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1.
《Geochimica et cosmochimica acta》1999,63(19-20):3059-3067
In order to test the ability of a surface complexation approach to account for metal-bacteria interactions in near surface fluid-rock systems, we have conducted experiments that measure the extent of adsorption in mixed metal, mixed bacteria systems. This study tests the surface complexation approach by comparing estimated extents of adsorption based on surface complexation modeling to those we observed in the experimental systems. The batch adsorption experiments involved Ca, Cd, Cu, and Pb adsorption onto the surfaces of 2 g positive bacteria: Bacillus subtilis and Bacillus licheniformis. Three types of experiments were performed: 1. Single metal (Ca, Cu, Pb) adsorption onto a mixture of B. licheniformis and B. subtilis; 2. mixed metal (Cd, Cu, and Pb; Ca and Cd) adsorption onto either B. subtilis or B. licheniformis; and 3. mixed or single metal adsorption onto B. subtilis and B. licheniformis. %Independent of the experimental results, and based on the site specific stability constants for Ca, Cd, Cu, and Pb interactions with the carboxyl and phosphate sites on B. licheniformis and B. subtilis determined by Fein et al. (1997), by Daughney et al. (1998) and in this study, we estimate the extent of adsorption that is expected in the above experimental systems.Competitive cation adsorption experiments in both single and double bacteria systems exhibit little adsorption at pH values less than 4. With increasing pH above 4.0, the extent of Ca, Cu, Pb and Cd adsorption also increases due to the increased deprotonation of bacterial surface functional groups. In all cases studied, the estimated adsorption behavior is in excellent agreement with the observations, with only slight differences that were within the uncertainties of the estimation and experimental procedures. Therefore, the results indicate that the use of chemical equilibrium modeling of aqueous metal adsorption onto bacterial surfaces yields accurate predictions of the distribution of metals in complex multicomponent systems.  相似文献   

2.
Extracellular polymeric substances (EPS) are heterogeneous biopolymers produced by Gram-negative and Gram-positive bacterial cells. Adsorption of EPS to minerals can alter the substrata physico-chemistry and influence initial bacterial adhesion processes via conditioning film formation, but the effects of solution chemistry on uptake of EPS remain poorly understood. In this study, the adsorption to goethite (α-FeOOH) of EPS isolated from the early stationary growth-phase culture of Bacillus subtilis was investigated as a function of pH and ionic strength (I) in NaCl background electrolyte using batch studies coupled with Fourier transform infrared spectroscopy and size-exclusion high-performance liquid chromatography. Proteins, particularly those of higher molar mass, and phosphorylated macromolecules were adsorbed preferentially. Increasing solution I (1-100 mM NaCl) or pH (3.0-9.0) resulted in a decrease in the mass of EPS adsorbed. Batch studies and diffuse reflectance infrared Fourier transform spectra are consistent with ligand exchange of EPS phosphate groups for surface hydroxyls at Fe metal centers. The data indicate that both electrostatic and chemical bonding interactions contribute to selective fractionation of the EPS solution. Proteins and phosphate groups in phosphodiester bridges of nucleic acids likely play an important role in conditioning film formation at Fe oxide surfaces.  相似文献   

3.
Nanometer-size (<50 nm) precipitates of amorphous silica globules were observed in laboratory systems containing nontronite NAu-1, Shewanella oneidensis strain MR-1, and lean aqueous media. Their formation was attributed to the release of polysilicic acids at the expense of dissolving NAu-1, and subsequent polymerization and stabilization mediated by biomolecules. Rapid (<24 h) silica globule formation was confirmed in the immediate vicinity of bacterial cells and extracellular polymeric substances in all experimental systems that contained bacteria, whether the bacteria were respiring dissolved O2 or Fe(III) originating from NAu-1, and whether the bacteria were viable or heat-killed. Silica globules were not observed in bacteria- and biomolecule-free systems. Thermodynamic calculations using disilicic acid, rather than monomeric silica, as the primary aqueous silica species suggest that the systems may have been supersaturated with respect to amorphous silica even though they appeared to be undersaturated if all aqueous silica was assumed to be monomeric H4SiO4. The predominant aqueous silica species in the experimental systems was likely polysilicic acids because aqueous silica was continuously supplied from the concurrent dissolution of aluminosilicate. Further polymerization and globule formation may have been driven by the presence of polyamines, a group of biologically produced compounds that are known to drive amorphous silica precipitation in diatom frustules. Globules were likely to be positively charged in our systems due to chemisorption of organic polycations onto silica surfaces that would have been otherwise negatively charged. We propose the following steps for the formation of nanometer-size silica globules in our experimental systems: (i) continuous supply of polysilicic acids due to NAu-1 dissolution; (ii) polysilicic acid polymerization to form <50 nm silica globules and subsequent stabilization mediated by microbially produced polyamines; (iii) charge reversal due to chemisorption of organic polycations; and (iv) electrostatic attraction of positively charged silica globules to net negatively charged bacterial cells. Rapid, biogenic precipitation of silica may be common in soil and sediment systems that appear to be undersaturated with respect to amorphous Si.  相似文献   

