Étude de la production des ions bromate lors de l'ozonation des eaux de la Banlieue de Paris : choix du mode d'ozonation et variation des param tres physico-chimiques

Cette étude a permis d'évaluer l'importance de la concentration en ions bromure, de la température et de la nature de la Matière Organique Naturelle (MON) sur la production des ions bromate en s'appuyant sur des expériences conduites en laboratoire et sur pilote semi-industriel (Centre d'Essais de Méry-sur-Oise).Trois campagnes d'ozonation effectuées en parallèle à Méry-sur-Oise et au LCEE (Laboratoire de Chimie de l'Eau et de l'Environnement) sur des eaux filtrées sable, ont montré que les expériences conduites en laboratoire et sur pilote semi-industriel mènent à des résultats similaires, soit une relation linéaire [BrO3-]=f (C∙τ) vérifiant une pente identique pour des conditions expérimentales données (teneur en ions bromure, température, origine de l'eau). Ces travaux ont montré de façon nouvelle qu'une faible variation de la concentration en ions bromure (± 15 à 20 µg.L-1) suffisait à modifier significativement la formation des ions bromate. A C∙τ=10 et T=21°C, la production des ions bromate est passée de 16 à 27 µg.L-1 pour une augmentation de la concentration en ions bromure de 80 à 95 µg.L-1. Les résultats obtenus ont montré de plus que la température est un facteur important puisqu'une différence de 8°C (13 à 21°C) a entraîné, pour la même eau (80 µg.L-1 d'ions bromure, C∙τ=10), une augmentation de la concentration en ions bromate de 10 à 16 µg.L-1. Pour d'autres eaux (Seine, Marne et Oise), trois autres campagnes conduites avec des eaux clarifiées ont été effectuées après ajustement de la teneur en ions bromure et régulation de la température, ces trois eaux présentant par ailleurs des caractéristiques similaires en ce qui concerne le pH et l'alcalinité. A C∙τ équivalent, la production d'ions bromate s'est avérée significativement plus faible pour l'eau de l'Oise que pour les deux autres eaux. La nature de la MON pourrait donc avoir une influence notable sur la formation des ions bromate.The publication of Kurokawa et al. in 1990 confirming the toxicity of bromate of rats and mice, initiated the research effort that was internationally conducted during the last seven years to better understand the reaction mechanisms of bromate formation during the ozonation of natural waters. Based on the research findings regarding the effect of a number of parameters (bromide, ozone dose, pH, temperature, alkalinity, DOC content, ammonia, ...), predictive models (empirical and reaction kinetic based models), including molecular and/or radical pathways, have been developed with more or less success. Complementary results are still needed to better understand this complex mechanism.The main objective of our work was to evaluate how the seasonal variation of the physical chemical characteristics of Paris-area source waters (i.e. bromide content, temperature, natural organic matter) can affect the production of bromate during ozonation. In order to confirm that lab-scale experiments could be proposed to develop such research program, parallel tests were first conducted at the bench- and pilot-scale based on comparable C∙τ conditions. The lab-scale reactor was a 380 ml glass column (internal diameter: 0.02 m; height: 1.2 m) equipped with a water jacket to allow temperature to be varied and maintained. These reactor was used as a continuous flow reactor with recirculation. The pilot-scale ozonation contactor installed at the Méry sur Oise water treatment plant was comprised of four 30-liter columns in series (diameter: 0.1m ; height: 4m). The first column is used as the application column while the three others are used as residence column. The results have shown that lab-scale ozonation experiments conducted on Méry sur Oise sand filtered water led to similar results compared to pilot ozonation conducted on the same water and at the same temperature (sampled the same day) using the Méry sur Oise pilot-scale reactor. For applied C∙τ that ranged from 4 to 20 mg O3/L.min, similar linear relationship between bromate formation and applied C∙τ was obtained with the two reactors.A survey conducted on the Oise River has shown that the bromide concentration ranged from 40 µg/L (winter period) to 80 µg/L (summer period). If it is already well known that