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1.
Small hexagonal and triangular platelets of molybdenite (MoS2), 5 to 25 m in diameter, were identified in phenocrysts and matrix glass of unaltered felsic volcanic rocks from Pantelleria, Italy. The MoS2 occurs commonly in pantellerites (peralkaline rhyolites), rarely in pantelleritic trachytes, and never in trachytes. The occurrence of euhedral MoS2 platelets in all phenocryst phases, in matrix glass, and even in some melt inclusions indicates that MoS2 precipitated directly from the peralkaline melt. Despite MoS2 saturation, the melt (glass) contains greater than 95% of the Mo in Pantellerian rocks: X-ray fluorescence analyses of 20 whole rocks and separated glasses show that whole rocks consistently contain less Mo than corresponding matrix glasses, the differences being in proportion to phenocryst abundances. The Mo contents increase with differentiation from trachytes (2–12 ppm) to pantellerites (15–25 ppm) and correlate positively with incompatible elements such as Th, Y, and Nb. The Mo concentrations, as determined by secondary ion mass spectrometry, are essentially the same in matrix glasses and melt inclusions, showing that Mo did not partition strongly into a volatile fluid phase during outgassing. The high Mo contents of the pantellerites (relative to metaluminous magmas with 1–5 ppm) may be due to several factors: (1) the enhanced stability of highly charged cations (such as Mo6+, U4+, and Zr4+) in peralkaline melts; (2) the rarity of Fe-Ti oxides and litanite into which Mo might normally partition; (3) reduced volatility of Mo in low fO2, H2O-poor (1–2 wt%) peralkaline magmas. Geochemical modeling indicates that the precipitation of MoS2 can be explained simply by the drop in temperature during magmatic differentiation. The occurrence of MoS2 in pantellerites may result from their high Mo concentrations and low redox state (Ni/NiO=-2.5) relative to metaluminous magmas, causing them to reach MoS2 saturation at magmatic temperatures. The apparent absence of MoS2 microphenocrysts in more oxidized, metaluminous rhyolites may indicate that Mo is dissolved primarily as a hexavalent ion in those magmas.  相似文献   

2.
Fixation of Mo in sulfidic environments is believed to be preceded by conversion of geochemically passive MoO42− to particle-reactive thiomolybdates (MoOxS4−x2−). In aqueous solution, these transformations are general-acid catalyzed, implying that proton donors can accelerate both the forward and reverse reactions. Here, we explore whether mineral surfaces also catalyze thiomolybdate interconversions. The rate of MoS42− hydrolysis is investigated in the presence and absence of natural kaolinite (KGa-1b) and synthetic Al2O3 and SiO2 phases. Comparison of rates achieved with these phases suggests that the Al oxyhydroxide component in kaolinite furnishes the catalytic activity. An anhydrous Al2O3 phase is catalytically inactive until hydrated (and therefore protonated). Surface kinetics with kaolinite at mildly alkaline pH are consistent with rate limitation by formation or decomposition of monomeric surface complexes; oligomeric surface intermediates may become important at MoS42− > 20 μmol/L, higher than is likely to be found in nature. The pH dependence of the kaolinite-catalyzed reaction suggests that weak-acid surface sites promote hydrolysis. Intermediate thiomolybdates or molybdate appears to compete for active sites, inhibiting MoS42− hydrolysis. Catalysis of MoOS32− hydrolysis is also observed but has not been studied systematically. Thiomolybdate hydrolysis is inhibited slightly by sulfate and more strongly by phosphate. Low NaCl concentrations (<10−2 mol/L) promote hydrolysis, but higher NaCl concentrations retard the reaction to a small extent. A mechanism is postulated involving expansion of the coordination number around Mo from 4 to 6 under the influence of the surface. The effective concentration of surface sites available to Mo in sediment pore waters is likely to be large enough to greatly accelerate thiomolybdate hydrolysis and sulfidation. Possibly this explains why Mo capture in seasonally or intermittently anoxic environments often occurs through processes operating within sediments but not in overlying waters.  相似文献   

3.
Erickson and Helz (2000) established that molybdate, MoO4−2, is quickly and completely transformed to thiomolybdate, MoS4−2, by reaction with sulfide. They monitored the equilibria and kinetics of this process by measuring the UV-visible spectra of solutions containing the different oxythiomolybdate species. There is interest in the analogous reactions for the ReO4− species but little experimental data. We have therefore calculated quantum-chemically the equilibrium constants in solution for the sulfidation reactions of both MoO4−2 and ReO4−, as well as recalculating their UV-visible charge-transfer spectra. Calculations using configuration interaction singles and time-dependent hybrid Hartree-Fock density functional methods give good absolute values and trends in UV-vis energies for both series. For MoO4−2 the calculated equilibrium constants for the various sulfidation steps match reasonably well against the experimental values (within two log K units). For the ReO4− sulfidation reaction the first two steps are considerably less favorable than for MoO4−2, suggesting that the “geochemical switch” of Erickson and Helz, a rapid transformation of oxyanion to thioanion highly dependent on sulfide concentration, will be less effective in the Re case. However, both our calculations and experiment indicate that ReO4− and ReS4− are both easier to reduce than their Mo analogs, so that reduction of these Re(VII) species will be the preferred mechanism for their removal from seawater. A previous suggestion that the neutral species MoO4H2 is actually the hydrated octahedral Mo(OH)6 species is found to be incorrect, but the MoO3(OH2)3 species, a highly distorted six-coordinate complex, is almost competitive in energy with MoO4H2 plus two H2O.  相似文献   

