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1.
Biofilm-embedded Mn oxides exert important controls on trace metal cycling in aquatic and soil environments. The speciation and mobility of Zn in particular has been linked to Mn oxides found in streams, wetlands, soils, and aquifers. We investigated the mechanisms of Zn sorption to a biogenic Mn oxide within a biofilm produced by model soil and freshwater MnII-oxidizing bacteria Pseudomonas putida. The biogenic Mn oxide is a c-disordered birnessite with hexagonal layer symmetry. Zinc adsorption isotherm and Zn and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy experiments were conducted at pH 6.9 to characterize Zn sorption to this biogenic Mn oxide, and to determine whether the bioorganic components of the biofilm affect metal sorption properties. The EXAFS data were analyzed by spectral fitting, principal component analysis, and linear least-squares fitting with reference spectra. Zinc speciation was found to change as Zn loading to the biosorbent [bacterial cells, extracellular polymeric substances (EPS), and biogenic Mn oxide] increased. At low Zn loading (0.13 ± 0.04 mol Zn kg−1 biosorbent), Zn was sorbed to crystallographically well-defined sites on the biogenic oxide layers in tetrahedral coordination to structural O atoms. The fit to the EXAFS spectrum was consistent with Zn sorption above and below the MnIV vacancy sites of the oxide layers. As Zn loading increased to 0.72 ± 0.04 mol Zn kg−1 biosorbent, Zn was also detected in octahedral coordination to these sites. Overall, our results indicate that the biofilm did not intervene in Zn sorption by the Mn-oxide because sorption to the organic material was observed only after all Mn vacancy sites were capped by Zn. The organic functional groups present in the biofilm contributed significantly to Zn removal from solution when Zn concentrations exceeded the sorption capacity of the biooxide. At the highest Zn loading studied, 1.50 ± 0.36 mol Zn kg−1 biosorbent, the proportion of total Zn sorption attributed to bioorganic material was 38 mol%. The maximum Zn loading to the biogenic oxide that we observed was 4.1 mol Zn kg−1 biogenic Mn oxide, corresponding to 0.37 ± 0.02 mol Zn mol−1 Mn. This loading is in excellent agreement with previous estimates of the content of cation vacancies in the biogenic oxide. The results of this study improve our knowledge of Zn speciation in natural systems and are consistent with those of Zn speciation in mineral soil fractions and ferromanganese nodules where the Mn oxides present are possibly biogenic.  相似文献   

2.
Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO6 octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite (δ-MnO2), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c∗ axis and a lack of c∗ periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide → 10-Å triclinic phyllomanganate → todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.  相似文献   

3.
The surface reactivity of biogenic, nanoparticulate UO2 with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO2. Synthesis of biogenic UO2 was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO2 as a function of particle size and surface-associated organic matter. The N2-BET surface areas of the two biogenic UO2 samples following the washing procedures are 128.63 m2 g−1 (NAUO2) and 92.56 m2 g−1 (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO2 (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U LIII-edge EXAFS spectra for biogenic UO2 (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO2. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO2 is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m−2 UO2 (bulk uraninite), 2.34 ± 0.12 μmol m−2 UO2 (NAUO2), and 2.57 ± 0.10 μmol m−2 UO2 (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO2 indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)6 sorbs as bidentate, edge-sharing complexes to UO8 polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO2 surface. Surface-associated organic matter on the biogenic UO2 particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO2 surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.  相似文献   

4.
The oxidation state and mineral phase association of Co, Ce, and Pb in hydrogenetic, diagenetic, and hydrothermal marine ferromanganese oxides were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. Cobalt is trivalent and associated exclusively with the Mn oxide component (vernadite). Cerium is tetravalent in all genetic-type oxides (detection limit for Ce(III) ∼ 5 at. %), including Fe-rich areas (ferrihydrite) of hydrogenetic oxides, and is associated primarily with vernadite. Thus, the extent of a Ce anomaly does not result from variations in redox conditions, but appears to be kinetically controlled, decreasing when the growth rate increases from hydrogenetic to diagenetic to hydrothermal oxides. Lead is divalent and associated with Mn and Fe oxides in variable proportions. According to EXAFS data, Pb is mostly sorbed on edge sites at chain terminations in Fe oxide and at layer edges in Mn oxide (ES complex), and also on interlayer vacancy sites in Mn oxide (TCS complex). Sequential leaching experiments, spectroscopic data, and electrochemical considerations suggest that the geochemical partitioning in favor of the Mn oxide component decreases from Co to Ce to Pb, and depends on their oxidative scavenging by Mn and Fe oxides.  相似文献   