4.
The synthesis of illite mixed-layer minerals at surface conditions is possible through precipitation of Al hydroxides from Si-, Mg- and K-containing solutions. It has been shown that amorphous hydroxides of Al, Fe, etc. are capable of coprecipitating silica even from very dilute solutions. By aging of these X-ray amorphous hydroxide—silica precipitates under certain conditions, clay minerals can be synthesized at low temperatures. The presence of Mg particularly favors the formation of three-layer clay minerals. Mg-rich Al hydroxide—silica precipitates permit formation of tri- and di-octahedral smectite, illite and chlorite. The formation of three-layer clay minerals is only possible when the precipitates contain at least 6% MgO. The precipitates stay amorphous if the Mg content is lower. The adsorption of Mg and K on the hydroxide—silica precipitate controls the illite or montmorillonite portion in the mixture of the three-layer silicates. There is a competition for K and Mg adsorption on the hydroxide—silica precipitates. Higher K concentration inhibits the three-layer mineral formation through the lowering of the Mg content in the precipitates. Illite mineral formation is favored under certain K/Mg ratios. Higher NaCl contents do not favor the three-layer mineral formation.The enrichment of Mg and K in the precipitates is not as large as the enrichment of Si in the hydroxides. This means that the illite mineral formation is only possible from solutions with a high-salt content like seawater.  相似文献   

5.
The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pHIEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.  相似文献   

6.
This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria (Rhodobacter sp.), cyanobacteria (Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria (P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ65Cu (solid-solution) = −1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively.Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution.Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.  相似文献   

7.
The bio-weathering of basalt, granite and gneiss was experimentally investigated in this study. These rock-forming minerals weathered more rapidly via the ubiquitous psychrotrophic heterotrophic bacteria. With indigenous bacteria of Bacillus spp. from sediments of Lake Baikal, we traced the degradation process of silicate minerals to understand the weathering processes occurring at the change temperature in the subsurface environment with organic input. The bacteria mediated dissolution of minerals was monitored with solution and solid chemistry, X-ray analyses as well as microscopic techniques. We determined the impact of the bacteria on the mineral surface and leaching of K, Ca, Mg, Si, Fe, and Al from silicate minerals. In the samples the release of major structural elements of silicates was used as an overall indicator of silicate mineral degradation at 4°C and 18°C from five medium exchanges over 255?days of rock bioleaching. The increase of temperature importantly affected the efficiency of Fe extraction from granite and basalt as well as Si extraction from granite and gneiss. In comparison with elemental extraction order at 4°C, Ca was substituted first by Fe or Si. It is evident that temperature influences rock microbial weathering and results in a change of elements extraction.  相似文献   

8.
This paper studied the reciprocity effect between wollastonite and a strain silicate bacterium from purple soil. We analyzed the changes of pH value, glucose (GLU) residual concentration, electrolyte and Mn, Si, Fe etc. in the culture liquid with wollastonite after 48 h. The results show that the GLU wastage of silicate bacteria with wollastonite is 2.5 times of the bacterial contrast. It showed wollastonite could obviously accelerate silicate bacteria growth, but bacterial cell broken and distorted badly have been found by SEM analysis. The solubilization of silicate bacteria to Si element of wollastonite reached above 10 times. At the same time, three apices in FTIR of wollastonite (898 cm-1, 925 cm-1, 962 cm-1) descended obviously after the action of silicate bacteria, which shows that a great deal of Si has dissolved out. So we can get that wollastonite has remarkable effect to the growth of silicate bacteria and silicate bacteria has obvious solubilization to Si of wollastonite.  相似文献   

