Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River, SW France)

International audienceMining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM-EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water-sediment interface of (i) dissolved SO4 promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), not, vert, similar6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary

Numerical Assessment of Morphological and Hydraulic Properties of Moss, Lichen and Peat from a Permafrost Peatland

Due to its insulating and draining role, assessing ground vegetation cover properties is important for high-resolution hydrological modeling of permafrost regions. In this study, morphological and effective hydraulic properties of Western Siberian Lowland ground vegetation samples (lichens, Sphagnum mosses, peat) are numerically studied based on tomography scans. Porosity is estimated through a void voxels counting algorithm, showing the existence of representative elementary volumes (REVs) of porosity for most samples. Then, two methods are used to estimate hydraulic conductivity depending on the sample's homogeneity. For homogeneous samples, direct numerical simulations of a single-phase flow are performed, leading to a definition of hydraulic conductivity related to a REV, which is larger than those obtained for porosity. For heterogeneous samples, no adequate REV may be defined. To bypass this issue, a pore network representation is created from computerized scans. Morphological and hydraulic properties are then estimated through this simplified representation. Both methods converged on similar results for porosity. Some discrepancies are observed for a specific surface area. Hydraulic conductivity fluctuates by 2 orders of magnitude, depending on the method used. Porosity values are in line with previous values found in the literature, showing that arctic cryptogamic cover can be considered an open and well-connected porous medium (over 99 % of overall porosity is open porosity). Meanwhile, digitally estimated hydraulic conductivity is higher compared to previously obtained results based on field and laboratory experiments. However, the uncertainty is less than in experimental studies available in the literature. Therefore, biological and sampling artifacts are predominant over numerical biases. This could be related to compressibility effects occurring during field or laboratory measurements. These numerical methods lay a solid foundation for interpreting the homogeneity of any type of sample and processing some quantitative properties' assessment, either with image processing or with a pore network model. The main observed limitation is the input data quality (e.g., the tomographic scans' resolution) and its pre-processing scheme. Thus, some supplementary studies are compulsory for assessing syn-sampling and syn-measurement perturbations in experimentally estimated, effective hydraulic properties of such a biological porous medium.</p

Gain-of-function human STAT1 mutations impair IL-17 immunity and underlie chronic mucocutaneous candidiasis

Chronic mucocutaneous candidiasis disease (CMCD) may be caused by autosomal dominant (AD) IL-17F deficiency or autosomal recessive (AR) IL-17RA deficiency. Here, using whole-exome sequencing, we identified heterozygous germline mutations in STAT1 in 47 patients from 20 kindreds with AD CMCD. Previously described heterozygous STAT1 mutant alleles are loss-of-function and cause AD predisposition to mycobacterial disease caused by impaired STAT1-dependent cellular responses to IFN-γ. Other loss-of-function STAT1 alleles cause AR predisposition to intracellular bacterial and viral diseases, caused by impaired STAT1-dependent responses to IFN-α/β, IFN-γ, IFN-λ, and IL-27. In contrast, the 12 AD CMCD-inducing STAT1 mutant alleles described here are gain-of-function and increase STAT1-dependent cellular responses to these cytokines, and to cytokines that predominantly activate STAT3, such as IL-6 and IL-21. All of these mutations affect the coiled-coil domain and impair the nuclear dephosphorylation of activated STAT1, accounting for their gain-of-function and dominance. Stronger cellular responses to the STAT1-dependent IL-17 inhibitors IFN-α/β, IFN-γ, and IL-27, and stronger STAT1 activation in response to the STAT3-dependent IL-17 inducers IL-6 and IL-21, hinder the development of T cells producing IL-17A, IL-17F, and IL-22. Gain-of-function STAT1 alleles therefore cause AD CMCD by impairing IL-17 immunity

Bilan géochimique du transport des éléments traces métalliques dans le système fluvial anthropisé Lot-Garonne-Gironde

