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1.
Nature ; 619(7968): 94-101, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37407683

RESUMO

Despite numerous studies on Himalayan erosion, it is not known how the very high Himalayan peaks erode. Although valley floors are efficiently eroded by glaciers, the intensity of periglacial processes, which erode the headwalls extending from glacial cirques to crest lines, seems to decrease sharply with altitude1,2. This contrast suggests that erosion is muted and much lower than regional rock uplift rates for the highest Himalayan peaks, raising questions about their long-term evolution3,4. Here we report geological evidence for a giant rockslide that occurred around 1190 AD in the Annapurna massif (central Nepal), involving a total rock volume of about 23 km3. This event collapsed a palaeo-summit, probably culminating above 8,000 m in altitude. Our data suggest that a mode of high-altitude erosion could be mega-rockslides, leading to the sudden reduction of ridge-crest elevation by several hundred metres and ultimately preventing the disproportionate growth of the Himalayan peaks. This erosion mode, associated with steep slopes and high relief, arises from a greater mechanical strength of the peak substratum, probably because of the presence of permafrost at high altitude. Giant rockslides also have implications for landscape evolution and natural hazards: the massive supply of finely crushed sediments can fill valleys more than 150 km farther downstream and overwhelm the sediment load in Himalayan rivers for a century or more.

2.
Proc Natl Acad Sci U S A ; 118(4)2021 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-33479173

RESUMO

The long-term fate of uranium-contaminated sediments, especially downstream former mining areas, is a widespread environmental challenge. Essential for their management is the proper understanding of uranium (U) immobilization mechanisms in reducing environments. In particular, the long-term behavior of noncrystalline U(IV) species and their possible evolution to more stable phases in subsurface conditions is poorly documented, which limits our ability to predict U long-term geochemical reactivity. Here, we report direct evidence for the evolution of U speciation over 3,300 y in naturally highly U-enriched sediments (350-760 µg ⋅ g-1 U) from Lake Nègre (Mercantour Massif, Mediterranean Alps, France) by combining U isotopic data (δ238U and (234U/238U)) with U L3 -edge X-ray absorption fine structure spectroscopy. Constant isotopic ratios over the entire sediment core indicate stable U sources and accumulation modes, allowing for determination of the impact of aging on U speciation. We demonstrate that, after sediment deposition, mononuclear U(IV) species associated with organic matter transformed into authigenic polymeric U(IV)-silica species that might have partially converted to a nanocrystalline coffinite (UIVSiO4·nH2O)-like phase. This diagenetic transformation occurred in less than 700 y and is consistent with the high silica availability of sediments in which diatoms are abundant. It also yields consistency with laboratory studies that proposed the formation of colloidal polynuclear U(IV)-silica species, as precursors for coffinite formation. However, the incomplete transformation observed here only slightly reduces the potential lability of U, which could have important implications to evaluate the long-term management of U-contaminated sediments and, by extension, of U-bearing wastes in silica-rich subsurface environments.

3.
Int J Mol Sci ; 23(6)2022 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-35328356

RESUMO

The replacement of fishmeal by plant proteins in aquafeeds imposes the use of synthetic methionine (MET) sources to balance the amino acid composition of alternative diets and so to meet the metabolic needs of fish of agronomic interest such as rainbow trout (RT-Oncorhynchus mykiss). Nonetheless, debates still exist to determine if one MET source is more efficiently used than another by fish. To address this question, the use of fish cell lines appeared a convenient strategy, since it allowed to perfectly control cell growing conditions notably by fully depleting MET from the media and studying which MET source is capable to restore cell growth/proliferation and metabolism when supplemented back. Thus, results of cell proliferation assays, Western blots, RT-qPCR and liquid chromatography analyses from two RT liver-derived cell lines revealed a better absorption and metabolization of DL-MET than DL-Methionine Hydroxy Analog (MHA) with the activation of the mechanistic Target Of Rapamycin (mTOR) pathway for DL-MET and the activation of integrated stress response (ISR) pathway for MHA. Altogether, the results clearly allow to conclude that both synthetic MET sources are not biologically equivalent, suggesting similar in vivo effects in RT liver and, therefore, questioning the MHA efficiencies in other RT tissues.


