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1.
The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, “dead-end” U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).  相似文献   

2.
Analytical methods of dissolved Se species in river water and seawater were established and applied to study dissolved Se speciation in the Kaoping and Erhjen rivers and estuaries, southwestern Taiwan. The Kaoping and Erhjen rivers and estuaries were respectively in relatively oxygenated and oxygen-deficient conditions as revealed from the distributions of dissolved oxygen, DOC, nutrients, and dissolved Mn. Concentrations of dissolved total Se increased downstream in the riverine sections, ranging from 0.6 nM to 1.2 nM for the Kaoping River and from 0.8 nM to 1.05 nM for the Erhjen River. The dissolved total Se was only slightly higher in the Erhjen middle estuary than in the Kaoping middle estuary in spite of heavier pollution in the former. The dissolved total Se behaved rather conservatively in the Kaoping estuary but nonconservatively in the Erhjen estuary resulting from anthropogenic inputs, and in this respect showed similarities with the behavior of redox-sensitive Mn. The predominant species of selenium were Se(VI) and organic Se in the Kaoping River and Se(VI) in the Kaoping estuary. The elevated concentration of Se(VI) in the Kaoping estuary may stem from the degradation of organic Se and oxidation of Se(IV). On the other hand, Se(IV) and organic Se were equally dominant in the Erhjen River, and Se(IV) was predominant through most of the Erhjen estuary. The elevated distribution of Se(IV) in the Erhjen middle estuary may result mostly from partial decomposition of organic Se, but further oxidation of Se(IV) was inhibited in reducing waters. However, Se(VI) became dominant at Erhjen outer estuary where water was oxygenated by the replacement of intruded coastal seawater. Apparently, the speciation of dissolved Se was mainly controlled by the biological and redox processes in the Kaoping and Erhjen rivers and estuaries.  相似文献   

3.
Characterization of Fe(III) (hydr)oxides in soils near the Ichinokawa mine was conducted using X-ray absorption fine structure (XAFS) and Mössbauer spectroscopies, and the structural changes were correlated with the release of As into pore-water. The Eh values decreased monotonically with depth. Iron is mainly present as poorly-ordered Fe(III) (hydr)oxides, such as ferrihydrite, over a wide redox range (from Eh = 360 to −140 mV). Structural details of the short-range order of these Fe(III) (hydr)oxides were examined using Mössbauer spectroscopy by comparing the soil phases with synthesized ferrihydrite samples having varying crystallinities. The crystallinity of the soil Fe (hydr)oxides decreased slightly with depth and Eh. Thus, within the redox range of this soil profile, ferrihydrite dominated, even under very reducing conditions, but the crystalline domain size, and, potentially, particle size, changed with the variation in Eh. In the soil–water system examined here, where As concentration and the As(III)/As(V) ratio in soil water increased with depth, ferrihydrite persisted and maintained or even enhanced its capacity for As retention with increased reducing conditions. Therefore, it is concluded that As release from these soils largely depends on the transformation of As(V) to As(III) rather than reductive dissolution of Fe(III) (hydr)oxide.  相似文献   

4.
The mechanisms of abiotic sequestration of Se(VI) and Se(IV) on a sample of coal waste rock collected from the Elk Valley, Canada and on three pure mineral species (i.e., siderite, pyrite, and sphalerite) present in coal waste rock were assessed using sterile batch testing under water-saturated, anoxic conditions. Only siderite removed measurable Se(VI) from the test solutions with ~90% removal after 100 d attributed to initial adsorption to the siderite surface as Se(VI) and subsequent reduction to Se(IV) and Se(0). In contrast to Se(VI), all samples removed Se(IV) from the aqueous solutions. The rate of Se(IV) removal was pyrite > siderite > waste rock > sphalerite. The waste rock sample removed Se(IV) from solution in two stages: up to ~40% of the aqueous Se(IV) was rapidly removed (by day 1) followed by slower removal of Se(IV) with up to ~97% removal after 99 d. Se(IV) removal is attributed to the adsorption of Se(IV) and subsequent reduction to Se(0) onto the siderite and pyrite phases of the waste rock. The initial (1 d) removal of Se(IV) by waste rock was characterized using a distribution coefficient (Kd) of 15.5 L/kg. Longer-term Se(IV) removal was fitted with zero and first order removal rates. The removal of Se(IV) by sphalerite was minor and deemed to have a minimal effect on Se sequestration in the waste rock. Desorption tests on waste rock showed that the fraction of sequestered Se susceptible to desorption decreased with time as adsorbed Se(IV) was reduced to insoluble Se(0). These findings show that abiotic Se sequestration can occur in saturated, anoxic zones in coal waste rock dumps.  相似文献   

