives, a mutual understanding of the main problematics and research methods in environmental health, their stakes for different actors, but also the requirements, strengths and limitations of these methods 2) identify expected benefits and points of vigilance related to stronger degrees of participation as part of such environmental health research projects. METHODS: LILAS gathered institutional researchers, academics and civil society representatives interested in multiple exposures (chemical, radiological). Several meetings allowed to collectively identify different types of study (including environmental epidemiological studies) and reflect about the added value, limitations, and methodological principles related to the introduction of growing participation as part of such studies. An analysis matrix was co-created and filled by participants. RESULTS:For different types of studies (studies for assessment of environmental exposures, identification of their determinants, interventions on these exposures, development of sensors, quantitative risk assessment, environmental epidemiological studies, experimental research, studies on the health of ecosystems…), the matrix lists expected benefits for several categories of stakeholders, fundamental methodological principles and practical constraints, advantages and limitations related to the use of participatory approaches (such as the living lab one) or more “classical” approaches. CONCLUSIONS:LILAS has allowed, through a cross-acculturation process, to develop consolidated grounds for the co-construction of future participatory research projects on multiple environmental exposures
Results of comparisons of the predictions of 17 dense gas dispersion models with observations from the Jack Rabbit II chlorine field experiment
No full textInternational audienceThe Jack Rabbit II (JR II) chlorine field trials in 2015 and 2016 involved nine 5–20 ton releases of pressurized liquefied chlorine from a tank mounted 1 m above a broad flat desert sand surface. A model comparison study was initiated, where 17 widely-used dense-gas dispersion models were run by scientists in seven countries. Predictions were submitted following specified formats, using specified emissions and meteorology inputs. To compare with the model predictions, sets of observations were defined for the arc-maximum 1–3 s averaged concentrations (arc max C) and for cloud widths and heights (to 20 ppm and 200 ppm contours) at distances from 0.2 to 11.0 km from the release. The initial focus is on the three field trials (1, 6, and 7) that have the highest observed concentrations and that have detailed emissions information. It is found that these models are able to satisfactorily simulate (generally within a factor of two) the observed arc max C's and their variation with downwind distance at this flat desert site. At each downwind distance, the scatter in the arc max C predictions covers about 1 ½ orders of magnitude, but the observed arc max C is within the range of the predictions. The median of the cloud width predictions is about 50% larger than the observed value for the three trials. The median of the cloud height predictions is within about 10% of the observed value. For both cloud width and/or height, there are a few models with large (factor of 3 or higher) overpredictions. Of the 17 models, when compared to observations, there is a core group of 5 or 6 with consistently (across all three trials and all distances) less mean error and scatter in their predictions of arc max C and cloud width and height. However, as a group, the 17 models are performing adequately (using the “factor of two” rule of thumb). An important caveat is that, at the JR II desert site, chlorine deposition is minimal. At a site with vegetation and/or organic-rich soil, the effects of removal of chlorine by deposition are expected to be significant
Human biomonitoring initiative (HBM4EU): Human biomonitoring guidance values (HBM-GVs) derived for bisphenol A
No full textInternational audienceThe "European Human Biomonitoring Initiative" (HBM4EU) derives human biomonitoring guidance values (HBM-GVs) for the general population (HBM-GV(GenPop)) and/or for occupationally exposed adults (HBM-GV(Worker)) for several priority substances and substance groups as identified by policy makers, scientists and stakeholders at EU and national level, including bisphenol A (BPA). Human exposure to BPA is widespread and of particular concern because of its known endocrine-disrupting properties. Unlike the conjugated forms of BPA circulating in the body, free BPA is known to interact with the nuclear estrogen receptors. Because free BPA is considered to be more toxicologically active than the conjugated forms (e.g. BPA-glucuronide (BPA-G) and BPA-sulfate (BPA-S)), its measurement in blood provides the superior surrogate of the biologically effective dose. However, considering the difficulty of implementing blood sampling in large HBM cohorts, as well as the current analytical capacities complying with the quality assurance (QA)/quality control (QC) schemes, total BPA in urine (i.e. the sum of free and conjugated forms of BPA measured after an hydrolysis of phase II metabolites) was retained as the relevant exposure biomarker for BPA. HBM-GV(GenPop) for total BPA in urine of 230 mu g/L and 135 mu g/L for adults and children, respectively, were developed on the basis of toxicological data. To derive these values, the concentrations of urinary total BPA consistent with a steady-state exposure to the temporary Tolerable Daily Intake (t-TDI) of 4 mu g/kg bw/day set in 2015 by the European Food Safety Authority (EFSA) were estimated. The BPA human physiologically-based pharmacokinetic (PBPK) model developed by Karrer et al. (2018) was used, assuming an oral exposure to BPA at the t-TDI level averaged over 24 h. Dermal uptake of BPA is suspected to contribute substantially to the total BPA body burden, which in comparison with the oral route, is generating a higher ratio of free BPA to total BPA in blood. Therefore, an alternative approach for calculating the HBM-GV(GenPop) according to the estimated relative contributions of both the oral and dermal mutes to the global BPA exposure is also discussed. Regarding BPA exposure at the workplace, the steady-state concentration of urinary total BPA was estimated after a dermal uptake of BPA that would generate the same concentration of free BPA in plasma (considered as the bioactive form) as would a 24 h-averaged intake to the European Chemicals Agency (ECHA)'s oral DNEL of 8 mu g BPA/kg bw/day set for workers. The predicted concentration of urinary total BPA at steady-state is equivalent to, or exceeds the 95th percentile of total BPA in urine measured in different European HBM studies conducted in the general population. Thus, no HBM-GV(Worker) was proposed, as the high background level of BPA coming from environmental exposure - mostly through food intake - is making the discrimination with the occupational exposure to BPA difficult