Assuntos
Oncorhynchus mykiss , Ração Animal/análise , Animais , Linhagem Celular , Dieta , Hepatócitos/metabolismo , Fígado/metabolismo , Metionina/análogos & derivados , Metionina/química , Oncorhynchus mykiss/metabolismo
4.
Environ Sci Technol ; 54(2): 797-806, 2020 01 21.
Artigo em Inglês | MEDLINE | ID: mdl-31821755

RESUMO

Stable Pb isotope ratios were measured and compared to U distributions in three soil cores located in a wetland highly impacted by water discharge of a former U-mine. Pb isotope ratios showed notable alignments in binary mixing plots, demonstrating the dissemination of radioactive-enriched material from the U-mine. Thanks to these alignments and to the measurement of the 204Pb isotope, a precise characterization of the Pb isotope composition of the U-ore was performed without the use of U-ore samples. The well-defined end-members with the help of a reevaluated isotope mixing model allowed the accurate determination of the radiogenic Pb percentages in the cores that were overall found to be >50%. Noncorrelated distributions of radiogenic 206Pb and U are observed in several of the wetland soil samples. They reveal postdepositional U redistribution explained by major U speciation changes due to redox cycling in the wetland. On the contrary, the radiogenic 206Pb showed no or little postdepositional mobility and thus can be considered to be a memory tracer of the dissemination of U-rich radioactive material: even after an important U loss, the radiogenic 206Pb is able to reveal past contamination by U-rich materials.


Assuntos
Chumbo , Poluentes do Solo , Monitoramento Ambiental , Isótopos , Solo , Áreas Alagadas
5.
Environ Sci Technol ; 53(17): 10208-10217, 2019 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-31390183

RESUMO

Peat layers within alluvial sediments are considered effective arsenic (As) sinks under reducing conditions due to the binding of As(III) to thiol groups in natural organic matter (NOM) and the formation of As-bearing sulfide phases. However, their possible role as sources of As for anoxic groundwaters remains unexplored. Here, we perform laboratory experiments to provide evidence for the role of a sediment peat layer in releasing As. Our results show that the peat layer, deposited about 8,000 years ago in a paleomangrove environment in the nascent Mekong Delta, could be a source of As to porewater under reducing conditions. X-ray absorption spectroscopy (XAS) analysis of the peat confirmed that As was bound to NOM thiol groups and incorporated into pyrite. Nitrate was detected in peat layer porewater, and flow-through and batch experiments evidenced the release of As from NOM and pyrite in the presence of nitrate. Based on poisoning experiments, we propose that the microbially mediated oxidation of arsenic-rich pyrite and organic matter coupled to nitrate reduction releases arsenic from this peat. Although peat layers have been proposed as As sinks in earlier studies, we show here their potential to release depositional- and/or diagenetically-accumulated As.


Assuntos
Arsênio , Água Subterrânea , Poluentes Químicos da Água , Sedimentos Geológicos , Oxirredução , Solo , Espectroscopia por Absorção de Raios X
6.
Environ Sci Technol ; 52(17): 9615-9624, 2018 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-29983058

RESUMO

Sorbed U(IV) species can be major products of U(VI) reduction in natural reducing environments as sediments and waterlogged soils. These species are considered more labile than crystalline U(IV) minerals, which could potentially influence uranium migration in natural systems subjected to redox oscillations. In this study, we examined the role of oxygen and carbonate on the remobilization of uranium from lake sediments, in which ∼70% of the 150-300 ppm U is under the form of mononuclear U(IV) sorbed species. Our results show that both drying and oxic incubation only slightly increase the amount of remobilized U after 8 days, compared to anoxic drying and anoxic incubation. In contrast, the amount of remobilized U increases with the quantity of added bicarbonate even under anoxic conditions. Moreover, U LIII-edge XANES data show that a significant amount of the solid U(IV) is mobilized in such conditions. Thermodynamic speciation calculations based on the supernatant composition indicates the predominance of aqueous UO2(CO3)34- and, to a lesser extent, CaUO2(CO3)32- complexes. These results suggest that monomeric U(IV) species could be oxidized into aqueous U(VI) carbonate complexes even under anoxic conditions via carbonate promoted oxidative dissolution, which emphasizes the need for considering such a process when modeling U dynamics in reducing environments.