9.
Iron silicate minerals (bronzite, fayalite), exposed to aqueous dissolution in the laboratory for up to 60 days at room temperature and pH 1, 1.5, and 6, have been studied for evidence of changes in surface composition, using XPS, and these results compared with those obtained from solution chemical analysis. In the absence of dissolved O2 or at low pH (1–1.5) dissolution proceeds congruently after the initial formation of a thin (<10 Å) protonated surface layer depleted in Fe relative to Si. This layer is unstable and does not grow with time as attested to by long term congruent dissolution and by the formation of an amorphous silica surficial breakdown product at pH 1 and 1.5. In bronzite the layer is also slightly depleted in Mg but much less than it is in Fe due to the preferential occupation by Fe+2 of more weakly bonded M2 sites. The behavior of the layer is similar to that found earlier on iron-free pyroxene (Schottet al., 1981); in other words, because of its thinness and instability it is not diffusion-inhibiting or protective toward dissolution.In the presence of dissolved O2, as would be the case in most weathering solutions, dissolution of bronzite and fayalite results in the formation of two surface layers whose compositions were deduced by measurements of XPS binding energies. The outer layer, consisting of hydrous ferric oxide, is readily removed by ultrasonic cleaning and, most likely, is not protective toward dissolution. The inner layer consists of Fe+3 in a protonated or hydroxylated silicate (Mg-silicate in the case of bronzite) matrix. This layer appears to impede dissolution over the time scale of the experiment as attested to by parabolic dissolution rates. However, the layer does not continue to grow on the time scale of weathering because ultrasonically cleaned soil grains (Berner and Schott, 1982) exhibit surface compositions similar to those found in the present month-long laboratory experiments. In other words, a thick, highly altered, diffusion-inhibiting, protective surface layer does not form at the acidic pH of most soils.  相似文献   

10.
《Sedimentology》2018,65(4):1213-1245
In a modern peritidal microbial mat from Qatar, both biomediated carbonates and Mg‐rich clay minerals (palygorskite) were identified. The mat, ca 5 cm thick, shows a clear lamination reflecting different microbial communities. The initial precipitates within the top millimetres of the mat are composed of Ca–Mg–Si–Al–S amorphous nanoparticles (few tens of nanometres) that replace the ultrastructure of extracellular polymeric substances. The extracellular polymeric substances are enriched in the same cations and act as a substrate for mineral nucleation. Successively, crystallites of palygorskite fibres associated with carbonate nanocrystals develop, commonly surrounding bacterial bodies. Micron‐sized crystals of low‐Mg calcite are the most common precipitates, together with subordinate aragonite, very high‐Mg calcite/dolomite and ankerite. Pyrite nanocrystals and framboids are present in the deeper layers of the mat. Calcite crystallites form conical structures, circular to triangular/hexagonal in cross‐section, evolving to crystals with rhombohedral terminations; some crystallite bundles develop into dumb‐bell and stellate forms. Spheroidal organo‐mineral structures are also common within the mat. Nanospheres, a few tens of nanometres in diameter, occur attached to coccoid bacteria and within their cells; these are interpreted as permineralized viruses and could be significant as nuclei for crystallite‐crystal precipitation. Microspheres, 1 to 10 μm in diameter, result from intracellular permineralization within bacteria or the mineralization of the bacteria themselves. Carbonates and clay minerals are commonly aggregated to form peloids, tens of microns in size, surrounded by residual organic matter. Magnesium silicate and carbonate precipitation are likely to have been driven by pH – saturation index – redox changes within the mat, related to microenvironmental chemical changes induced by the microbes – extracellular polymeric substances – viruses and their degradation.  相似文献   

11.
Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)aq - oxide interaction will produce low δ56Fe values for Fe(II)aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ56Fe Fe(II)aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ56Fe aqueous Fe(II) in many natural systems.  相似文献   

12.
The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (mFe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H2O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (Nedge = 1-2; Ncorner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Feedge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe2Si1-2 and Fe3Si2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO6-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (RFe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.  相似文献   

13.
Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ∼2-7), with adsorption increasing with pH to a maximum at pH ∼6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO5Hn)n−8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1pK basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere RCOOCu+ surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K RCOOCu+ = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.  相似文献   

