Caractérisation physico-chimique des interactions métaux-diatomées

Cette étude expérimentale a consisté en la caractérisation de l'interaction entre les métaux et les parois cellulaire des diatomées. Une approche combinant des mesures spectroscopiques, IR et XPS, avec des titrages acido-basiques et des déterminations de mobilité électrophorétiques, ont permis l'élaboration d'un modèle thermodynamique de surface des diatomées. La complexation des cations métalliques, Zn2+, Cd2+, et Pb2+ sur les parois cellulaires a été déterminée par des expériences d'adsorption en fonction du pH et de la concentration en métal et a permis de développer un modèle de complexation surfacique. Il indique que i) le frustule siliceux intervient très peu dans les processus d'adsorption ii) la complexation des métaux s'effectue principalement sur les groupes carboxyliques de la surface en accord avec les mesures XAFS effectuées pour l'adsorption du zinc. Des mesures d'isotopie du zinc ont mis en évidence un fractionnement induit par les diatomées.The aim of this experimental study was to characterize the interactions between metals and diatom cell walls. Spectroscopic measurements, FT-IR and XPS, in combination with titrations and electrokinetic experiments allowed the construction of a surface thermodynamic model for diatoms. Complexation between metal cations Zn2+, Cd2+, Pb2+ and diatom cell walls were investigated by adsorption experiments as a function of pH and a surface complexation model was developed. It indicates i) that siliceous frustule plays a minor rule during adsorption process and ii) metal complexation is governed by carboxylic groups from the surface in agreement with XAFS determination for zinc adsorption. Isotopic measurements for zinc indicate an isotopic fractionation induced by diatom cells

Social anxiety and negative early life events in university students

Abstract Introduction: There is substantial evidence regarding the impact of negative life events during childhood on the aetiology of psychiatric disorders. We examined the association between negative early life events and social anxiety in a sample of 571 Spanish University students. Methods: In a cross-sectional survey conducted in 2007, we collected data through a semistructured questionnaire of sociodemographic variables, personal and family psychiatric history, and substance abuse. We assessed the five early negative life events: (i) the loss of someone close, (ii) emotional abuse, (iii) physical abuse, (iv) family violence, and (v) sexual abuse. All participants completed the Liebowitz Social Anxiety Scale. Results: Mean (SD) age was 21 (4.5), 75% female, LSAS score was 40 (DP = 22), 14.2% had a psychiatric family history and 50.6% had negative life events during childhood. Linear regression analyses, after controlling for age, gender, and family psychiatric history, showed a positive association between family violence and social anxiety score (p = 0.03). None of the remaining stressors produced a significant increase in LSAS score (p > 0.05). Conclusion: University students with high levels of social anxiety presented higher prevalence of negative early life events. Thus, childhood family violence could be a risk factor for social anxiety in such a population

Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio

Zn Isotope Fractionation during Sorption onto Kaolinite

International audienceIn this study, we quantify zinc isotope fractionation during its sorption onto kaolinite, by performing experiments under various pH, ionic strength, and total Zn concentrations. A systematic enrichment in heavy Zn isotopes on the surface of kaolinite was measured, with Delta Zn-66(adsorbed-solution) ranging from 0.11 parts per thousand at low pH and low ionic strength to 0.49 parts per thousand at high pH and high ionic strength. Both the measured Zn concentration and its isotopic ratio are correctly described using a thermodynamic sorption model that considers two binding sites: external basal surfaces and edge sites. Based on this modeling approach, two distinct Zn isotopic fractionation factors were calculated: Delta Zn-66(adsorbed-solution) = 0.18 +/- 0.06 parts per thousand for ion exchange onto basal sites, and Delta Zn-66(adsorbed-solution) = 0.49 +/- 0.06 parts per thousand for specific complexation onto edge sites. These two distinct factors indicate that Zn isotope fractionation is dominantly controlled by the chemical composition of the solution (pH, ionic strength

Metals in the Aquatic Environment—Interactions and Implications for the Speciation and Bioavailability: A Critical Overview

International audienceIn most case scenarios, individual metals exist as components in mixtures with organic and inorganic substances and/or particulate matter. While the concepts encompassing mixture toxicity and modeling have been around for decades, only recently have new approaches (dynamic speciation techniques and fate and bioavailability models) been expanded to consider metal mixture scenarios. For example, the kinetic features of humic substances and inorganic colloids on the complexation of metals are generally considered. Although current environmental regulations rarely require an assessment of chemicals mixtures, research on these mixtures in the environment is essential for future regulatory demands and is vital for ensuring adequate environmental protection. Interpretation of speciation and bioavailability data from metal mixtures can be very complex and demanding, due to the existence of kinetic physicochemical transformations of the dynamic components. This kinetic effect largely affects metals' dynamic speciation, culminating in different transformed metal-containing products with different contributions for the metal uptake by a consuming interface. This manuscript is focused on the environmental fate of metal mixtures, which determines how the mixture is biogeochemically processed and which receptors are most exposed (organisms and exposure route), with a special focus on their dynamic speciation, including a critical evaluation of the current challenges and available dynamic speciation techniques as well as computer codes and model

