Combination of 13 C/ 113 Cd NMR, potentiometry, and voltammetry in characterizing the interactions between Cd and two models of the main components of soil organic matter

International audienceThis work allowed the characterization of the Cd-binding sites of two compounds taken as models for exudates, the main components of soil organic matter (SOM). The studied compounds were exopolysaccharides (EPS), specifically exudates of roots (polygalacturonic acid) and of soil bacteria (Phytagel). Potentiometric acid– base titrations were performed and fitting of the obtained results indicated the presence of two main classes of acidic sites, defined by their pK a values, for both EPS but of a different nature when comparing the two compounds. The two studied exopolysaccharides presented different acidic/ basic site ratios: 0.15 for Phytagel and 0.76 for polyga-lacturonic acid. Spectroscopic techniques (13 C/ 113 Cd NMR, FTIR) distinguished different Cd surroundings for each of the studied EPS, which is in agreement with the titration results. Furthermore, these analyses indicated the presence of –COOH and –OH groups in various proportions for each exopolysaccharide, which should be linked to their reactiv-ity towards cadmium. Cadmium titrations (voltammetric measurements) also differentiated different binding sites for each compound and allowed the determination of the strength of the Cd-binding site of the EPS. Fitting of the results of such voltammetric measurements was performed using PROSECE (Programme d'Optimisation et de Speci-ation Chimique dans l'Environnement), a software coupling chemical speciation calculation and binding parameter optimization. The fitting, taking into account the Cd 2+ /H

Études de taphonomie archéologique en milieu périglaciaire actuel : le Projet Gavarnie

Un programme d’archéologie expérimentale a été initié en milieu périglaciaire actuel. Le site sélectionné est localisé dans les Pyrénées centrales, sur le versant sud du Massif du Taillon, secteur de Gavarnie. Les expériences entreprises traitent des points suivants : (1) vitesse de déplacement des vestiges et évolution des structures anthropiques – amas de taille – par solifluxion et par reptation sur talus gravitaire ; (2) fragmentation des ossements et altération des états de surface ; (3) vitesse d’acquisition d’une orientation préférentielle des vestiges lithiques déplacés par solifluxion ou reptation. Après un an de fonctionnement, certains paramètres contrôlant la nature et la vitesse des modifications peuvent être identifiés. Pour les ossements, le caractère frais ou sec détermine les déplacements, tandis que le caractère brûlé / non brûlé apparaît prééminent par rapport à leur fragmentation. Dans le cas des vestiges lithiques déposés sur coulée de solifluxion, les déplacements diffèrent selon la disposition initiale des objets – en amas ou dispersés –. Ces premiers résultats permettent de réexaminer la validité des précédentes expériences de taphonomie archéologique en contexte périglaciaire.A set of long-term experiments have been initiated in an active periglacial environment. The experimental site is located on the south slope of the Taillon Mountain, near Gavarnie, Spain. Experiments address the following points: 1) the rate of displacement of archaeological particles and the disturbance of archaeological features on solifluction sheets and by creep on rockfall screes; 2) the fragmentation of bones and their surface alteration, with emphasis on cutmark disappearance; 3) the rate of linear fabric acquisition of knapped flint displaced by solifluction or creep. After one year, disturbances are observed. Considering bones, factors responsible for the changes noted are 1) green versus dry nature of items with regard to displacements 2) burnt versus unburnt status in respect of alteration. For lithic assemblage, we observe that initial artifact distribution – in regimented intervals or replicating knapping spot – controls the rate of displacement. This last point is crucial to the application of experimental data to archaeological sites. Previous experiments can be discussed in light of these preliminary results

Etudes de taphonomie archéologique en milieu périglaciaire actuel : le projet Gavarnie.