higher the bromide content, higher the bromate formation, our work has also pointed out that even a small increase of the bromide concentration from 80 to 95 µg/L (15 µg/L of bromide spiked as KBr) can significantly impact the bromate formation (same experimental conditions) that, as an example, increased from 16 to 27 µg/L for C.t of 10 at 21 °C.The temperature of the Oise river can vary from 5 °C up to 25 °C. Using carefully controlled temperature conditions, one can observed that the slope of the bromate production versus applied C∙τ increased with increasing temperature (same water). For example, the production of bromate during the ozonation (applied C∙τ=10) of the Méry sur Oise sand filtered water was 7, 10 and 16 µg/L for 5, 13 and 21 °C, respectively. Complementary experiments, have shown that the impact of the variation of the initial bromide concentration was proportionally more important for low-temperature water (5 to 13 °C) than for moderate-temperature water (20 °C).The origin and nature of the water is considered to play a significant role on the formation of bromate during ozonation, however few studies have evaluated the importance of these parameters using carefully controlled experimental conditions. In order to better define how important is the change in bromate production with the modification of the quality of the Paris suburbs water sources, especially the organic content (nature and concentration of the NOM), two sets of experiments were conducted.In the first part of the work, the Méry sur Oise sand filtered water was sampled at three different periods of the year 1996 (June, July and December), and the ozonation experiments were conducted at the same temperature (21 °C) after bromide concentration was adjust to 80 µg/L. The three water samples had the same pH and did not contain ammonia. Significant differences were observed in the bromate production, showing a larger production with the winter water as compared to the summer water. The fact that the winter water was enriched in DOC (3.7 mg/L of DOC) as compared to the two others (2.6 - 2.7 mg/L of DOC) may explain this difference since a larger ozone dose was probably necessary (ozone transfert not controlled because of the small size of the lab-scale reactor) to reach the same applied C∙τ due to a higher ozone consumption from the natural organic matter. The slightly lower alkalinity of the winter sample (200 mg/L as CaCO3 as compared to 250 mg/L CaCO3 for the summer samples) could have led to a less pronounced scavenger effect, condition that favors the radical pathway which is generally predominant. However, it is also known that carbonate species can also promote the formation of bromate due to the production of carbonate radicals. Comparing the results obtained with the water samples collected during the summer period, more bromate was produced in July than in June. The higher hydrophobic character (more aromatic in character) of the NOM of the water sampled in July (SUVA=2.15) as compared to the June sample (SUVA=1.88), characteristic that favor the ozone consumption and consequently the OH radical production, may justify this finding.In the second part of the work, the bromate formation obtained during the ozonation of the three major water sources of the Paris suburbs (sampled after clarification), Oise River, Marne River and Seine River, was compared (same temperature) after the bromide content was adjust to 80 µg/L. Similar results were obtained with the clarified Marne river and Seine River, the two waters showing the same physical chemical characteristics (2.2 and 2.5 mg/L of DOC; pH 7.9 and 7.8; Alkalinity: 225 and 210 mg/L as CaCO3). A lower production of bromate as a function of the applied C∙τ was observed with the clarified Oise river, result that is in contradiction with our previous hypotheses since this water source showed the highest DOC content, the highest SUVA and the lowest alkalinity among the three waters studied.More work needs to be done to better understand the impact of the origin and nature of the NOM on the bromate formation mechanisms. As a general conclusion, this work also confirmed that the physical chemical characteristics of source water (DOC, temperature, alkalinity, bromide content,…) are more important factors as compared to the hydraulic characteristics of the reactor.Keywords

