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1.
Statistical analysis of a data bank of the compositions of glasses and melt inclusions in minerals from ocean-island basalts. The initial database contains more than 45 000 published analyses of ocean-island igneous rocks from around the world. Much attention was given to the contents of volatiles (H2O, Cl, F, and S) and their ratios to one another and to nonvolatile components of close incompatibility (Ti, P, K, and Ce). The average compositions of melt inclusions are similar to those of glasses of the rocks, including volatiles, with consideration for a somewhat higher degree (by approximately 20%) of the differentiation of glasses. The average compositions of ocean-island melts differ from those of mid-ocean basalts in having wider variations and elevated contents of some of the most incompatible elements (Sr, Nb, Ta, Ba, U, Th, and others), as well as H2O, F, and Cl. Based on the correlation of volatiles to one another and to incompatible elements, three groups of ocean-island basalts are distinguished: (I) low-K, P, Ti magma compositions approximating mid-ocean ridge magmas, (II) high-K, Ce, P, and Ti magmas that resemble continental rift magmas but differ from them in low H2O content, and (III) high-K, H2O, Ce, P, and Ti magmas close to continental rift magma. All three types of the melts were found only in the Hawaiian Archipelago, whereas other ocean islands are dominated by any one of these types. The distinguished melt types presumably reflect the differences (heterogeneity) in the compositions of the sources.  相似文献   

2.
Mean concentrations of major components, trace elements, and volatile components in magmatic melts from Earth’s major geodynamic environments are estimated using our database (which comprises more than 1200000 analyses for 75 chemical elements—state for the beginning of 2016) on melt inclusions and quench glasses of rocks). The geodynamic environments are classified into (I) environments of oceanic plate spreading (mid-oceanic ridges), (II) areas affected by mantle plumes in oceanic plates (oceanic islands and lava plateaus), (III and IV) subduction-related environments (III are magmatic zones in island arcs, and IV are magmatic zones in active continental margins, in which magma-generating processes involve the continental crust), (V) continental rifts in areas with continental hotspots, and (VI) backarc spreading zones. The distribution of SiO2 concentrations (>71000 analyses) in natural magmatic melts in all geodynamic environments is obviously bimodal, with maxima at 50–52 and 72–76 wt % SiO2. Herein we discuss only mafic melts (40–54 wt % SiO2). Mean concentrations and confidence levels are calculated for each geodynamic environment for the first time in three variants: from melt inclusions in minerals, from quench glasses in rocks, and from all data. Systematic variations in the mean compositions of melt inclusions and glasses in rocks are detected for all geodynamic environments. Primitive mantle-normalized multielemental patterns for mean concentrations of elements are constructed for magmatic melts from all geodynamic environments, and the mean ratios and their variations are calculated for trace incompatible and volatile components (H2O/Ce, K2O/Cl, La/Y, Nb/U, Ba/Rb, Ce/Pb, etc.) in melts from all environments.  相似文献   

3.
Major- and trace-element compositions of zircons and whole rocks from 14 barren and seven ore-bearing calc-alkaline intrusions from the Chuquicamata-El Abra porphyry copper belt of northern Chile have been measured in situ by excimer laser ablation (ELA) ICP-MS. These data permit the Ce(IV)/Ce(III) ratio within zircon to be calculated using a lattice-strain model for mineral-melt partitioning of Ce(IV) and Ce(III). Zircon Ce(IV)/Ce(III) and EuN/EuN* ratios, and by inference magmatic oxidation states, generally increase from older, mafic to younger, felsic units. Within this sequence, porphyry copper mineralization is directly associated only with intrusions with zircon Ce(IV)/Ce(III)>300 and EuN/EuN*>0.4. Such trends can be understood in terms of interdependent relations between oxygen fugacity, sulfur speciation and solubility, and chalcophile element partitioning in silicate magmas. Because zircon occurs in most calc-alkaline intrusions and is resistant to subsolidus alteration, zircon Ce(IV)/Ce(III) ratios provide a useful tool for evaluating the economic potential of such rocks for magmatic-hydrothermal Cu-Au mineralization. The approach is general and may provide a means to infer relative oxidation state in a wide range of intermediate to felsic igneous rocks.  相似文献   