5.
Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal “clouds”. Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (∼1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (∼40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O2 concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO2-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria. Overall, these results reveal a vigorous Mn biogeochemical cycle in the GB hydrothermal plume, where a distinct microbial community enzymatically catalyzes rapid Mn(II) oxidation and the production of Mn biooxides.  相似文献   

6.
Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.  相似文献   

7.
Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.  相似文献   

8.
The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the VIZn/IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn4+ vacancies (i.e., no Mn3+ for Mn4+ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.  相似文献   

9.
Formation of todorokite from vernadite in Ni-rich hemipelagic sediments   总被引：1，自引：0，他引：1  
Todorokite is considered to form from vernadite in nature and commonly concentrates nickel. However, this mineralogical transformation has never been imaged nor explained mechanistically, and its effect on the uptake of nickel has never been quantified at the molecular-level. We have characterized these reactions at the macroscopic, microscopic, nanoscopic and atomic scales in a marine manganese concretion by combining transmission electron microscopy, electron and X-ray microprobe analysis, powder and micro X-ray diffraction, and Mn and Ni K-edge EXAFS spectroscopy. The concretion was collected during the Ticoflux II expedition near the Nicoya Peninsula, Costa Rica, and is representative of Mn deposits in hemipelagic sediments. It consists of 5 to 25 μm aggregates, shaped like sea-urchins, with a core of 7Å-vernadite (1.0 wt% Ni), a rim of 10Å-vernadite (3.8 wt% Ni), and an outermost region of todorokite fibers (1.9 wt% Ni) that extend outwards. The crystallites of 7Å-vernadite are single- to bi-layered, with hexagonal layer symmetry (a = b = 2.83 Å), and an average structural formula of . The crystallites of 10Å-vernadite contain 10 to 20 layers semi-coherently stacked in the ab plane and uniformly separated in the [0 0 1] direction by ∼9 Å due to the intercalation of hydrated Mg2+ cations. The average structural formula of 10Å-vernadite is if the layers contain vacancy sites, or alternately , if they contain Mn3+. The average formula of todorokite is .A genetic model is proposed based on combining these new data with previously published results. The thermodynamically unstable 7Å-vernadite transforms via dissolution-recrystallization to semi-ordered Mg-rich 10Å-vernadite. Nickel is released from dissolved biogenic silica or reduced organic matter, and taken up mainly in the Mn layer of 10Å-vernadite. Interlayer magnesium serves as a template to the further topotactic transformation of 10Å-vernadite to todorokite. The dimension of the todorokite tunnels in the [0 0 1] direction is uniform and determined by the size of the hydrated Mg2+ ion (8.6 Å). The tunnel dimension in the [1 0 0] direction depends on the density of Mg2+ in the interlayer and the superstructure of the phyllomanganate layer. If the parent phyllomanganate contains high amounts of Mg2+ (i.e., high layer charge), or Mn3+ and Mn4+ cations ordered following the Mn3+-Mn4+-Mn4+ sequence as in synthetic triclinic birnessite, then the tunnel dimension is ideally 3 × 3 octahedral chain widths in both crystallographic directions. Otherwise, the tunnel dimension is incoherent in the [1 0 0] direction (i.e., T(3,n) tunnel structure), as has been observed in all natural todorokites. Natural todorokite is defective because the precursor natural phyllomanganates either have a layer charge deficit below 0.33e per octahedral site, or rarely are triclinic birnessite. The abundance of Mg in seawater and its key role in converting phyllomanganate to tectomanganate with T(3,n) tunnel structure explain why todorokite is common in marine ferromanganese oxides, and seldom present in terrestrial environments. The topotactic phase transformation described here is the only known route to todorokite crystallization. This implies that all natural todorokites may be authigenic because they are formed in situ from a phyllomanganate precursor.  相似文献   