Influence of Gamma-Ray Emission on the Isotopic Composition of Clouds in the Interstellar Medium

We investigate one mechanism of the change in the isotopic composition of cosmologically distant clouds of interstellar gas whose matter was subjected only slightly to star formation processes. According to the standard cosmological model, the isotopic composition of the gas in such clouds was formed at the epoch of Big Bang nucleosynthesis and is determined only by the baryon density in the Universe. The dispersion in the available cloud composition observations exceeds the errors of individual measurements. This may indicate that there are mechanisms of the change in the composition of matter in the Universe after the completion of Big Bang nucleosynthesis. We have calculated the destruction and production rates of light isotopes (D, 3He, 4He) under the influence of photonuclear reactions triggered by the gamma-ray emission from active galactic nuclei (AGNs). We investigate the destruction and production of light elements depending on the spectral characteristics of the gamma-ray emission. We show that in comparison with previous works, taking into account the influence of spectral hardness on the photonuclear reaction rates can increase the characteristic radii of influence of the gamma-ray emission from AGNs by a factor of 2-8. The high gamma-ray luminosities of AGNs observed in recent years increase the previous estimates of the characteristic radii by two orders of magnitude. This may suggest that the influence of the emission from AGNs on the change in the composition of the medium in the immediate neighborhood (the host galaxy) has been underestimated.Comment: 13 pages, 13 figures, 3 table

Combined approaches, including long-read sequencing, address the diagnostic challenge of HYDIN in primary ciliary dyskinesia

Primary ciliary dyskinesia (PCD), a disorder of the motile cilia, is now recognised as an underdiagnosed cause of bronchiectasis. Accurate PCD diagnosis comprises clinical assessment, analysis of cilia and the identification of biallelic variants in one of 50 known PCD-related genes, including HYDIN. HYDIN-related PCD is underdiagnosed due to the presence of a pseudogene, HYDIN2, with 98% sequence homology to HYDIN. This presents a significant challenge for Short-Read Next Generation Sequencing (SR-NGS) and analysis, and many diagnostic PCD gene panels do not include HYDIN. We have used a combined approach of SR-NGS with bioinformatic masking of HYDIN2, and state-of-the-art long-read Nanopore sequencing (LR_NGS), together with analysis of respiratory cilia including transmission electron microscopy and immunofluorescence to address the underdiagnosis of HYDIN as a cause of PCD. Bioinformatic masking of HYDIN2 after SR-NGS facilitated the detection of biallelic HYDIN variants in 15 of 437 families, but compromised the detection of copy number variants. Supplementing testing with LR-NGS detected HYDIN deletions in 2 families, where SR-NGS had detected a single heterozygous HYDIN variant. LR-NGS was also able to confirm true homozygosity in 2 families when parental testing was not possible. Utilising a combined genomic diagnostic approach, biallelic HYDIN variants were detected in 17 families from 242 genetically confirmed PCD cases, comprising 7% of our PCD cohort. This represents the largest reported HYDIN cohort to date and highlights previous underdiagnosis of HYDIN-associated PCD. Moreover this provides further evidence for the utility of LR-NGS in diagnostic testing, particularly for regions of high genomic complexity.</p

Opera and poison : a secret and enjoyable approach to teaching and learning chemistry

The storyline of operas, with historical or fictional characters, often include potions and poisons. This has prompted a study of the chemistry behind some operatic plots. The results were originally presented as a lecture given at the University of Minho in Portugal, within the context of the International Year of Chemistry. The same lecture was subsequently repeated at other universities as an invited lecture for science students and in public theaters for wider audiences. The lecture included a multimedia and interactive content that allowed the audience to listen to arias and to watch video clips with selected scenes extracted from operas. The present article, based on the lecture, demonstrates how chemistry and opera can be related and may also serve as a source of motivation and inspiration for chemistry teachers looking for alternative pedagogical approaches. Moreover, the lecture constitutes a vehicle that transports chemistry knowledge to wider audiences through examples of everyday molecules, with particular emphasis on natural products.The author is pleased to express his gratitude to Jorge Calado and Michael John Smith for useful discussions. The author also thanks the reviewers of the manuscript for their helpful comments and suggestions. Thanks are due to the Foundation for Science and Technology (FCT,Portugal), QREN and FEDER/EU for financial support through the research centers, CQ/UM PEst-C/QUI/UI0686/2011. Ciencia Viva, Portugal, is also acknowledged for financial support of the activities organized by the University of Minho during the International Year of Chemistry. The author also expresses his gratitude to Ana Paula Ferreira and Andre Cunha Leal from RTP Antena 2 who contributed immensely to the popularization of the lecture on which this paper is based on