4.
温泉斑岩钼矿床位于西秦岭东段,是该区发现的一个具有大型矿前景的斑岩型钼矿床。围岩温泉复式岩体发育5个岩相单元(Ⅰ~Ⅴ),钼矿体(化)主要赋存于复式岩体Ⅱ单元富含镁铁质包体的黑云母二长花岗斑岩和Ⅲ单元富含镁铁质包体的似斑状二长花岗岩及其接触带内,其余岩相(包括单元Ⅴ似斑状正长花岗岩)很少发育矿化。该研究使用全岩地球化学数据和锆石微量元素含量数据,计算得到不同岩相单元的氧逸度。Ⅱ单元和Ⅲ单元含矿斑岩相对氧逸度ΔFMQ分别为1.35和1.38。Ⅰ单元黑云母花岗岩和Ⅳ单元二长花岗斑岩相对氧逸度ΔFMQ分别为-0.61和-0.73,明显低于含矿斑岩。富集地幔物质的加入与否可能是造成不同岩相之间氧逸度差异的主要原因。高氧逸度的熔体可以将秦岭地区古生代富钼沉积物中的钼氧化萃取出来,并使钼与高价态硫络合,不断在熔体中高度富集,最终成矿。氧逸度较低的熔体很难萃取和保存足够的钼,因而很少发育矿化。  相似文献   

5.
During solidification of magma chambers as systems closed to chemical exchange with environs, the residual siliceous melt may follow a trend of rising, constant, or decreasing oxidation state, relative to reference buffers such as nickel?+?nickel oxide (NNO) or fayalite?+?magnetite?+?quartz. Titanomagnetite–hemoilmenite thermometry and oxybarometry on quenched volcanic suites yield temperature versus oxygen fugacity arrays of varied positive and negative slopes, the validity of which has been disputed for several years. We resolve the controversy by introducing a new recorder of magmatic redox evolution employing temperature- and redox-sensitive trace-element abundances in zircon. The zircon/melt partition coefficients of cerium and uranium vary oppositely in response to variation of magma redox state, but vary in tandem as temperature varies. Plots of U/Pr versus Ce4+/Ce3+ in zircon provide a robust test for change in oxidation state of the melt during zircon crystallisation from cooling magma, and the plots discriminate thermally induced from redox-induced variation of Ce4+/Ce3+ in zircon. Temperature-dependent lattice strain causes Ce4+/Ce3+ in zircon to increase strongly as zircon crystallises from cooling magma at constant Ce4+/Ce3+ ratio in the melt. We examine 19 zircon populations from igneous complexes in varied tectonic settings. Variation of zircon Ce4+/Ce3+ due to minor variation in melt oxidation state during crystallisation is resolvable in 11 cases but very subordinate to temperature dependence. In many zircon populations described in published literature, there is no resolvable change in redox state of the melt during tenfold variation of Ce4+/Ce3+ in zircons. Varied magmatic redox trends indicated by different slopes on plots of zircon U/Pr versus Ce4+/Ce3+ are corroborated by Fe–Ti-oxide-based T–?O2 trends of correspondingly varied slopes. Zircon and Fe–Ti-oxide compositions agree that exceptionally, H2O-rich arc magmas tend to follow a trend of rising oxidation state of the melt during late stages of fluid-saturated magmatic differentiation at upper-crustal pressures. We suggest that H2 and/or SO3 and/or Fe2+ loss from the melt to segregating fluid is largely responsible. Conversely, zircon and Fe–Ti-oxide compositions agree in indicating that H2O-poor magmas tend to follow a T–?O2 trend of decreasing oxidation state of the melt during late stages of magmatic differentiation at upper-crustal pressures, because the precipitating mineral assemblage has higher Fe3+/Fe2+ than coexisting rhyolitic melt. We present new evidence showing that the Fe–Ti-oxide oxybarometer calibration by Ghiorso and Evans (Am J Sci 308(9):957–1039, 2008) retrieves experimentally imposed values of ?O2 in laboratory syntheses of Fe–Ti-oxide pairs to a precision of ±?0.2 log unit, over a large experimental temperature range, without systematic bias up to at least log ?O2?≈?NNO?+?4.4. Their titanomagnetite–hemoilmenite geothermometer calibration has large systematic errors in application to Ti-poor oxides that precipitate from very oxidised magmas. A key outcome is validation of Fe–Ti-oxide-based values of melt TiO2 activity for use in Ti-in-zircon thermometry and Ti-in-quartz thermobarometry.  相似文献   