5.
The vertical distributions of dissolved Se species [Se(IV), Se(VI) and organic Se] and diagenetic constituents [Fe(II) and Mn(II)] were obtained in porewater samples of two Sudbury area lakes (Clearwater and McFarlane). The sedimentary concentration profiles of total Se, Se species bound to Fe–Mn oxyhydroxides and to organic matter, and of elemental Se were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicated that the concentrations of total dissolved Se in porewater samples were very low, varying from around 2.0 nM to a maximum level of 6.5 nM, while the concentrations of total Se species in the solid phase varied between 2 and 150 nmol/g on a dry weight basis. The two lakes showed striking differences in the presence of Se(IV) and Se(VI) at the sediment–water interface (SWI). In Clearwater Lake, Se(VI) was present at this interface and Se(IV) was not detectable, whereas the opposite was found in McFarlane Lake. This suggests that reducing conditions might have existed near the SWI of McFarlane Lake at the sampling time; this hypothesis was confirmed by several other measured chemical parameters. The profiles of total dissolved Se of both lakes suggest upward and downward diffusion of dissolved Se species along the concentration gradients. Assuming that no precipitation occurred at the SWI, the fluxes of dissolved Se species across the SWI in Clearwater and McFarlane lakes were estimated to be 0.108 and 0.034 nmol cm−2 a−1, respectively. These values do not include the possible losses of volatile Se species due to microbial methylation. In the reducing sediments of both lakes, the formation of elemental Se and pyritic Se were found to be important mechanisms for controlling the solubility of Se in this environment. The main geochemical processes involving Se identified in this study are: the adsorption of Se onto Fe–Mn oxyhydroxides at or near the SWI, the release of adsorbed Se by the reduction of the same oxyhydroxides and the mineralization of organic matter, and the removal of Se from porewaters to form elemental Se and a S mineral phase such as Se–pyrite or pure ferroselite.  相似文献   

6.
In the Lower Saxonian Basin, cores from three drill holes provide a cross-section from the basin centre towards the margin through the upper Barremian/lowermost Aptian pyritic claystones and marls. Microscopic analyses distinguish six types of pyrite (I: ‘cones and tubes’, II: ‘tubes’, III: ‘isometric crystal aggregates’, IV: ‘pseudomorphs of fossils’, V: ‘star-like concretions’, and VI: ‘filiform pyrite-marcasite intergrowths’) which are associated with subordinate amounts of Fe carbonate, chalcopyrite, sphalerite and wurtzite. The crystal morphology of these sulphides shows a clear-cut diagenetic sequence from pyrite crystals dominated by the octahedron to those dominated by the cube. Among these early to late diagenetic pyrites, the conversion of crystal habits is accompanied by a striking variation in trace element contents, some of which have extremely low values (e.g. Au, Se, Te, Tl, Co). In this context, classification of crystal habits and analyses of As and Ni establishes a sequence of pyritization which may help define a basin zonation for these argillaceous sedimentary rocks, categorized as ‘normal facies’—oxygenated bottom waters—interrupted by short episodes of bottom water oxygen depletion (‘bituminous facies’). Substitution of the cube for the octahedron in the Fe bisulphide aggregates led to a continuous removal of As and Ni from the pyrite, attesting to a steady decrease of those elements in the pore fluids with time. By contrast, within each type of pyrite, As and Ni contents increase from the margin towards the centre of the basin, owing to pre-concentration of both elements in the basinal sediments, which are more abundant in organic matter. Some other elements, however, such as Mn, Cu, Sb and Ag, do not follow this trend and are unrelated to the lattice transformation of the Fe bisulphides. Their sometimes anomalously high quantities in Fe bisulphides are controlled by the host rock chemistry (presence of volcaniclastic material) and accessory minerals intergrown with pyrite (e.g. chalcopyrite). Pyrite I through III formed in tubular hollows of burrowing organisms, and type IV in tests of fossils. Types V and VI did not result from replacement or void filling but were generated by diffusion of sulphate along inhomogeneties, such as bedding planes, shrinkage cracks or water escape structures.  相似文献   