Iron Accumulation with Age, Oxidative Stress and Functional Decline

Identification of biological mediators in sarcopenia is pertinent to the development of targeted interventions to alleviate this condition. Iron is recognized as a potent pro-oxidant and a catalyst for the formation of reactive oxygen species in biological systems. It is well accepted that iron accumulates with senescence in several organs, but little is known about iron accumulation in muscle and how it may affect muscle function. In addition, it is unclear if interventions which reduced age-related loss of muscle quality, such as calorie restriction, impact iron accumulation. We investigated non-heme iron concentration, oxidative stress to nucleic acids in gastrocnemius muscle and key indices of sarcopenia (muscle mass and grip strength) in male Fischer 344 X Brown Norway rats fed ad libitum (AL) or a calorie restricted diet (60% of ad libitum food intake starting at 4 months of age) at 8, 18, 29 and 37 months of age. Total non-heme iron levels in the gastrocnemius muscle of AL rats increased progressively with age. Between 29 and 37 months of age, the non-heme iron concentration increased by approximately 200% in AL-fed rats. Most importantly, the levels of oxidized RNA in gastrocnemius muscle of AL rats were significantly increased as well. The striking age-associated increase in non-heme iron and oxidized RNA levels and decrease in sarcopenia indices were all attenuated in the calorie restriction (CR) rats. These findings strongly suggest that the age-related iron accumulation in muscle contributes to increased oxidative damage and sarcopenia, and that CR effectively attenuates these negative effects

The Virtual Sociality of Rights: The Case of Women\u27s Rights are Human Rights

This essay traces the relationship between activists and academics involved in the campaign for women\u27s rights as human rights as a case study of the relationship between different classes of what I call knowledge professionals self-consciously acting in a transnational domain. The puzzle that animates this essay is the following: how was it that at the very moment at which a critique of rights and a reimagination of rights as rights talk proved to be such fertile ground for academic scholarship did the same rights prove to be an equally fertile ground for activist networking and lobbying activities? The paper answers this question with respect to the work of self-reflexivity in creating a virtual sociality of rights

Proteomic Modeling for HIV-1 Infected Microglia-Astrocyte Crosstalk

Background: HIV-1-infected and immune competent brain mononuclear phagocytes (MP; macrophages and microglia) secrete cellular and viral toxins that affect neuronal damage during advanced disease. In contrast, astrocytes can affect disease by modulating the nervous system’s microenvironment. Interestingly, little is known how astrocytes communicate with MP to influence disease. Methods and Findings: MP-astrocyte crosstalk was investigated by a proteomic platform analysis using vesicular stomatitis virus pseudotyped HIV infected murine microglia. The microglial-astrocyte dialogue was significant and affected microglial cytoskeleton by modulation of cell death and migratory pathways. These were mediated, in part, through F-actin polymerization and filament formation. Astrocyte secretions attenuated HIV-1 infected microglia neurotoxicity and viral growth linked to the regulation of reactive oxygen species. Conclusions: These observations provide unique insights into glial crosstalk during disease by supporting astrocytemediated regulation of microglial function and its influence on the onset and progression of neuroAIDS. The results open new insights into previously undisclosed pathogenic mechanisms and open the potential for biomarker discovery an

'Dressed in a Little Brief Authority': Authority Before, During, and After Shakespeare's Plays