A set of long-term experiments have been initiated in active periglacial environment. The experimental site is located on the south slope of Taillon Mountain, near Gavarnie, Spain. Experiments address the following points: 1) rate of displacement of archaeological particles and disturbance of archaeological features on solifluction sheet and by creep on rockfall screes; 2) fragmentation of bones and their surface alteration, with emphasis on cutmarks disappearance; 3) the rate of linear fabric acquisition of knapped flint displaced by solifluction or creep. After one year, disturbances are observed. Considering bones, factors responsible for the changes noted are 1) green versus dry nature of items with regard to displacements 2) burnt versus unburnt status in respect of alteration. For lithic assemblage, we observe that initial setting of artifacts - in regimented intervals or replicating knapping spot - controls the rate of displacement. This last point is crucial in the application of experimental data to the application of experimental data to archaeological sites. Previous experiments can be discussed in light of these preliminary results.Un programme d'archéologie expérimentale a été entrepris en milieu périglaciaire actuel. Le site sélectionné est localisé dans les Pyrénées centrales, sur le versant sud du Massif du Taillon, secteur de Gavarnie. Les expériences entreprises traitent des points suivants : 1) vitesse de déplacement des vestiges et évolution des structures anthropiques - amas de taille - par solifluxion et par reptation sur talus gravitaire ; 2) fragmentation des ossements et altération des états de surface ; 3) vitesse d'acquisition d'une orientation préférentielle des vestiges lithiques déplacés par solifluxion ou reptation. Après un an de fonctionnement, certains paramètres contrôlant la nature et la vitesse des modifications peuvent être identifiés. Pour les ossements, le caractère frais ou sec détermine les déplacements, tandis que le caractère brûlé / non brûlé apparaît prééminent par rapport à leur fragmentation. Dans le cas des vestiges lithiques déposés sur coulées de solifluxion, les déplacements diffèrent selon la disposition initiale des objets - en amas ou dispersés -. Ces premiers résultats permettent de réexaminer la validité des précédentes expériences de taphonomie archéologique en contexte périglaciaire

A case report of unilateral cerebral vasculitis in adults: keep in mind Lyme neuroborreliosis

Abstract Background Lyme neuroborreliosis (LNB), due to infection of the nervous system by the spirochete Borrelia burgdorferi, occurs in 15% of Lyme disease cases. However, neurovascular involvement is uncommon, especially recurrent stroke related to cerebral vasculitis in the absence of CSF pleocytosis. Case presentation We report the case of a 58-year-old man without any medical history who exhibited recurrent strokes in the same vascular territory (left internal carotid). Multiple biological screening, neuroimaging methods, and cardiovascular examinations failed to provide a diagnosis and treatment that could have prevented recurrences. Finally, B. burgdorferi sensu lato serology testing in blood and cerebrospinal fluid enabled diagnosis of LNB, in relation to a cerebral vasculitis. The patient experienced no further stroke after four weeks of doxycycline treatment. Conclusion B. burgdorferi central nervous system infection must be considered in case of unexplained recurrent and/or multiple strokes, especially if cerebral vasculitis is suspected or demonstrated on neuroimaging

Significance of data treatment and experimental setup on the determination of copper complexing parameters by anodic stripping voltammetry

International audiencea b s t r a c t Different procedures of voltammetric peak intensities determination, as well as various experimental setups were systematically tested on simulated and real experimental data in order to identify critical points in the determination of copper complexation parameters (ligand concentration and conditional stability constant) by anodic stripping voltammetry (ASV). Varieties of titration data sets (Cu measured vs. Cu total) were fitted by models encompassing discrete sites distribution of one-class and two-class of binding ligands (by PROSECE software). Examination of different procedures for peak intensities determi-nation applied on voltammograms with known preset values revealed that tangent fit (TF) routine should be avoided, as for both simulated and experimental titration data it produced an additional class of strong ligand (actually not present). Peak intensities determination by fitting of the whole voltammogram was found to be the most appropriate, as it provided most reliable complexation parameters. Tests performed on real seawater samples under different experimental conditions revealed that in addition to importance of proper peak intensities determination, an accumulation time (control of the sensitivity) and an equilibration time needed for complete complexation of added copper during titration (control of complexation kinetics) are the keypoints to obtain reliable results free of artefacts. The consequence of overestimation and underestimation of complexing parameters is supported and illustrated by the example of free copper concentrations (the most bioavailable/toxic specie) calculated for all studied cases. Errors up to 80% of underestimation of free copper concentration and almost two orders of magnitude overestimation of conditional stability constant were registered for the simulated case with two ligands

Have decades of abiotic studies in sediments been misinterpreted?