Assuntos
Urânio , Bicarbonatos , Carbonatos , Sedimentos Geológicos , Oxirredução , Solo
7.
Environ Sci Technol ; 52(22): 13099-13109, 2018 11 20.
Artigo em Inglês | MEDLINE | ID: mdl-30339761

RESUMO

Wetlands have been proposed to naturally attenuate U transfers in the environment via U complexation by organic matter and potential U reduction. However, U mobility may depend on the identity of particulate/dissolved uranium source materials and their redox sensitivity. Here, we examined the fate of uranium in a highly contaminated wetland (up to 4500 mg·kg-1 U) impacted by former mine water discharges. Bulk U LIII-EXAFS and (micro-)XANES combined with SEM-EDXS analyses of undisturbed soil cores show a sharp U redox boundary at the water table, together with a major U redistribution from U(IV)-minerals to U(VI)-organic matter complexes. Above the water table, U is fully oxidized into mono- and bidentate U(VI)-carboxyl and monodentate U(VI)-phosphoryl complexes. Minute amounts of U(VI)-phosphate minerals are also observed. Below the water table, U is fully reduced and is partitioned between U(IV)-phosphate minerals (i.e., ningyoite and a lermontovite-like phase), and bidentate U(IV)-phosphoryl and monodentate U(IV)-carboxyl complexes. Such a U redistribution from U-minerals inherited from mine water discharge deposits could result from redox cycling nearby the water table fluctuation zone. Oxidative dissolution of U(IV)-phosphate minerals could have led to U(VI)-organic matter complexation, followed by subsequent reduction into U(IV)-organic complexes. However, uranium(IV) minerals could have been preserved in permanently waterlogged soil.


Assuntos
Urânio , França , Minerais , Oxirredução , Fosfatos , Solo , Áreas Alagadas
8.
Environ Sci Technol ; 52(6): 3431-3439, 2018 03 20.
Artigo em Inglês | MEDLINE | ID: mdl-29451383

RESUMO

Arsenic contamination in groundwater is pervasive throughout deltaic regions of Southeast Asia and threatens the health of millions. The speciation of As in sediments overlying contaminated aquifers is poorly constrained. Here, we investigate the chemical and mineralogical compositions of sediment cores collected from the Mekong Delta in Vietnam, elucidate the speciation of iron and arsenic, and relate them to the sediment depositional environment. Gradual dissolution of ferric (oxyhydr)oxides with depth is observed down to 7 m, corresponding to the establishment of reducing conditions. Within the reduced sediment, layers originating from marine, coastal or alluvial depositional environments are identified and their age is consistent with a late Holocene transgression in the Mekong Delta. In the organic matter- and sulfur-rich layers, arsenic is present in association with organic matter through thiol-bonding and in the form of arsenian pyrite. The highest arsenic concentration (34-69 ppm) is found in the peat layer at 16 m and suggests the accumulation of arsenic due to the formation of thiol-bound trivalent arsenic (40-55%) and arsenian pyrite (15-30%) in a paleo-mangrove depositional environment (∼8079 yr BP). Where sulfur is limited, siderite is identified, and oxygen- and thiol-bound trivalent arsenic are the predominant forms. It is also worth noting that pentavalent arsenic coordinated to oxygen is ubiquitous in the sediment profile, even in reduced sediment layers. But the identity of the oxygen-bound arsenic species remains unknown. This work shows direct evidence of thiol-bound trivalent arsenic in the Mekong Delta sediments and provides insight to refine the current model of the origin, deposition, and release of arsenic in the alluvial aquifers of the Mekong Delta.


Assuntos
Arsênio , Água Subterrânea , Poluentes Químicos da Água , Monitoramento Ambiental , Sedimentos Geológicos , Vietnã
9.
Appl Microbiol Biotechnol ; 102(22): 9803-9813, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30155752