4.
As is known, a variable parameter for partial ionicity is often involved in the techniques of modeling structure and properties of inorganic crystals by energy-minimization methods. In such a case, to make a calculated energy comparable to experimental estimate (atomization energy) there is a need to involve an intraatomic energy term, the so-called charge-transfer energy (Urusov and Eremin 1995). For this purpose a set of charge-transfer energies for valence states of many elements is compiled. The procedure based on aspiration of equalizing the electronic levels electronegativities is proposed to estimate the total contribution of the charge-transfer energy in the cohesive energy of a crystal. The other prescribed quantities are repulsive potential parameters which are related to the energetic propertis of valence shells of bonded atoms. The final potential function consists of an effective Coulomb attraction, repulsion and covalent Morse type term, properly weighted. The energy-minimization procedure is performed for various values of the ionicity degree parameter of the crystal under study. Thereafter the charge-transfer energy correction is introduced in order for the cohesive energy calculations to be made. The calculations of structure, energy and elastic properties were performed using the METAPOCS code with ionicity variation for halides (NaCl, CaF2), oxides (MgO, Al2O3, SiO2 quartz and SnO2), sulphide ZnS and silicate CaSnSiO5. The resulting cohesive energies usually agree with experiment much better than those calculated in pure ionic or covalent approximations. As to elastic properties of crystals under consideration, they are generally functions of the ionicity parameter too and in most instances the predicted properties at intermediate values of the ionicity degree are in a satisfactory accordance with experimental data.  相似文献   

5.
Oxidation of As(III) by natural manganese (hydr)oxides is an important geochemical reaction mediating the transformation of highly concentrated As(III) in the acidic environment such as acid mine drainage (AMD) and industrial As-contaminated wastewater, however, little is known regarding the presence of dissolved Fe(II) on the oxidation process. In this study, oxidation of As(III) in the absence and presence of Fe(II) by MnO2 under acidic conditions was investigated. Kinetic results showed that the presence of Fe(II) significantly inhibited the removal of As(III) (including oxidation and sorption) by MnO2 in As(III)-Fe(II) simultaneous oxidation system even at the molar ratio of Fe(II):As(III) = 1/64:1, and the inhibitory effects increased with the increasing ratios of Fe(II):As(III). Such an inhibition could be attributed to the formation of Fe(III) compounds covering the surface of MnO2 and thus preventing the oxidizing sites available to As(III). On the other hand, the produced Fe(III) compounds adsorbed more As(III) and the oxidized As(V) on the MnO2 surface with an increasing ratio of Fe(II):As(III) as demonstrated in kinetic and XPS results. TEM and EDX results confirmed the formation of Fe compounds around MnO2 particles or separated in solution in Fe(II) individual oxidation system, Fe(II) pre-treated and simultaneous oxidation processes, and schwertmannite was detected in Fe(II) individual and Fe pre-treated oxidation processes, while a new kind of mineral, probably amorphous FeOHAs or FeAsO4 particles were detected in Fe(II)-As(III) simultaneous oxidation process. This suggests that the mechanisms are different in Fe pre-treated and simultaneous oxidation processes. In the Fe pre-treated and MnO2-mediated oxidation pathway, As(III) diffused through a schwertmannite coating formed around MnO2 particles to be oxidized. The newly formed As(V) was adsorbed onto the schwertmannite coating until its sorption capacity was exceeded. Arsenic(V) then diffused out of the coating and was released into the bulk solution. The diffusion into the schwertmannite coating and the oxidation of As(III) and sorption of both As(V) and As(III) onto the coating contributed to the removal of total As from the solution phase. In the simultaneous oxidation pathway, the competitive oxidation of Fe(II) and As(III) on MnO2 occurred first, followed by the formation of FeOHAs or FeAsO4 around MnO2 particles, and these poorly crystalline particles of FeOHAs and FeAsO4 remained suspended in the bulk solution to adsorb As(III) and As(V). The present study reveals that the formation of Fe(III) compounds on mineral surfaces play an important role in the sorption and oxidation of As(III) by MnO2 under acidic conditions in natural environments, and the mechanisms involved in the oxidation of As(III) depend upon how Fe(II) is introduced into the As(III)-MnO2 system.  相似文献   