6.
Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ? structural Fe(II) in phyllosilicates ? Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with 56Fe-goethite with adsorbed 57Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.  相似文献   

7.
Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state and less mobile in the reduced form [Tc(IV)O2·nH2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.  相似文献   

8.
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   

9.
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   

10.
Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO2) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti3+ under fO2 conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% [IV]Ti4+ in the pyroxene. In addition, our results can help to better constrain the Ti3+/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.  相似文献   

11.
We compiled a database containing more than 480000 determinations for 73 elements in melt inclusions in minerals and quenched glasses of volcanic rocks. These data were used to estimate the mean contents of major, volatile, and trace elements in igneous melts from main geodynamic settings. The following settings were distinguished: (I) oceanic spreading zones (mid-ocean ridges); (II) zones of mantle plume activity on oceanic plates (oceanic islands and plateaus); (III) and (IV) settings related to subduction processes, including (III) zones of island-arc magmatism generated on the oceanic crust and (IV) magmatic zones of active continental margins involving the continental crust into magma generation processes; (V) intracontinental rifts and continental hot spots; and (VI) back-arc spreading centers. The histogram of SiO2 contents in the natural igneous melts of all geodynamic settings exhibits a bimodal distribution with two maxima at SiO2 contents of 50–52 wt % and 72–74 wt %. The range 62–64 wt % SiO2 comprises the minimum number of determinations. Primitive mantle-normalized spidergrams were constructed for average contents of elements in the igneous melts of basic, intermediate, and acidic compositions from settings I–V. The diagrams reflect the characteristic features of melt compositions for each geodynamic setting. On the basis of the analysis of data on the composition of melt inclusions and glasses of rocks, average ratios of incompatible trace and volatile components (H2O/Ce, K2O/Cl, Nb/U, Ba/Rb, Ce/Pb, etc.) were estimated for the igneous melts of all of the settings. Variations of these ratios were determined, and it was shown that, in most cases, the ratios of incompatible elements are significantly different between settings. The difference is especially pronounced for the ratios of elements with different degrees of incompatibility (e.g., Nb/Yb) and for some ratios with volatile components (e.g., K2O/H2O).  相似文献   

12.
The dacite pumice erupted from Mt. Pinatubo on June 15, 1991 (whole-rock, rhyolitic groundmass glasses and homogenized melt inclusions) has been analyzed using inductively coupled plasma-mass spectrometry (ICP-MS), nanosecond and femtosecond laser ablation ICP-MS and secondary ion mass spectrometry (SIMS) to evaluate its ore-forming potential. Data suggest that adakite magmas are metal-rich and concentrate ore metals during magmatic differentiation. Sulfides segregate in limited amounts under the hydrous, oxidizing conditions typical of adakitic magmas resulting in incompatible behavior for Au (6-22 ppb), Cu (26-77 ppm), and Pb, Mo, As, and Sb in melts of dacitic to rhyolitic compositions. Metal transfer from this adakite magma to the coexisting aqueous phase was favored by the peraluminous composition of the rhyolitic melt and high aqueous chloride concentrations. Mass balance calculations suggest that the pre-eruptive aqueous phase could have extracted a minimum of 100 t Au and 5 × 105 t Cu from the Mt. Pinatubo magma. Our data suggest that intrusives having adakitic signatures are genetically associated with Au-Cu and Cu-Mo mineralization, auriferous porphyry copper deposits, and epithermal gold veins. High H2O, Cl, Sr/Y, Pb/Ce, Mo/Ce, As/Ce and Sb/Ce in Mt. Pinatubo melts reflect the contribution of deep fluids derived from subducted sediments and altered MORBs in the dacite genesis. The slab-derived fluids carrying mobile elements are likely responsible for the enrichment of adakite magmas in gold, associated metals and H2O, and may explain the exceptional ore-forming potential of adakite magmatism.  相似文献   