RESUMO

Arsenic removal consecutive to biological iron oxidation and precipitation is an effective process for treating As-rich acid mine drainage (AMD). We studied the effect of hydraulic retention time (HRT)-from 74 to 456 min-in a bench-scale bioreactor exploiting such process. The treatment efficiency was monitored during 19 days, and the final mineralogy and bacterial communities of the biogenic precipitates were characterized by X-ray absorption spectroscopy and high-throughput 16S rRNA gene sequencing. The percentage of Fe(II) oxidation (10-47%) and As removal (19-37%) increased with increasing HRT. Arsenic was trapped in the biogenic precipitates as As(III)-bearing schwertmannite and amorphous ferric arsenate, with a decrease of As/Fe ratio with increasing HRT. The bacterial community in the biogenic precipitate was dominated by Fe-oxidizing bacteria whatever the HRT. The proportion of Gallionella and Ferrovum genera shifted from respectively 65 and 12% at low HRT to 23 and 51% at high HRT, in relation with physicochemical changes in the treated water. aioA genes and Thiomonas genus were detected at all HRT although As(III) oxidation was not evidenced. To our knowledge, this is the first evidence of the role of HRT as a driver of bacterial community structure in bioreactors exploiting microbial Fe(II) oxidation for AMD treatment.


Assuntos
Arsênio/metabolismo , Bactérias/isolamento & purificação , Bactérias/metabolismo , Reatores Biológicos/microbiologia , Águas Residuárias/microbiologia , Poluentes Químicos da Água/metabolismo , Ácidos/química , Ácidos/metabolismo , Arsênio/análise , Bactérias/classificação , Bactérias/genética , Biodegradação Ambiental , Biodiversidade , Ferro/química , Cinética , Mineração , Oxirredução , Fatores de Tempo , Águas Residuárias/química , Poluentes Químicos da Água/análise
10.
Environ Sci Technol ; 51(1): 150-158, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27966928

RESUMO

Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As-I is usually assigned to the occupation of tetrahedral S-I sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of AsIII and AsII have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for AsII,III incorporation into pyrite at octahedral FeII sites and for As-I at tetrahedral S-I sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As-I incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of AsII,III for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.


Assuntos
Arsênio , Compostos Ferrosos , Ferro/química , Oxirredução , Temperatura , Espectroscopia por Absorção de Raios X
11.
Environ Sci Technol ; 50(5): 2281-91, 2016 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-26828118

RESUMO

The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.


Assuntos
Arsênio/química , Compostos Ferrosos/química , Ferro/química , Fosfatos/química , Shewanella/metabolismo , Arseniatos/metabolismo , Arsênio/metabolismo , Compostos Férricos/química , Compostos Ferrosos/metabolismo , Água Subterrânea , Oxirredução , Fosfatos/metabolismo , Espectroscopia por Absorção de Raios X
12.
Proc Natl Acad Sci U S A ; 110(37): 14883-8, 2013 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-23980143

RESUMO

The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.


Assuntos
Óxido Ferroso-Férrico/metabolismo , Magnetospirillum/metabolismo , Compostos Férricos/metabolismo , Nanopartículas de Magnetita/ultraestrutura , Magnetossomos/metabolismo , Magnetossomos/ultraestrutura , Magnetospirillum/ultraestrutura , Microscopia Eletrônica de Transmissão e Varredura , Microscopia Eletrônica de Transmissão , Fosfatos/metabolismo , Espectroscopia por Absorção de Raios X
13.
Environ Sci Technol ; 49(7): 4506-14, 2015 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-25756496

RESUMO

Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants.


Assuntos
Ferro/química , Nanopartículas de Magnetita/química , Ácido Nalidíxico/química , Adsorção , Cromatografia Líquida de Alta Pressão/métodos , Compostos Férricos/química , Óxido Ferroso-Férrico/química , Radical Hidroxila , Oxirredução , Espectrometria de Massas em Tandem , Espectroscopia por Absorção de Raios X , Difração de Raios X
14.
Environ Sci Technol ; 49(24): 14065-75, 2015 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-26544528

RESUMO

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.