7.
Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(III)-(hydr)oxide mineral was varied to give equivalent Fe(III)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 growth, along with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and, to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L3-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)-(hydr)oxides are incompletely reduced.  相似文献   

8.
Structural Fe(II) has been shown to reduce several oxidized environmental contaminants, including NO3, chlorinated solvents, Cr(VI), and U(VI). Studies investigating reduction of U(VI) by soils and sediments, however, suggest that abiotic reduction of U(VI) by Fe(II) is not significant, and that direct enzymatic reduction of U(VI) by metal-reducing bacteria is required for U(VI) immobilization as U(IV). Here evidence is presented for abiotic reduction and immobilization of U(VI) by structural Fe(II) in a redoximorphic soil collected from a hillside spring in Iowa. Oxidation of Fe(II) in the soil after reaction with U(VI) was demonstrated by Mössbauer spectroscopy and reduction of U(VI) by the pasteurized soil using U LIII-edge X-ray absorption spectroscopy (XAS). XAS indicates that both reduced U(IV) and oxidized U(VI) or U(V) are present after U(VI) interaction with the Fe(II) containing soil. The EXAFS data show the presence of a non-uraninite U(IV) phase and evidence of the oxidized U(V) or U(VI) fraction being present as a non-uranyl species. Little U(VI) reduction is observed by soil that has been exposed to air and oxidation of Fe(II) to goethite has occurred. Soil characterization based on chemical extractions, Mössbauer spectroscopy, and Fe K-edge XAS indicate that the majority of Fe(II) in the soil is structural in nature, existing in clay minerals and possibly a green rust-like phase. These data provide compelling evidence for abiotic reduction of U(VI) by structural Fe(II) from soil near Fe-rich oxic–anoxic boundaries in natural environments. The work highlights the potential for abiotic reduction of U(VI) by Fe(II) in reduced, Fe-rich environments.  相似文献   

9.
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10.
This paper deals with the trace elements Ag, Sb, Bi in galens and Fe, Mn, Cd, Se, Te, Ga and In in sphalerite from 60 Pb-Zn deposits in China and other countries. The contents of the selected trace elements and their ratios show regular variations from one type of Pb-Zn deposits to another. These elements or their ratios are plotted onto Pb-lnAg, lnSb-lnBi, lnGa-lnIn, Fe-Cd, Fe-Cd-Mn and Zn/Cd-Se/Te-Ga/In diagrams. On the basis of these diagrams, the deposits associated with magmatism(type I), those associated with volcanism(type II), the sedimentary-reformed deposits (type III) and sedimentary-metamorphic deposits(type IV) can be well distinguished. Types I and III have the definite fields in all the diagrams. Types II and IV also have their own fields in lnGa-lnIn and Zn/Cd-Se/Te-Ga/In diagrams. The author considers that these diagrams are applicable to distinguishing the genetic types of Pb-Zn deposits.  相似文献   

11.
Speciation of Cr in geochemical reference materials was characterised by sequential extraction and X‐ray absorption near‐edge structure (XANES) spectroscopy to identify Cr(III) resulting from the reduction of pollutant Cr(VI). Sequential extraction suggested that the amount of Cr associated with an acetic acid soluble fraction was low; Cr associated with a reducible phase and an oxidisable phase was extracted at 5–10% of the total Cr concentration, and the residual phase was found to be the dominant Cr‐containing fraction. Cr speciation in soil artificially doped with Cr(VI) and sediment samples collected from highly populated and industrialised areas was different from that in naturally occurring materials. Substantial Cr was extracted as a reducible phase (15–30%) and an oxidisable phase (30–60%) for these samples. Through subsequent XANES spectroscopy analysis, the reducible phase was explained by Cr bound to Fe hydroxide, while the oxidisable phase was a mixture of Cr bound to humic substances and Cr hydroxides. That is, Cr(VI) present as a contaminant in sediments and soils was reduced to Cr(III), which then bound to Fe hydroxide and humic substances, precipitating as a hydroxide. Thus, a combination of sequential extraction and XANES spectroscopy allows for effective identification and quantification of the chemical forms of Cr in sediments and soils.  相似文献   