13.
《Applied Geochemistry》2004,19(11):1785-1800
Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, Eh +700 mV) to moderate pH and weakly reducing (pH 7.6, Eh 15 mV). The waters are rich in SO4 and Ca and have variable As (0.05–95 mg L−1) and Fe concentrations (0.07–141 mg L−1). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured Eh appears to fall between the calculated Eh of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.  相似文献   

14.
The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10−9 atm O2). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. 57Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O2·nH2O(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O2·nH2O(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99Tc remobilization upon the return of oxidizing conditions.  相似文献   

15.
Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe3+ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe2+, Fe3+) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe3+ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe3+ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe2+ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe3+ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe3+ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.  相似文献   

16.
Mössbauer spectroscopy was applied to characterize the valence states Fe(II) and Fe(III) in sedimentary minerals from a core of the Peru Basin. The procedure in unraveling this information includes temperature-dependent measurements from 275?K to very low temperature (300?mK) in zero–field and also at 4.2?K in an applied field (up to 6.2?T) and by mathematical procedures (least-squares fits and spectral simulations) in order to resolve individual spectral components. The depth distribution of the amount of Fe(II) is about 11% of the total Fe to a depth of 19?cm with a subsequent steep increase (within 3?cm) to about 37%, after which it remains constant to the lower end of the sediment core (at about 40?cm). The steep increase of the amount of Fe(II) defines a redox boundary which coincides with the position where the tan/green color transition of the sediment occurs. The isomer shifts and quadrupole splittings of Fe(II) and Fe(III) in the sediment are consistent with hexacoordination by oxygen or hydroxide ligands as in oxide and silicate minerals. Goethite and traces of hematite are observed only above the redox boundary, with a linear gradient extending from about 20% of the total Fe close to the sediment surface to about zero at the redox boundary. The superparamagnetic relaxation behavior allows to estimate the order of magnitude for the size of the largest goethite and hematite particles within the particle-site distribution, e.g. ～170?Å and ～50?Å, respectively. The composition of the sediment spectra recorded at 300?mK in zero-field, apart from the contributions due to goethite and hematite, resembles that of the sheet silicates smectite, illite and chlorite, which have been identified as major constituents of the sediment in the <2?μm fraction by X-ray diffraction. The specific “ferromagnetic” type of magnetic ordering in the sediment, as detected at 4.2?K in an applied field, also resembles that observed in sheet silicates and indicates that both Fe(II) and Fe(III) are involved in magnetic ordering. This “ferromagnetic” behavior is probably due to the double-exchange mechanism known from other mixed-valence Fe(II)–Fe(III) systems. A significant part of the clay-mineral iron is redox sensitive. It is proposed that the color change of the sediment at the redox boundary from tan to green is related to the increase of Fe(II)–Fe(III) pairs in the layer silicates, because of the intervalence electron transfer bands which are caused by such pairs.  相似文献   