14.
谢玉玲  潘琳  徐九华  邱士东  刘玉堂 《新疆地质》2005,23(1):10-13,i001
地幔捕虏体中存在不同产状的熔体包裹体和各种硅酸盐玻璃相,包括主矿物内部的蠕虫状、长圆形、圆形、不规则状包裹体(I型)、边部的连通的管状包裹体(T型)、主矿物边部和粒间的片状熔融体——“浆胞”(C型),三者可见明显过渡关系,它们是地幔流体交代地幔岩石过程中由交代重熔形成的,是研究地幔流体的特征和地幔交代作用的对象之一,从I型、T型到C型,其成分呈规律变化,其中S、Cu、Ni,K、Na含量呈明显的降低趋势．包裹体中玻璃相的成分较主矿物富Si、Al、S、Cu、Ni、K和Na,再加上C02包裹体的发现,表明地幔流体的成分富碱金属、Si、Al、S、Cu、Ni和CO2,地幔交代作用可以使交代产物中Si、Al含量升高而形成中酸性岩浆,也可由于硫化物熔体聚集而形成矿浆．不同地区的地幔流体性质可能存在差异,这些不同性质的地幔流体町能与不同类型的地幔成矿作用有关．  相似文献   

15.

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2–0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

  相似文献   

16.
Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils.  相似文献   

17.
Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3-Fe(II)aq fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.  相似文献   

18.
In order to compare the chemical compositions and physical properities of dusts on silicate bacteria S35, the chemical compositions of six kinds of mineral dusts have been analyzed and the changes of pH value, glucose （GLU）, electrolyte and Mn, Si, Fe before and after the dusts reacted with silicate bacteria S35 have been measured. The SEM analysis has been used to study the bacterial form and interface action status in the course of reaction between dusts and bacteria. The results show that these mineral dusts have different effects on experiment bacteria. Therefore, it is concluded that the effect of mineral dusts on silicate bacteria has correlation with the chemical compositions and physical properities of dusts.  相似文献   

19.
Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low 56Fe/54Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ56Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ56Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.  相似文献   

20.
Previous research by our group (e.g., [Chem. Geol. 132 (1996) 25; Geochim. Cosmochim. Acta 64 (2000) 1363]) has shown that an aerobic Pseudomonas mendocina bacterium enhances Fe(hydr)oxide dissolution in order to obtain Fe under Fe-limited conditions. The P. mendocina is incapable of utilizing Fe as a terminal electron acceptor and requires several orders of magnitude lower Fe concentrations than do dissimilatory Fe reducing bacteria. The research reported here compared the effects of the P. mendocina on dissolution of well and poorly ordered Clay Minerals Society Source Clay kaolinites KGa-1b and KGa-2, respectively, under Fe-limited conditions. KGa-1b and KGa-2 contain 0.04 and 0.94 bulk wt.% Fe, respectively, and their surface Fe/Si atomic RATIOS=0.008 and 0.012. Following strong cleaning of the kaolinites in 5.8 M HCl at 85 °C, the surface Fe/Si atomic ratios decreased to 0.004 and 0.008, respectively. Both kaolinites also developed a Si-enriched surface precipitate upon strong cleaning.

Because the P. mendocina take up Fe, we could not measure Fe release from the kaolinite directly, but rather had to monitor it indirectly by comparing microbial populations sizes under Fe-limited growth conditions. We found that microbial growth on uncleaned, weakly cleaned, and strongly cleaned kaolinites increased with the amount of Fe readily available to organic ligands as estimated by dissolution in 0.001 M oxalate (pH 3). This suggests that it is the amount of readily accessible Fe that controls Fe acquisition and hence microbial growth. The trend is based on only a relatively small range of kaolinite Fe contents, and the research thus needs to be expanded to include kaolinites with a broader range of bulk and surface Fe concentrations.

Significant enhancement of Al release was observed in the presence of the bacteria, along with generally some enhancement of Si release. This enhancement of kaolinite dissolution could be related to an observed pH increase from 7–8 to 9 in the presence of the bacteria and/or to production of Al chelating agents. The P. mendocina produce a variety of organic exudates, including siderophores [Chem. Geol. 132 (1996) 25; Geomicrobiology (2001b)], and further studies into the effects of the siderophores on Al complexation and on kaolinite dissolution are ongoing.  相似文献   


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