12.
Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (pCO2 = 10−3.45 atm).  相似文献   

13.
The mobility and availability of the toxic metalloid selenium in the environment are largely controlled by sorption and redox reactions, which may proceed at temporal scales similar to that of subsurface water movement under saturated or unsaturated conditions. Since such waters are often anaerobic and rich in Fe2+, we investigated the long-term (?1 month) kinetics of selenite sorption to montmorillonite in the presence of Fe2+ under anoxic conditions. A synthetic montmorillonite was used to eliminate the influence of structural Fe. In the absence of aqueous Fe2+, selenite was sorbed as outer-sphere sorption complex, covering only part of the positive edge sites, as verified by a structure-based MUSIC model and Se K-edge XAS (X-ray absorption spectroscopy). When selenite was added to montmorillonite previously equilibrated with Fe2+ solution however, slow reduction of Se and formation of a solid phase was observed with Se K-edge XANES (X-ray absorption near-edge spectroscopy) and EXAFS (extended X-ray absorption fine-structure) spectroscopy. Iterative transformation factor analysis of XANES and EXAFS spectra suggested that only one Se reaction product formed, which was identified as nano-particulate Se(0). Even after one month, only 75% of the initially sorbed Se(IV) was reduced to this solid species. Mössbauer spectrometry revealed that before and after addition and reduction of Se, 5% of total sorbed Fe occurred as Fe(III) species on edge sites of montmorillonite (≈2 mmol kg−1). The only change observed after addition of Se was the formation of a new Fe(II) species (15%) attributed to the formation of an outer-sphere Fe(II)-Se sorption complex. The combined Mössbauer and XAS results hence clearly suggest that the Se and Fe redox reactions are not directly coupled. Based on the results of a companion paper, we hypothesize that the electrons produced in the absence of Se by oxidation of sorbed Fe(II) are stored, for example by formation of surface H2 species, and are then available for the later Se(IV) reduction. The slow reaction rate indicates a diffusion controlled process. Homogeneous precipitation of an iron selenite was thermodynamically predicted and experimentally observed only in the absence of clay. Interestingly, half of Fe was oxidized in this precipitate (Mössbauer). Since DFT calculations predicted the oxidation of Fe at the water-FeSe solid interface only and not in the bulk phase, we derived an average particle size of this precipitate which does not exceed 2 nm. A comparison with the Mössbauer and XAS spectra of the clay samples demonstrates that such homogenous precipitation can be excluded as a mechanism for the observed slow Se reduction, emphasizing the role of abiotic, heterogeneous precipitation and reduction for the removal of Se from subsurface waters.  相似文献   

14.
A small-scale field test was initiated in September 1994 to evaluate the in situ remediation of groundwater contaminated with chromate using a permeable reactive barrier composed of a mixture of zero-valent Fe, sand and aquifer sediment. The site used was an old chrome-plating facility located on a U.S. Coast Guard air base near Elizabeth City, North Carolina. Dissolved chromate concentrations were reduced to less than 0.01 mg/L via reduction from Cr(VI) to Cr(III) as a result of the corrosion of the Fe. As the Fe corrodes, pH increases, oxidation-reduction potential declines, dissolved oxygen is consumed, and Fe(II) is generated. Mineral phases formed as a result of the Fe corrosion include ferrous sulfides and various Fe oxides, hydroxides, and oxyhydroxides.  相似文献   