10.
Sorption of rare earth elements (REEs) and Ce oxidation on natural and synthetic Mn oxides have been investigated by many researchers. Although Mn(II)-oxidizing microorganisms are thought to play an important role in the formation of Mn oxides in most natural environments, Ce oxidation by biogenic Mn oxide and the relevance of microorganisms to the Ce oxidation process have not been well understood. Therefore, in this study, we conducted sorption experiments of REEs on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. The distribution coefficients, Kd(REE), between biogenic Mn oxide (plus hyphae) and 10 mmol/L NaCl solution showed a large positive Ce anomaly and convex tetrad effect variations at pH 3.8, which was consistent with previous works using synthetic Mn oxide. The positive Ce anomaly was caused by oxidation of Ce(III) to Ce(IV) by the biogenic Mn oxide, which was confirmed by analysis of the Ce LIII-edge XANES spectra. With increasing pH, the positive Ce anomaly and convex tetrad effects became less pronounced. Furthermore, negative Ce anomalies were observed at a pH of more than 6.5, suggesting that Ce(IV) was stabilized in the solution (<0.2 μm) phase, although Ce(III) oxidation to Ce(IV) on the biogenic Mn oxide was confirmed by XANES analysis. It was demonstrated that no Ce(III) oxidation occurred during sorption on the hyphae of strain KR21-2 by the Kd(REE) patterns and XANES analysis. The analysis of size exclusion HPLC-ICP-MS showed that some fractions of REEs in the filtrates (<0.2 μm) after sorption experiments were bound to organic molecules (40 and <670 kDa fractions), which were possibly released from hyphae. A line of our data indicates that the negative Ce anomalies under circumneutral pH conditions arose from Ce(III) oxidation on the biogenic Mn oxide and subsequent complexation of Ce(IV) with organic ligands. The suppression of tetrad effects is also explained by the complexation of REEs with organic ligands. The results of this study demonstrate that the coexistence of the biogenic Mn oxide and hyphae of strain KR21-2 produces a specific redox chemistry which cannot be explained by inorganic species.  相似文献   

11.
A synergistic experimental-computational approach was used to study the molecular-scale mechanisms of Ni sorption at varying loadings and at pH 6-8 on the biogenic hexagonal birnessite produced by Pseudomonas putida GB-1. We found that Ni is scavenged effectively by bacterial biomass-birnessite assemblages. At surface excess values below 0.18 mol Ni kg−1 sorbent (0.13 mol Ni mol−1 Mn), the biomass component of the sorbent did not interfere with Ni sorption on mineral sites. Extended X-ray absorption fine structure (EXAFS) spectra showed two dominant coordination environments: Ni bound as a triple-corner-sharing (Ni-TCS) complex at vacancy sites and Ni incorporated (Ni-inc) into the MnO2 sheet, with the latter form of Ni favored at high sorptive concentrations and decreased proton activity. In parallel to our spectral analysis, first-principles geometry optimizations based on density functional theory (DFT) were performed to investigate the structure of Ni surface complexes at vacancy sites. Excellent agreement was achieved between EXAFS- and DFT-derived structural parameters for Ni-TCS and Ni-inc. Reaction-path calculations revealed a pH-dependent energy barrier associated with the transition from Ni-TCS to Ni-inc. Our results are consistent with the rate-limited incorporation of Ni at vacancy sites in our sorption samples, but near-equilibrium state of Ni in birnessite phases found in nodule samples. This study thus provides direct and quantitative evidence of the factors governing the occurrence of Ni adsorption versus Ni incorporation in biogenic hexagonal birnessite, a key mineral in the terrestrial manganese cycle.  相似文献   

12.
Solid materials such as suspended particulate matter (SPM), deposited sediment (DS) and natural surface coatings (NSC, composed of biofilms and associated minerals) are important sinks and potential sources of pollutants in natural aquatic environments. Although these materials can exist in the same water body, few studies have been conducted to compare their ability to adsorb trace metals. In this study, the adsorption of Pb, Cu and Cd by these solids, collected from an urban lake, was investigated. In addition, the metal adsorption properties of the main components of these solids, namely Mn and Fe oxides and organics, were also investigated using the method of selective extraction followed by metal adsorption. The solids that co-existed in water showed similarities and differences in their compositions. For each metal, adsorption to the solids occurred in the same order: NSC > SPM > DS. For Pb and Cd, Fe and Mn oxides and organics contributed to the adsorption by NSC and SPM, and the adsorption by DS was dominated by Fe oxides. For Cu, the organics were the main adsorptive phase. The specific adsorption capability of these components decreases in the following order: Mn oxides > Fe oxides > organics. Overall, the results presented herein indicate that different solids and their components played important roles in the adsorption of trace metals.  相似文献   