Le système fluvial Lot-Garonne est affecté par une pollution chronique polymétallique issue du drainage de terrils miniers par le Riou-Mort, un affluent du Lot. Sur la base d'une banque de données couvrant plus d'une décennie de mesures mensuelles des concentrations métalliques nous proposons un modèle empirique d'estimation des flux annuels de Cd à l'estuaire de la Gironde. Nous avons calculé que le Riou-Mort contribue jusqu'à 47 % (Cd), 20 % (Zn), 4 % (Cu) et 9 % (Pb) des flux bruts de la Garonne à l'estuaire de la Gironde. Notre étude montre que l'oxydation des sulfures des terrils miniers contrôle complètement les fortes concentrations de la fraction <0,2 µm des éléments traces métalliques (ETM) du Riou-Mort qui sont 400 (Zn) et 1200 (Cd) fois supérieures aux concentrations du Lot en amont de la pollution. Les résultats d'extractions sélectives montrent que dans le système Lot-Garonne, la spéciation particulaire des ETM est dominée par la fraction résiduelle, à l'exception de Cd, Zn, Mn. Dans le Riou-Mort, Zn et Cd sont associés à la fraction "échangeable" et montre le plus fort potentiel de mobilisation. Dans le Lot et la Garonne ils apparaissent moins mobilisables car principalement associés à la matière organique et/ou aux sulfures et aux carbonates. L'étude de la diagenèse précoce dans des sédiments de barrages a montré une superposition des réactions de minéralisation de la matière organique ; cette minéralisation étant majoritairement conduite par les oxydants secondaires. Toutefois, les réactions de diagenèse précoce n'ont pas semblé affecter significativement l'enregistrement sédimentaire historique de la pollution polymétallique dans les sédiments du Lot. Les profils des concentrations particulaires des ETM, chronologiquement recalés (137Cs), permettent de suivre les changements majeurs de l'activité industrielle responsable de la pollution. Les stocks de polluants métalliques des sédiments du Lot ont été estimés : ~10 000 t de Zn, ~1000 t de Pb, et ~300 t de Cu. Enfin, notre étude propose des valeurs du bruit de fond géochimique régional (en mg.kg-1) : 57 (V), 54 (Cr), 8,6 (Co), 19 (Ni), 17 (Cu), 81 (Zn), 0,56 (Cd), 31 (Pb), 10 (Th) et 2 (U).The Lot-Garonne-Gironde fluvial system is affected by heavy metal pollution resulting from acid mine drainage from the Riou-Mort River, a tributary of the Lot River. Based on a 10-year data set of monthly Cd concentrations, an empiric model for estimation of Cd fluxes to the Gironde estuary is proposed. We calculated that the Riou-Mort contributes up to 47 % (Cd), 20 % (Zn), 4% (Cu) et 9% (Pb) of the gross input of the Garonne River into the Gironde estuary. This study showed the oxydation of the mining waste sulfides is responsible for the high dissolved heavy metal concentrations found in the Riou-Mort. These concentrations are 400 (Zn) and 1200 (Cd) times higher than that of the Lot River upstream the pollution. Selective extractions showed that, in the Lot- Garonne fluvial system, particulate heavy metal speciation is dominated by the residual fraction, except for Cd, Zn and Mn which are mainly associated with the “exchangeable” fraction and consequently show the highest mobilization potentiality. In the Lot and Garonne Rivers, Cd and Zn are less mobilizable as mainly associated with organic matter/sulfides and carbonates. The study of the early diagenesis processes in dam lake sediments showed the overlap of reactions of organic matter oxidation. Our results suggest that reactions involving all ‘secondary' oxidants (nitrate, manganese and iron oxides and sulfate) are the main pathway for carbon remineralization in these sediments. Nevertheless, we show that early diagenesis processes did not change significantly the sedimentary record of the heavy metal pollution. The particulate heavy metal concentration profiles, coupled with 137Cs geochronology, permit to follow the main changes of the industrial activity responsible for the heavy metal pollution. The present day heavy metal stock in the Lot River sediment were estimated: ~10,000 t of Zn, ~1,000 t of Pb, and ~300 t of Cu. Finally, we propose natural background values for heavy metal in the Lot-Garonne watershed (mg.kg-1) : 57 (V), 54 (Cr), 8,6 (Co), 19 (Ni), 17 (Cu), 81 (Zn), 0,56 (Cd), 31 (Pb), 10 (Th) et 2 (U)

Effect of estuarine sediment resuspension on early diagenesis, sulfide oxidation and dissolved molybdenum and uranium distribution in the Gironde estuary, France

International audienceVertical distributions of dissolved major redox parameters, Mo and U from the water to the sediment were sampled in the salinity gradient of the Gironde estuary. In the water, sulfate and Mo are conservatively transported throughout the salinity gradient. In contrast, U shows a significant removal rate of 85 mu mol m(-2) a(-1) related to reductive sequestration of U in the anoxic sediment. Early diagenesis is highly transient and characterized by a three-zone regime related to three density layers functioning at different timescales. Excess of sulfate (up to 1 mM) is observed in the soft mud layer and is assigned to sulfide oxidation by both abiotic Mn- and Fe-oxide reduction and bacterial nitrate reduction. During early diagenesis, Mo and U are released in the sediment porewater from Mn- and Fe-oxides. In not-dredged anoxic sediments, authigenic precipitation of Mo and U with iron sulfides is proposed to explain their removal from solution. In contrast, in dredged sediments, authigenic precipitation of U is inhibited probably owing to the less effective reduction of soluble U(VI) to insoluble U(IV) due to oxidizing transient conditions. Mixing of anoxic sediment porewater with oxygenated water, due to (i) cyclical resuspension of the soft mud layer and (ii) dredging operations in the navigation channel, induces addition of dissolved sulfate (produced from diagenetic sulfide oxidation), Mo and U to the water. This addition is equivalent to 2% (sulfate), 5.5% (Mo) and 0.5% (U) of the dissolved fluvial inputs into the estuary for the natural resuspension, and 0.4% (Mo), less than 0.2% (sulfate, U) for dredge-induced resuspension. Addition of dissolved Mo and U, produced by oxidation of sulfide phases in the dredged sediments redeposited in dynamic environments, are equivalent to 12% (Mo) and 0.8% (U) of their respective fluvial inputs. Additional Mo and U inputs into the water originate from diffusive outflow from muddy sediments and are equivalent to 2% (Mo) and 0.3% (U) of their respective fluvial inputs. However, we show that all these dissolved inputs are scavenged by solid phases

Sources, mobility and bioavailability of metals in the mining and smelter impacted altiplanean city of Oruro, Bolivia

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

International audienceVertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O2 dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities

A proto-telomere is elongated by telomerase in a shelterin-dependent manner in quiescent fission yeast cells

International audienceAbstract Telomere elongation is coupled with genome replication, raising the question of the repair of short telomeres in post-mitotic cells. We investigated the fate of a telomere-repeat capped end that mimics a single short telomere in quiescent fission yeast cells. We show that telomerase is able to elongate this single short telomere during quiescence despite the binding of Ku to the proto-telomere. While Taz1 and Rap1 repress telomerase in vegetative cells, both shelterin proteins are required for efficient telomere extension in quiescent cells, underscoring a distinct mode of telomerase control. We further show that Rad3ATR and Tel1ATM are redundantly required for telomere elongation in quiescence through the phosphorylation of Ccq1 and that Rif1 and its associated-PP1 phosphatases negatively regulate telomerase activity by opposing Ccq1 phosphorylation. The distinct mode of telomerase regulation in quiescent fission yeast cells may be relevant to that in human stem and progenitor cells