Flow and fate of silver nanoparticles in small French catchments under different land-uses: The first one-year study

International audienc

The Fate of Polyol-Made ZnO and CdS Nanoparticles in Seine River Water (Paris, France)

International audienceThis study aims to characterize nanoparticles with different compositions and structures as well as seeing their evolutions over time in a natural environment such as Seine river water (Paris, France). Face centered cubic (fcc) and hexagonal (hcp) CdS as well as hexagonal (hcp) ZnO nanoparticles were synthesized by the Polyol method. CdS nanoparticles (i) cfc structure: are agglomerated, present 100 nm length with heterogeneous diameter and 10 m(2) g(-1) specific surface area (S-g) from Brunauer Emett and Teller (BET) measurements; (ii) hcp structure: 20 nnn and S-g = 67 m(2) g(-1). ZnO hcp nanoparticles presents 50 nm length and 15 nm diameter and S-g = 54 m(2) g(-1). These results are in agreement with X-ray diffraction (XRD), and small angle X-ray scattering (SAXs). After 48 h interaction with Seine river water, cryo-TEM analysis showed that ZnO nanoparticles form spherical agglomerates with 300 nnn diameter; CdS nanoparticles (fcc) are agglomerated presenting large diameters (>500 nm); and CdS nanoparticles (hcp) are not agglomerated and present the same characteristics of the starting material. After 168h of contact with Seine river water, CdS (fcc) presents only 14% of dissolution, CdS (hcp) presents both 60% dissolution and 30% reprecipitation in a cadmium carbonate form and finally almost 90% of ZnO nanoparticles are dissolved

How Microbial Biofilms Control the Environmental Fate of Engineered Nanoparticles?

International audiencePredicting the fate of engineered nanoparticles (ENPs) once they are released in the environment is essential to evaluate their impacts to ecosystems. Microbial biofilms, as highly reactive compartments in soils and sediments, have the potential to impose strong controls on ENPs life cycle in natural settings. However, information regarding impacts of biofilms toward ENPs environmental fate are not easily accessible, and such evidences are collected and discussed in this review, in order to identify common trends and to better constrain the role played by these microbial structures. Biofilms are reported to exhibit important ENPs accumulation capacities, and short to long-term ENPs immobilization can thus be expected. Mechanisms that govern such accumulation and ENPs migration within biofilms depend strongly on electrostatic and hydrophobic interactions, as well as biofilm structural properties, such as density and permeability. They are a combination of key parameters that include ENPs size and surface properties, mineral substrate reactivity, ability to develop organic corona around ENPs, or formation of aggregates within the biofilm thickness. In addition, these microbial structures exhibit highly reactive microenvironments, and are consequently able to impose major ENPs transformations such as dissolution, through ligand- or redox-mediated pathways, as well as passivation or stabilization processes. Interestingly, exposure to toxic ENPs can even trigger a response from micro-organisms biofilms which has the potential to strongly modify ENPs speciation. Promising approaches to investigate the role of microbial biofilms for ENPs cycling in realistic systems are introduced through the use of mesocosms, medium-size replicated ecosystems that allow to integrate the complexity of natural settings. Finally, biofilm-mediated nanoparticles synthesis in man-impacted systems is presented. This raises important questions regarding biofilms role as secondary sources of nanoparticles

Exopolysaccharides protect Synechocystis against the deleterious effects of Titanium dioxide nanoparticles in natural and artificial waters

International audienceWe have studied the effect of TiO2 nanoparticles (NPs) on the model cyanobacteria Synechocystis PCC6803. We used well-characterized NPs suspensions in artificial and natural (Seine River, France) waters. We report that NPs trigger direct (cell killing) and indirect (cell sedimentation precluding the capture of light, which is crucial to photosynthesis) deleterious effects. Both toxic effects increase with NPs concentration and are exacerbated by the presence of UVAs that increase the production of Reactive Oxygen Species (hydroxyl and superoxide radicals) by TiO2 NPs. Furthermore, we compared the responses of the wild-type strain of Synechocystis, which possesses abundant exopolysaccharides surrounding the cells, to that of an EPS-depleted mutant. We show, for the first time, that the exopolysaccharides play a crucial role in Synechocystis protection against cell killing caused by TiO2 NP

Mass-dependent and -independent signature of Fe isotopes in magnetotactic bacteria

International audienceMagnetotactic bacteria perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the earliest microorganisms capable of biomineralization on Earth, identifying their activity in ancient sedimentary rocks remains challenging because of the lack of a reliable biosignature. We determined Fe isotope fractionations by the magnetotactic bacterium Magnetospirillum magneticum AMB-1. The AMB-1 strain produced magnetite strongly depleted in heavy Fe isotopes, by 1.5 to 2.5 per mil relative to the initial growth medium. Moreover, we observed mass-independent isotope fractionations in 57Fe during magnetite biomineralization but not in even Fe isotopes (54Fe, 56Fe, and 58Fe), highlighting a magnetic isotope effect. This Fe isotope anomaly provides a potential biosignature for the identification of magnetite produced by magnetotactic bacteria in the geological record