Assuntos
Compostos Férricos/química , Ferro/química , Sphaerotilus/química , Urânio/química , Adsorção , Biofilmes , Precipitação Química , Análise dos Mínimos Quadrados , Microscopia Eletrônica de Varredura , Minerais/química , Fosfatos/química , Espectrometria por Raios X , Urânio/isolamento & purificação
15.
Antonie Van Leeuwenhoek ; 107(5): 1135-44, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25666377

RESUMO

Sphaerotilus natans is a neutrophilic iron-related sheath-forming filamentous microorganism that presents dual morphotype: single cells and ensheathed cells forming filaments. As S. natans has been proposed as a sorbent for inorganic pollutants and it is occasionally involved in bulking episodes, elucidating factors affecting its filamentous growth is of crucial interest. The purpose of this work was to evaluate the effect of dissolved oxygen (DO) as a factor affecting S. natans filamentation from single cells. A method to quantify S. natans in its filamentous and single-cell morphotypes, based on a differential filtration procedure coupled with quantitative real-time PCR, was developed here. Scanning Electron Microscopy was used to validate the filtration step. Under actively aerated conditions (DO maintained at 7.6 ± 0.1 mg l(-1)), S. natans grew mainly as single cells throughout the experiment, while a depletion in DO concentration (to ~3 mg l(-1)) induced its filamentous growth. Indeed, when oxygen was reduced the proportion of single cells diminished from 83.3 ± 5.9 to 14.3 ± 3.4% while the filaments increased from 16.7 ± 5.9 to 85.7 ± 3.4%. Our results suggest that oxygen plays a key role in S. natans filamentation and contribute to better understanding of the filamentous proliferation of this bacterium. In addition, the proposed method will be helpful to evaluate other factors favouring filamentous growth.


Assuntos
Oxigênio/metabolismo , Sphaerotilus/crescimento & desenvolvimento , Sphaerotilus/metabolismo , Meios de Cultura/análise , Meios de Cultura/metabolismo , Oxigênio/análise , Reação em Cadeia da Polimerase em Tempo Real , Sphaerotilus/genética
16.
Environ Sci Technol ; 48(24): 14282-90, 2014 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-25425339

RESUMO

Bioreduction of As(V) and As-bearing iron oxides is considered to be one of the key processes leading to arsenic pollution in groundwaters in South and Southeast Asia. Recent laboratory studies with simple aqueous media showed that secondary Fe(II)-bearing phases (e.g., magnetite and green rust), which commonly precipitate during bioreduction of iron oxides, captured arsenic species. The aim of the present study was to follow arsenic speciation during the abiotic Fe(II)-induced transformation of As(III)- and As(V)-doped lepidocrocite to magnetite, and to evaluate the influence of arsenic on the transformation kinetics and pathway. We found green rust formation is an intermediate phase in the transformation. Both As(III) and As(V) slowed the transformation, with the effect being greater for As(III) than for As(V). Prior to the formation of magnetite, As(III) adsorbed on both lepidocrocite and green rust, whereas As(V) associated exclusively with green rust, When magnetite precipitated, As(III) formed surface complexes on magnetite nanoparticles and As(V) is thought to have been incorporated into the magnetite structure. These processes dramatically lowered the availability of As in the anoxic systems studied. These results provide insights into the behavior of arsenic during magnetite precipitation in reducing environments. We also found that As(V) removal from solution was higher than As(III) removal following magnetite formation, which suggests that conversion of As(III) to As(V) is preferred when using As-magnetite precipitation to treat As-contaminated groundwaters.


Assuntos
Arsênio/química , Compostos Férricos/química , Óxido Ferroso-Férrico/química , Poluentes Químicos da Água/química , Adsorção , Arsênio/classificação , Água Subterrânea/química , Cinética , Nanopartículas de Magnetita
17.
Environ Sci Technol ; 48(20): 11901-9, 2014 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-25226238

RESUMO

Among trace metal pollutants, zinc is the major one in the rivers from the Paris urban area, such as the Orge River, where Zn concentration in the suspended particulate matter (SPM) can reach 2000 mg/kg in the most urbanized areas. In order to better understand Zn cycling in such urban rivers, we have determined Zn speciation in SPM as a function of both the seasonal water flow variations and the urbanization gradient along the Orge River. Using TEM/SEM-EDX and linear combination fitting (LCF) of EXAFS data at the Zn K-edge, we show that Zn mainly occurs as tetrahedrally coordinated Zn(2+) sorbed to ferrihydrite (37-46%), calcite (0-37%), amorphous SiO2 (0-21%), and organic-P (0-30%) and as octahedrally coordinated Zn(2+) in the octahedral layer of phyllosilicates (18-25%). Moreover, the Zn speciation pattern depends on the river flow rate. At low water flow, Zn speciation changes along the urbanization gradient: geogenic forms of Zn inherited from soil erosion decrease relative to Zn bound to organic-phosphates and amorphous SiO2. At high water flow, Zn speciation is dominated by soil-borne forms of Zn regardless the degree of urbanization, indicating that erosion of Zn-bearing minerals dominates the Zn contribution to SPM under such conditions.