International audienceSterilization techniques are largely employed to distinguish biotic and abiotic processes in biogeochemical studies as they inhibit microbial activity. Since one century, chemical sterilizers, supposed to preserve original environmental samples, have taken precedence over physical sterilization techniques considered too destructive. Sodium azide (NaN3) is nowadays the most commonly used inorganic chemical sterilizer. It is sufficiently purified to study trace metals, as well. Nevertheless, its (in)activity in physico-chemical processes was never ascertained. Through the investigation of sediment resuspension in seawater, the present work unequivocally demonstrated that NaN3 can impact carbon and trace metals' transfers by altering the redox balance and pH. Unlike decades of blind practice, NaN3 should be used with great care to track abiotic processes from organic matter rich and reductive matrices

Dissolved organic matter controls of arsenic bioavailability to bacteria

International audienceThe presence of arsenic in irrigation and drinking waters is a threat to worldwide human health. Dissolved organic matter (DOM) is a ubiquitous and photoreactive sorbent of arsenic, capable of both suppressing and enhancing its mobility. Microbes can control the mobilization of mineral-bound arsenic, through redox processes thought to occur intracellularly. The role that DOM plays on the bioavailability of arsenic to microbes is often invoked but remains untested experimentally. Here, using a whole-cell biosensor, we tested the role of DOM on As (III) and As(V) bioavailability. Using cation amendments, we explored the nature of As-DOM interactions. We found As bioavailability to be dependent on [As]/[DOM] ratio and on the strength of As binding to DOM which varied as a function of time. We further tested the role of DOM on As(III) photooxidation and showed that As (III) photooxidation rate is limited by the strength of its interactions with DOM and sensitive to ionic competitive desorption. Our study demonstrates the dynamic control that photoreactive DOM poses on the bioavailability and reactivity of As in the environment and highlights the kinetic controls that DOM can possibly exert on As toxicity at various levels in foodwebs

Root-induced changes in pH and dissolved organic matter binding capacity affect copper dynamic speciation in the rhizosphere

International audienceDue to only few experimental evidences, the importance of root-induced alteration of metal dynamic speciation in the rhi-zosphere in the determination of metal bioavailability to plants is still a matter for debate. The present study thus investigated how root-induced changes in pH and dissolved organic matters (DOM) altered copper (Cu) dynamic speciation in the rhizo-sphere of durum wheat (Triticum turgidum durum L.). Plants were exposed to a Cu-contaminated soil previously alkalised by liming to cover soil pH values ranging from 4.8 to 7.5. A range of analytical techniques was deployed on soil exposed (i.e. in the rhizosphere) or not (i.e. in the bulk soil) to plant roots, including the measurement and the modelling (using the Humic Ion-Binding Model VI) of Cu 2+ activity, the measurement of labile Cu concentration and Cu lability by Differential Pulse Anodic Stripping Voltammetry (DPASV) and Diffusive Gradients in Thin films (DGT). Due to root-induced alkalisation, pH reached about 7.3 in the rhizosphere whatever the initial bulk soil pH. Compared to the most acidic bulk soil (pH % 4.8), Cu 2+ activity decreased by three orders of magnitude in the rhizosphere while DPASV-Cu concentration decreased by 6-fold. DOM became the key driver of Cu dynamic speciation in the rhizosphere, where roots induced up to an order of magnitude increase in DOM concentration compared to bulk soils. This resulted in an increase in labile-Cu (both DPASV and DGT) concentrations, in spite of a decrease in Cu 2+ activity. Model VI calculations supported a decrease in DOM binding capacity towards Cu in the rhizosphere. DPASV measurements unequivocally demonstrated that the increase in Cu lability in the rhizosphere solution can be attributed to a greater lability of organically-bound Cu. Collectively, our data introduce a consistent picture of root-induced changes of Cu dynamic speciation in the rhizosphere that were notably related to substantial alterations of DOM binding capacity

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

International audienceAn interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K i equ), total ligands concentration (L iT) and association/dissociation rate constants (k i 1 ,k i -1). A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K 1 equ : 11.2–13.0, log K 2 equ :8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter. Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k 1 1 :6.1–20 × 10 3 (M s) − 1 , k 2 1 : 1.3–6.3 × 10 3 (M s) − 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h. It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM C , i.e. 1 mg C L − 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM)

Assessment and modelling of Ni(II) retention by an ion-imprinted polymer: Application in natural samples

International audienc