This essay discusses the concept of authority from Shakespeare’s time to our own, considers examples of Shakespeare’s own explorations of authority, and provides a concise history of the ways in which Shakespeare has been constructed as cultural authority in different historical periods. It summarises the essays contained in the book, and argues that the book illuminates not only how Shakespeare became the archetypal figure of English cultural authority, but, perhaps more interestingly, why

Iron Behaving Badly: Inappropriate Iron Chelation as a Major Contributor to the Aetiology of Vascular and Other Progressive Inflammatory and Degenerative Diseases

The production of peroxide and superoxide is an inevitable consequence of aerobic metabolism, and while these particular "reactive oxygen species" (ROSs) can exhibit a number of biological effects, they are not of themselves excessively reactive and thus they are not especially damaging at physiological concentrations. However, their reactions with poorly liganded iron species can lead to the catalytic production of the very reactive and dangerous hydroxyl radical, which is exceptionally damaging, and a major cause of chronic inflammation. We review the considerable and wide-ranging evidence for the involvement of this combination of (su)peroxide and poorly liganded iron in a large number of physiological and indeed pathological processes and inflammatory disorders, especially those involving the progressive degradation of cellular and organismal performance. These diseases share a great many similarities and thus might be considered to have a common cause (i.e. iron-catalysed free radical and especially hydroxyl radical generation). The studies reviewed include those focused on a series of cardiovascular, metabolic and neurological diseases, where iron can be found at the sites of plaques and lesions, as well as studies showing the significance of iron to aging and longevity. The effective chelation of iron by natural or synthetic ligands is thus of major physiological (and potentially therapeutic) importance. As systems properties, we need to recognise that physiological observables have multiple molecular causes, and studying them in isolation leads to inconsistent patterns of apparent causality when it is the simultaneous combination of multiple factors that is responsible. This explains, for instance, the decidedly mixed effects of antioxidants that have been observed, etc...Comment: 159 pages, including 9 Figs and 2184 reference

The Natural Products Atlas : an open access knowledge base for microbial natural products discovery

Despite rapid evolution in the area of microbial natural products chemistry, there is currently no open access database containing all microbially produced natural product structures. Lack of availability of these data is preventing the implementation of new technologies in natural products science. Specifically, development of new computational strategies for compound characterization and identification are being hampered by the lack of a comprehensive database of known compounds against which to compare experimental data. The creation of an open access, community-maintained database of microbial natural product structures would enable the development of new technologies in natural products discovery and improve the interoperability of existing natural products data resources. However, these data are spread unevenly throughout the historical scientific literature, including both journal articles and international patents. These documents have no standard format, are often not digitized as machine readable text, and are not publicly available. Further, none of these documents have associated structure files (e.g., MOL, InChI, or SMILES), instead containing images of structures. This makes extraction and formatting of relevant natural products data a formidable challenge. Using a combination of manual curation and automated data mining approaches we have created a database of microbial natural products (The Natural Products Atlas, www.npatlas.org) that includes 24 594 compounds and contains referenced data for structure, compound names, source organisms, isolation references, total syntheses, and instances of structural reassignment. This database is accompanied by an interactive web portal that permits searching by structure, substructure, and physical properties. The Web site also provides mechanisms for visualizing natural products chemical space and dashboards for displaying author and discovery timeline data. These interactive tools offer a powerful knowledge base for natural products discovery with a central interface for structure and property-based searching and presents new viewpoints on structural diversity in natural products. The Natural Products Atlas has been developed under FAIR principles (Findable, Accessible, Interoperable, and Reusable) and is integrated with other emerging natural product databases, including the Minimum Information About a Biosynthetic Gene Cluster (MIBiG) repository, and the Global Natural Products Social Molecular Networking (GNPS) platform. It is designed as a community-supported resource to provide a central repository for known natural product structures from microorganisms and is the first comprehensive, open access resource of this type. It is expected that the Natural Products Atlas will enable the development of new natural products discovery modalities and accelerate the process of structural characterization for complex natural products libraries