Assuntos
Cidades , Material Particulado/química , Rios , Estações do Ano , Urbanização , Zinco/isolamento & purificação , França , Espectrometria por Raios X , Poluentes Químicos da Água/análise
18.
Environ Sci Technol ; 48(8): 4505-14, 2014 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-24708473

RESUMO

The present study investigates for the first time the reduction of nitrite by biogenic hydroxycarbonate green rusts, bio-GR(CO3), produced from the bioreduction of ferric oxyhydroxycarbonate (Fohc), a poorly crystalline solid phase, and of lepidocrocite, a well-crystallized Fe(III)-oxyhydroxide mineral. Results show a fast Fe(II) production from Fohc, which leads to the precipitation of bio-GR(CO3) particles that were roughly 2-fold smaller (2.3 ± 0.4 µm) than those obtained from the bioreduction of lepidocrocite (5.0 ± 0.4 µm). The study reveals that both bio-GR(CO3) are capable of reducing nitrite ions into gaseous nitrogen species such as NO, N2O, or N2 without ammonium production at neutral initial pH and that nitrite reduction proceeded to a larger extent with smaller particles than with larger ones. On the basis of the identification of intermediates and end-reaction products using X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge, our study shows the formation of hydroxy-nitrite green rust, GR(NO2), a new type of green rust 1, and suggests that the reduction of nitrite by biogenic GR(CO3) involves both external and internal reaction sites and that such a mechanism could explain the higher reactivity of green rust with respect to nitrite, compared to other mineral substrates possessing only external reactive sites.


Assuntos
Carbonatos/metabolismo , Compostos Férricos/metabolismo , Compostos Ferrosos/metabolismo , Nitritos/metabolismo , Biodegradação Ambiental , Minerais/química , Oxirredução , Shewanella/metabolismo , Espectroscopia por Absorção de Raios X , Difração de Raios X
19.
iScience ; 27(2): 108894, 2024 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-38318367

RESUMO

Amino acid (AA) transporters (AAT) control AA cellular fluxes across membranes, contributing to maintain cellular homeostasis. In this study, we took advantage of rainbow trout metabolic feature, which highly relies on dietary AA, to explore the cellular and physiological consequences of unbalanced diets on AAT dysregulations with a particular focus on cationic AAs (CAA), frequently underrepresented in plant-based diets. Results evidenced that 24 different CAAT are expressed in various trout tissues, part of which being subjected to AA- and CAA-dependent regulations, with y+LAT2 exchanger being prone to the strongest dysregulations. Moreover, CAA were shown to control two major AA-dependent activation pathways (namely mTOR and GCN2) but at different strength according to the CAA considered. A new feed formulation strategy has been put forward to improve specifically the CAA supplemented absorption in fish together with their growth performance. Such "precision formulation" strategy reveals high potential for nutrition practices, especially in aquaculture.

20.
Environ Sci Technol ; 47(22): 12784-92, 2013 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-24102216

RESUMO

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure of aluminum-rich Fh, and their role in arsenic scavenging in river-bed sediments from a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. TEM-EDXS elemental mapping and SEM-EDXS analyses combined with EXAFS analysis indicates that Al(3+) substitutes for Fe(3+) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 25-30 ± 10 mol %Al range. Synthetic aluminous Fh prepared in the present study are found to be less Al-substituted (14-20 ± 5 mol %Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidence for the scavenging of arsenic by natural Al-Fh, which emphasize the possible implication of such material for scavenging pollutants in natural or engineered systems.


Assuntos
Ácidos/química , Alumínio/química , Arsênio/isolamento & purificação , Compostos Férricos/química , Mineração , Rios/química , França , Sedimentos Geológicos/química , Microscopia Eletrônica de Transmissão , Minerais/química , Espectrometria por Raios X , Espectroscopia por Absorção de Raios X , Difração de Raios X
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