15.
贵州遵义中南村黑色岩系黄铁矿的成分标型与成因探讨   总被引：14，自引：5，他引：9  
对贵州遵义中南村黑色岩系多元素矿床黄铁矿中的Co、Ni、As、Se、Te、n(s)／n(Fe)、w(Co)／w(Ni)、w(S)／w(Se)、w(Se)／w(Te)等标型进行了研究,井将其与4个胶东热液型金矿的黄铁矿的相应数据进行了对比。通过成分标型分析,并结合黄铁矿的形态、内部结构和同位素特征以及前人的研究成果．认为此黑色岩系多元素矿床应为海底热水沉积和生物沉积混合成因。该黑色岩系黄铁矿同胶东界河金矿的黄铁矿、胶东金青顶金矿中的黄铁矿、胶东玲珑金矿西山矿区中的黄铁矿和胶东三山岛金矿床中的黄铁矿等热液金矿型黄铁矿在10000×w(Co+Ni)／w(Fe)-10000×w(As十Se十Te)／w(S)-100×(n(S)／n(Fe)-1.8)三角图上的投点明显不同,前者投点甚为分散,后者投点较集中。从成因角度分析认为：后者的物质来自花岗岩,主成矿过程受单一的温度变化范围不大的岩浆热液控制;前者物质来源复杂,受高温阶段的深部循环热水和低温阶段的海水一热水混合流体甚至生物作用的制约。由此可以初步提出以下一般判据：在10000×w(Co十Ni)／w(Fe)一10000×w(As十Se+Te)／w(S)一100x(n(S)／n(Fe)一1.8)三角图上,成因简单的黄铁矿的投点较集中,成因复杂的黄铁矿的投点较分散。  相似文献   

16.
《International Geology Review》2012,54(11):1400-1414
Gossans may be distinguished from sedimentary and infiltrational accumulations of iron hydroxides by their positions in the section, often by their burial under loose Mesozoic-Cenozoic sediments, certain mineralogical criteria, and particularly by the following associations of minor metals, typical of the brown ironstones: a) over pyritic ores: Cu, Pb, Ag, Ba, Sr, Hg, As, Sb, Bi, Se, Te; Te:Se = 1,8 to 1.10; b) over chalcopyritic and copper-zinc-pyritic ores; Cu, Pb, Ag, Ba, Se, Te, Zn, Mo, As, Sr, Hg, Au, Bi, K, Na; Te:Se = 1.2 to 1.7. The tellurium-selenium ratio in infiltra tiorial ironstones is characteristically variable within a wide range and their minor metals are even more varied and numerous than in the gossans. --IGR Staff.  相似文献   

17.
The vertical distributions of Se (IV), Se (VI) and dissolved organic Se have been determined in the oxic and non-sulfide-bearing anoxic zones of the Orca Basin. In the oxic waters, the concentration of Se (IV) increases with depth gradually from 0.25 nmole/kg at the surface to a maximum of 0.46 nmole/kg at 750 m and then decreases with depth to a relatively constant concentration of 0.39 nmole/ kg below 1,230 m. The concentration of Se (VI) is rather uniform in the top 250 m at about 0.24 nmole/ kg. Below 250 m it increases with depth to 0.50 nmole/kg at 1.230 m, and it stays relatively constant below this depth. The concentration of organic Se increases from 0.50 nmole/kg at the surface to 1.39 nmole/kg at 78 m. A pronounced broad maximum of organic Se exists between 78 and 250 m. The concentration decreases with depth below 250 m, dropping sharply between 250 and 380 m and more gradually at greater depths. It becomes undetectable at 1,230 m. Organic Se is the dominant species above 250 m. Se (IV) is the most abundant between 250 and 1,000 m while Se (VI) becomes the dominant species below 1,000 m. The distributions of these three species can be explained by the biological uptake of Se in the surface waters and the multi-step regeneration of Se from biogenic particles at greater depths. In suboxic waters at the oxic-anoxic interface, the concentration of Se (IV) increases while that of Se (VI) decreases reflecting a change in redox conditions in the environment. In the anoxic brine, the concentration of Se (IV) is around 0.25 nmole/kg while Se (VI) is undetectable. The concentration of organic Se increases sharply in the suboxic waters and reaches 2.6 nmole/kg in the anoxic brines probably as a result of the decomposition of organic matter and/or a diffusive flux from the underlying sediment.  相似文献   