17.
A rare earth element (REE) study was made by isotope-dilutionmass spectrometry of plagioclase separates from a variety ofcumulates stratigraphically spanning the Banded series of theStillwater Complex, Montana. Evaluation of parent liquid REEpatterns, calculated on the basis of published plagioclase-liquidpartition coefficients, shows that the range of REE ratios istoo large to be attributable to fractionation of a single magmatype. At least two different parental melts were present throughoutthe Banded series. This finding supports hypotheses of previousworkers that the Stillwater Complex formed from two differentparent magma types, designated the anorthositic- or A-type liquidand the ultramafic- or U-type liquid. On the basis of our data,one melt has a REE pattern with a distinctive shallow slopeand is represented by samples from the thick, massive Anorthositezones I and II (AN I and AN II) of the Middle Banded series.Although samples from AN I and AN II are separated by as muchas 1400 m stratigraphically, they have remarkably similar calculatedparent liquid characteristics, with (Ce/Sm)n = 1.7–1.9,(Nd/Sm)n = 1.3–1.4 and (Ce/Yb)n = 2.9–4.6 (wheren denotes chondrite-normalized). These calculated liquids areprobably close to representing A-type magma. In addition, plagioclase-bronzitecumulates from Norite zones I and II (N I and N II), althoughthought to be U-type cumulates, contain plagioclase that hasA-type REE characteristics, implying that A-type magmas wereinjected into the magma chamber during formation of those zones.In contrast, calculated parent liquids of cumulus augite-bearingrocks have REE patterns that display distinctly steeper slopesthan the A-type REE pattern. The extreme is the calculated parentliquid of a plagioclase-bronzite-augite cumulated with (Ce/Sm)n= 2.9, (Nd/Sm)n = 1.7, and (Ce/Yb)n = 10.1. Analysis of published REE and Nd isotopic data for Stillwatercumulates reveals similarities between AN I, AN II, and otherthin plagioclase cumulate layers in the Lower and Upper Bandedseries, which supports the notion that they were all derivedfrom similar (A-type) parent melts. In contrast, plagioclaseseparates from cumulus augite-bearing rocks display light REEand Nd isotopic characteristics that are similar to U-type cumulatesfrom the Ultramafic series as described by previous studies.Thus far, the only cumulates from the Banded series that displayU-type REE and Nd isotopic characteristics are those that containcumulus augite. Therefore, cumulus augite appears to be an importantindicator of magmatic parentage. The REE and Nd isotopic ratios show erratic variation with stratigraphicposition, indicating that the magmas from which the Banded seriescrystallized were injected at various levels into the magmachamber. Different cumulate types crystallized from discreteliquids, as indicated by the correlation between REE signatureand cumulate type. Samples from Olivine-bearing zones III andIV (stratigraphically between AN I and AN II) display a rangein REE ratios; e.g., (Ce/Sm)n = 1.8–2.8 and (Ce/Yb)n =3.9–6.1, results that rule out the crystallization ofthe Middle Banded series from a single magma type. Furthermore,the possibility that AN I and AN II are directly related tothe underlying Ultramafic series, either as flotation cumulatesor as crystallization products of expelled liquids, is not substantiatedby the REE data because the calculated parent magma of AN Iand AN II was different from that of the Ultramafic series asdefined by previous studies. The REE data of this study further constrain interpretationsof published Pb isotopic data (Wooden et al., 1991) and indicatethat the magmas from which the Stillwater Complex formed werederived from two sources that had only small differences inPb isotopic composition. The REE and isotopic data, as wellas crystallization sequences of the two main parental magmas,indicate that the magmas were probably derived from two closelyrelated upper-mantle sources, one harzburgitic and the otherlherzolitic in composition, resulting in the U-type and A-typemagmas, from which orthopyroxene crystallized before and afterclinopyroxene, respectively. Both sources had been enrichedin large-ion lithophile elements, probably owing to mantle metasomatism.  相似文献   

18.
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   

19.
Melt inclusions were investigated in olivine phenocrysts from the New Caledonia boninites depleted in CaO and TiO2 and enriched in SiO2 and MgO. The rocks are composed of olivine and pyroxene phenocrysts in a glassy groundmass. The olivine phenocrysts contain melt inclusions consisting of glass, a fluid vesicle, and daughter olivine and orthopyroxene crystals. The daughter minerals are completely resorbed in the melt at 1200?C1300°C, whereas the complete dissolution of the fluid phase was not attained in our heating experiments. The compositions of reheated and naturally quenched melt inclusions, as well as groundmass glasses were determined by electron microprobe analysis and secondary ion mass spectrometry. Partly homogenized melts (with gas) contain 12?C16 wt % MgO. The glasses of inclusions and groundmass are significantly different in H2O content: up to 2 wt % in the glasses of reheated inclusions, up to 4 wt % in naturally quenched inclusions, and 6?C8 wt % in groundmass glasses. A detailed investigation revealed a peculiar zoning in olivine: its Mg/(Mg + Fe) ratio increased in a zone directly adjacent to the glass of inclusions. This effect is probably related to partial water (hydrogen) loss and Fe oxidation after inclusion entrapment. The numerical modeling of such a process showed that the water loss was no higher than a few tenths of percent and could not be responsible for the considerable difference between the compositions of inclusions and groundmass glasses. It is suggested that the latter were enriched in H2O after the complete solidification of the rock owing to interaction with seawater. Based on the obtained data, the compositions of primary boninite magmas were estimated, and it was supposed that variations in melt composition were related not only to olivine and pyroxene fractionation from a single primary melt but also to different degrees and (or) depths of magma derivation.  相似文献   

20.
Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO2, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO2. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.  相似文献   

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