13.
Manganese oxides form typically in natural aqueous environments via Mn(II) oxidation catalyzed by microorganisms, primarily bacteria, but little is known about the structure of the incipient solid-phase products. The Mn oxide produced by a Pseudomonas species representative of soils and freshwaters was characterized as to composition, average Mn oxidation number, and N2 specific surface area. Electron microscopy, X-ray diffraction, and X-ray absorption near edge structure spectroscopy were applied to complement the physicochemical data with morphological and structural information. A series of synthetic Mn oxides also was analyzed by the same methods to gain better comparative understanding of the structure of the biogenic oxide. The latter was found to be a poorly crystalline layer type Mn(IV) oxide with hexagonal symmetry, significant negative structural charge arising from cation vacancies, and a relatively small number of randomly stacked octahedral sheets per particle. Its properties were comparable to those of δ-MnO2 (vernadite) and a poorly crystalline hexagonal birnessite (“acid birnessite”) synthesized by reduction of permanganate with HCl, but they were very different from those of crystalline triclinic birnessite. Overall, the structure and composition of the Mn oxide produced by P. putida were similar to what has been reported for other freshly precipitated Mn oxides in natural weathering environments, yielding further support to the predominance of biological oxidation as the pathway for Mn oxide formation. Despite variations in the degree of sheet stacking and Mn(III) content, all poorly crystalline oxides studied showed hexagonal symmetry. Thus, there is a need to distinguish layer type Mn oxides with structures similar to those of natural birnessites from the synthetic triclinic variety. We propose designating the unit cell symmetry as an addition to the current nomenclature for these minerals.  相似文献   

14.
Iron(III) (hydr)oxides formed at extracellular biosurfaces or in the presence of exopolymeric substances of microbes and plants may significantly differ in their structural and physical properties from their inorganic counterparts. We synthesized ferrihydrite (Fh) in solutions containing acid polysaccharides [polygalacturonic acid (PGA), alginate, xanthan] and compared its properties with that of an abiotic reference by means of X-ray diffraction, transmission electron microscopy, gas adsorption (N2, CO2), X-ray absorption spectroscopy, 57Fe Mössbauer spectroscopy, and electrophoretic mobility measurements. The coprecipitates formed contained up to 37 wt% polymer. Two-line Fh was the dominant mineral phase in all precipitates. The efficacy of polymers to precipitate Fh at neutral pH was higher for polymers with more carboxyl C (PGA ∼ alginate > xanthan). Pure Fh had a specific surface area of 300 m2/g; coprecipitation of Fh with polymers reduced the detectable mineral surface area by up to 87%. Likewise, mineral micro- (<2 nm) and mesoporosity (2-10 nm) decreased by up to 85% with respect to pure Fh, indicative of a strong aggregation of Fh particles by polymers in freeze-dried state. C-1s STXM images showed the embedding of Fh particles in polymer matrices on the micrometer scale. Iron EXAFS spectroscopy revealed no significant changes in the local coordination of Fe(III) between pure Fh and Fh contained in PGA coprecipitates. 57Fe Mössbauer spectra of coprecipitates confirmed Fh as dominant mineral phase with a slightly reduced particle size and crystallinity of coprecipitate-Fh compared to pure Fh and/or a limited magnetic super-exchange between Fh particles in the coprecipitates due to magnetic dilution by the polysaccharides. The pHiep of pure Fh in 0.01 M NaClO4 was 7.1. In contrast, coprecipitates of PGA and alginate had a pHiep < 2. Considering the differences in specific surface area, porosity, and net charge between the coprecipitates and pure Fh, composites of exopolysaccharides and Fe(III) (hydr)oxides are expected to differ in their geochemical reactivity from pure Fe(III) (hydr)oxides, even if the minerals have a similar crystallinity.  相似文献   