18.
In laboratory experiments, we investigated the effect of five individual Fe-binding ligands: phaeophytin, ferrichrome, desferrioxamine B (DFOB), inositol hexaphosphate (phytic acid), and protoporphyrin IX (PPIX) on the Fe(II) photoproduction using seawater of the open Southern Ocean. Addition of 10-100 nM Fe(III) to open Southern Ocean seawater without the model ligands and containing; 1.1 nM dissolved Fe(III), 1.75 ± 0.28 equivalents of nM Fe of natural ligands with a conditional stability constant (log K′) of 21.75 ± 0.34 and a concentration DOC of 86.8 ± 1.13 μM C leads to the formation of amorphous Fe(III) hydroxides. These amorphous Fe(III) hydroxides are the major source for the photoproduction of Fe(II). The addition of the model ligands changed the Fe(II) photoproduction considerably and in various ways. Phaeophytin showed higher Fe(II) photoproduction than ferrichrome and the control, i.e., amorphous Fe(III) hydroxides. Additions of phytic acid between 65 and 105 nM increased the concentration of photoproduced Fe(II) with 0.16 nM Fe(II) per nM phytic acid, presumably due to the co-aggregation of Fe(III) and phytic acid leading via an increasing colloidal surface to an increasing photoreducible Fe(III) fraction. DFOB and PPIX strongly decreased the photoproduced Fe(II) concentration. The low Fe(II) photoproduction with DFOB confirmed reported observations that Fe(III) complexed to DFOB is photo-stable. The PPIX hardly binds Fe(III) in the open Southern Ocean seawater but decreased the photoproduced Fe(II) concentration by complexing the Fe(II) with a binding rate constant of kFe(II)PPIX = 1.04 × 10−4 ± 1.53 × 10−5 s−1 nM−1 PPIX. Subsequently, PPIX is suggested to act as a photosensitizing producer of superoxide, thus increasing the dark reduction of Fe(III) to Fe(II). Our research shows that the photochemistry of Fe(III) and the resulting photoproduced Fe(II) concentration is strongly depending on the identity of the Fe-binding organic ligands and that a translation to natural conditions is not possible without further characterization of the natural occurring ligands.  相似文献   

19.
In the present study, we investigated As behavior in a high-As hot spring (Sambe hot spring, Shimane, Japan) by coupling direct chemical speciation by synchrotron-based XAFS and HPLC–ICP-MS with microbial As-redox transformation gene analysis. The concentration of soluble As in the spring streamwater decreased immediately along the flow in correlation with Fe behavior, indicating that As in the streamwater was naturally attenuated in the streamwater. Iron XAFS analysis suggested deposition of Fe(III) oxyhydroxides along the flow. Thus, considering the strong affinity of As to Fe oxyhydroxides, the observed attenuation in As was possibly caused by sorption (or incorporation) of As on Fe(III) oxyhydroxides. Both dissolved As(III) and As(V) were present in the aqueous phase, and As(III) was rapidly oxidized to As(V) (<30 s) along the flow. The oxidation kinetics indicated the occurrence of biotic As(III) oxidation, because obtained As(III) oxidation rate (6.7–7.8 μM min−1) was much faster than the reported abiotic oxidation rates. Furthermore, the bacterial arsenite oxidase gene (aioA) was detected in DNA extracted from all samples (average of 2.0 × 105 copies dry g−1), which also supported potential attributes of biological As(III) oxidation in situ. In solid phase samples from sampling points analyzed by XAFS, most of the As existed as oxidized pentavalent form, As(V). This result indicated that this form was preferentially partitioned to the solid phase because of the much higher affinity of As(V) than of As(III) to Fe(III) oxyhydroxides. Considering the kinetic and microbiological findings, it is indicated that biotic process was predominantly responsible for As(III) oxidation at the present site, and this biotic As(III) oxidation to As(V) controlled the observed attenuation of As, because oxidized As(V) was removed from the aqueous phase by Fe(III) oxyhydroxides more efficiently.  相似文献   

20.
To increase the understanding of uranium transport in the environment and in the presence of steel corrosion products, the interaction of U(VI) with natural magnetite has been studied. Sorption studies have been carried out using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). The XPS results clearly indicate the reduction of U(VI) to U(IV) on the surface of magnetite facilitated by electron transfer between the Fe and U, leading to a coupled oxidation of Fe(II) to Fe(III).  相似文献   

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