15.
Ferrihydrite (Fh) is a short-range ordered nanocrystalline iron(III) (oxyhydr)oxide that has been recognized to play an important role in contaminant sequestration and in iron cycling in geological and biological systems. Despite intensive research for the two last decades, the structure of Fh is still a subject of debate. In the present study, we report extended X-ray absorption fine structure (EXAFS) spectroscopy data collected on a large set of ferrihydrites and model compounds samples including especially nano-crystalline maghemite (Mh), goethite (Gt), and akaganeite (Aka). This set of EXAFS data recorded at cryogenic temperature over a wide energy range allows us to precisely determine the Fe-O mean distance (〈Fe-O〉) in the first coordination shell of iron for this large set of iron (oxyhydr)oxides. Our EXAFS analysis includes both classical shell-by-shell fits of Fourier-filtered and unfiltered data as well as analysis of Fe-O distance distribution in the first coordination shell of iron using the Landweber iteration method. 〈Fe-O〉 determined by these complementary EXAFS analyses are similar: 〈Fe-O〉 is shorter in Mh (1.96 ± 0.01 Å) that contains 37.5% of tetrahedral iron, than in Gt (2.01 ± 0.01 Å), Aka (2.00 ± 0.01 Å) and hematite (Hm) (2.01 ± 0.01 Å) that do not contain tetrahedral iron. 〈Fe-O〉 for the five Fh samples investigated (1.97 ± 0.01 Å) was found to be slightly longer than in Mh and significantly shorter than those in Gt, Aka and Hm. This short 〈Fe-O〉 distance in Fh indicates the presence of significant amount of tetrahedrally coordinated iron(III) in all Fh samples studied, which ranges between 20 ± 5% and 30 ± 5% of total iron. In addition, our analysis of Fe-Fe distances observed by EXAFS is consistent with a Keggin-like motif at a local scale (∼5 Å) in the Fh structure.  相似文献   

16.
The Ni geochemistry of limonite and saprolite laterite ores from Pujada in the Philippines has been investigated using a mixture of laboratory and synchrotron techniques. Nickel laterite profiles are typically composed of complicated mineral assemblages, with Ni being distributed heterogeneously at the micron scale, and thus a high degree of spatial resolution is required for analysis. This study represents the first such analysis of Philippine laterite ores. Synchrotron bulk and microprobe X-ray absorption spectroscopy (XAS), comprising both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, together with synchrotron microprobe X-ray fluorescence microscopy (XFM) and diffraction (XRD) have been applied to provide quantitative analysis of the mineral components and Ni speciation.Synchrotron microprobe EXAFS spectroscopy suggests that the limonite Ni is associated with phyllomanganate via adsorption onto the Mn oxide layers and substitution for Mn within these layers. Laboratory scanning electron microscopy, coupled to electron dispersive spectroscopy analyses, indicates that Ni is also associated with concentrated Fe containing particles and this is further confirmed by synchrotron bulk and microprobe investigation. Linear combination fitting of the bulk EXAFS limonite data suggests 60 ± 15% of the Ni is associated with phyllomanganate, with the predominant fraction adsorbed above vacancies in the MnO6 layers with the remainder being substituted for Mn within these layers. The remaining 40 ± 10% of the Ni in the limonite ore is incorporated into goethite through replacement of the Fe. In the saprolite ore, 90 ± 23% of the Ni is associated with a serpentine mineral, most likely lizardite, as a replacement for Mg. The remaining Ni is found within phyllomanganate adsorbed above vacancies in the MnO6 layers.  相似文献   

17.
Calcium oxalate monohydrate (CaC2O4·H2O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II)aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr]aq, ranging from 1 × 10−4 to 1 × 10−3 M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sraq for two days, the solution Ca concentration, [Ca]aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sraq removed from solution was nearly equal to the total [Ca]aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC2O4 of mixed hydration state (i.e. SrOx·nH2O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO3 phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.  相似文献   

18.
Isotope analyses (K–Ar, δ18O and δD) were performed on illite from both the sandstone cover and the underlying basement, close to and distant from Shea Creek, an unconformity-type U deposit (Athabasca Basin, Canada); the illite had previously been characterized crystallographically. In the barren areas away from deposit, illite is mainly of the cis-vacant 1M polytype occurring as relatively coarse-grained lath-shaped particles, while it occurs as fine-grained particles of the trans-vacant 1M type next to and in the U mineralized strata. The tectonic-induced hydrothermal system that favored illite crystallization was multi-episodic 1453 ± 2, 1330 ± 20 and probably about 1235 Ma ago. These illite-forming episodes appear to have occurred contemporaneously to those favoring the concentration of the associated U oxides, which were dated independently by the U–Pb method in the Shea Creek deposits and elsewhere in the Athabasca Basin.  相似文献   

19.
The speciation of iron (Fe) in soils, sediments and surface waters is highly dependent on chemical interactions with natural organic matter (NOM). However, the molecular structure and hydrolysis of the Fe species formed in association with NOM is still poorly described. In this study extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry and hydrolysis of Fe(III) in solution of a peat humic acid (5010-49,200 μg Fe g−1 dry weight, pH 3.0-7.2). Data were analyzed by both conventional EXAFS data fitting and by wavelet transforms in order to facilitate the identification of the nature of backscattering atoms. Our results show that Fe occurs predominantly in the oxidized form as ferric ions and that the speciation varies with pH and Fe concentration. At low Fe concentrations (5010-9920 μg g−1; pH 3.0-7.2) mononuclear Fe(III)-NOM complexes completely dominates the speciation. The determined bond distances for the Fe(III)-NOM complexes are similar to distances obtained for Fe(III) complexed by desferrioxamine B and oxalate indicating the formation of a five-membered chelate ring structure. At higher Fe concentrations (49,200 μg g−1; pH 4.2-6.9) we detect a mixture of mononuclear Fe(III)-NOM complexes and polymeric Fe(III) (hydr)oxides with an increasing amount of Fe(III) (hydr)oxides at higher pH. However, even at pH 6.9 and a Fe concentration of 49,200 μg g−1 our data indicates that a substantial amount of the total Fe (>50%) is in the form of organic complexes. Thus, in environments with significant amounts of organic matter organic Fe complexes will be of great importance for the geochemistry of Fe. Furthermore, the formation of five-membered chelate ring structures is in line with the strong complexation and limited hydrolytic polymerization of Fe(III) in our samples and also agrees with EXAFS derived structures of Fe(III) in organic soils.  相似文献   

20.
Lime treatment of acid mine drainage (AMD) generates large volumes of neutralization sludge that are often stored under water covers. The sludge consists mainly of calcite, gypsum and a widespread ferrihydrite-like Fe phase with several associated species of metal(loid) contaminants. The long-term stability of metal(loid)s in this chemically ill-defined material remains unknown. In this study, the stability and speciation of As in AMD sludge subjected to prolonged anoxic conditions is determined. The total As concentration in the sludge is 300 mg kg−1. In the laboratory, three distinct water cover treatments were imposed on the sludge to induce different redox conditions (100%N2, 100%N2 + glucose, 95%N2:5%H2). These treatments were compared against a control of oxidized, water-saturated sludge. Electron micro-probe (EMP) analysis and spatially resolved synchrotron X-ray fluorescence (SXRF) results indicate that As is dominantly associated with Fe in the sludge. In all treatments and throughout the experiment, measured concentrations of dissolved As were less than 5 μg L−1. Dissolved Mn concentration in the N2 + glucose treatment increased significantly compared to other treatments. Manganese and As K-edge X-ray absorption near edge structure spectroscopy (XANES) analyses showed that Mn was the redox-active element in the solid-phase, while As was stable. Arsenic(V) was still the dominant species in all water-covered sludges after 9 months of anoxic treatments. In contrast, Mn(IV) in the original sludge was partially reduced into Mn(II) in all water-covered sludges. The effect was most pronounced in the N2 + glucose treatment, suggesting microbial reduction. Micro-scale SXRF and XANES analysis of the treated sludge showed that Mn(II) accumulated in areas already enriched in Fe and As. Overall, the study shows that AMD sludges remain stable under prolonged anoxic conditions. External sources of chemical reductants or soluble C were needed to induce lower redox state in the systems, and even under these imposed treatments, only weakly reducing conditions (Mn threshold) developed. The results suggest that As(V) in AMD sludge will remain stable under prolonged anoxic conditions as long as Mn(IV) is present and organic matter accumulation is negligible.  相似文献   

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