6.
Edet E. Isuk 《Lithos》1983,16(1):17-22
The effects of excess SiO2 and CO2 on the solubility of molybdenite in hydrous sodium disilicate melts were experimentally determined at 680 bars and 650°C. The molybdenite solubility decreases with increasing SiO2 and CO2. Under the experimental conditions, the MoS2 content of the vapor-saturated liquid decreases from 10 wt.% to 2.5 wt.% at SiO2 saturation. In the presence of CO2, the solubility decreases to 4.6 wt.% MoS2 and becomes negligible at high PCO2. These results are explained as deriving from the increased polymerization and hence decreased NBO/Si ratio of the melt with increasing SiO2 content and CO2, respectively. Sulfur dissolves principally as SO4?2 at the relatively high fo2 of the experiments. Consequently, the effect of sulfur is to lower the Mo solubility by effectively decreasing the NBO/Si ratio of the melt. Sulfur saturation is, therefore, likely to be a limiting factor in the Mo content of alkali silicate melts because of the chalcophile affinities of molybdenum.  相似文献   

7.
Three (Cr1?x Al x )N (x = 0.33, 0.5, 0.66) coatings were deposited on Ni-super alloy IN718 using reactive magnetron sputtering. The oxidation behavior of all coatings at 900 °C up to 500 h in air was studied. Furthermore, the corrosion behavior of the (Cr0.33,Al0.66)N coating at 900 °C (corrosion type I) by spraying a uniform salt scale of Na2SO4 on the sample surface (1 mg/cm2) was investigated. It was found that the coated samples indicate significantly higher oxidation and corrosion resistance compared to uncoated Ni super alloy. This is mainly due to the formation of protective Cr2O3 and Al2O3 layers on the coating surface. With the increase of Al content, the coatings exhibited improved oxidation resistance. The formation of thin and adherent Al2O3 scale on the surface of Al rich coating is the reason for its better oxidation behavior. The detailed structures of the oxide scales and the interdiffusion between coating and substrate were studied using energy dispersive X-ray spectroscopy-analysis.  相似文献   

8.
In order to investigate the effect of Thiobacillusferrooxidans on the oxidation of pyrite, two parallel experiments, which employed H2SO4 solutions and acidic solutions inoculated with ThiobaciUus ferrooxidans, were designed and carried out at 30℃. The initial pH of the two solutions was adjusted to 2.5 by dropwise addition of concentrated sulphuric acid. The surfaces of pyrite before exposure to leaching solutions and after exposure to the H2SO4 solutions and acidic solutions inoculated with Thiobacillus ferrooxidans were observed by scanning electron microscopy （SEM）. There were a variety of erosion patterns by Thiobacillusferrooxidans on the bio-leached pyrite surfaces. A conclusion can be drawn that the oxidation of pyrite might have been caused by erosion of the surfaces. Attachment of the bacteria to pyrite surfaces resulted in erosion pits, leading to the oxidation of pyrite. It is possible that the direct mechanism plays the most important role in the oxidation of pyrite. The changes in iron ion concentrations of both the experimental solutions with time suggest that ThiobaciUus ferrooxidans can enhance greatly the oxidation of pyrite.  相似文献   

9.
Understanding the mechanisms of selenium behavior under near-surface conditions is a topical problem of modern mineralogy and geochemistry that is very important in solving some environmental problems. The objective of this study is to develop techniques of synthesizing a chalcomenite analog and to study its speciation and properties. The synthesis was performed by boiling-dry aqueous Cu2(CO3)(OH)2 solutions and selenium acid H2SeO3. The obtained samples were identified by X-ray diffraction and IR spectroscopy. The Eh-pH diagrams were calculated using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams have been calculated for the Cu-Se-CO2-H2O system for the average content of these elements in underground waters and their contents in acidic waters in the oxidation zones of sulfide deposits. The formation of chalcomenite and malachite under near-surface conditions is discussed.  相似文献   

10.
Manganese carbonate can be converted to many kinds of manganese oxides when it is aerated in air and oxygen.Pure manganese carbonate can be changed into Mn3O4 and γ-MnOOH,and manganese carbonate ore can be converted to MnO2 under the air-aerating and oxygen-aerating circumstances.The oxidation process of manganese carbonate is a changing process of mineral association,and is also a converting process of valence of manganese itself.Not only equilibrium stat,but also nonequilibrium state are involved in this whole process,This process is an irreversible heterogeneous complex reaction,and oberys the nonequilibrium thermodynamic model,The oxidation rate of manganese cabonate is controlled by many factors,especially nonmanganese metallic ions which play an important role in the oxidation process of manganese carbonate.  相似文献   

11.
The approach coupled with computation fluid dynamics (CFD) and complex chemical kinetic computation to predict the oxidation of the elemental mercury in flue gas was discussed in this paper. According to the oxidation mechanism of the elemental mercury, the reactions which were in close relationship with mercury oxidation were determined by the sensitivity analysis method. The mercury oxidation process was simulated under the atmospheric pressure condition with different flue-gas compositions. The three-dimensional concentration distribution of mercury within the cylindrical flue duct and the impact of the temperature, concentration of Cl2, HCl, NO, and O2 on the mercury oxidation were also obtained. The simulation results were compared with the experimental results of Mamani-Paco and Widmer. The results show that coupling computation solves the problem of the combination of the CFD with the complex kinetic mechanism. The promotion effect of Cl2 on the oxidation of elemental mercury is much better than that of HCl. The temperature window ranged from 950 to 1,150 K for the higher oxidizing rate of the elemental mercury was determined. The slight enhancement of NO on mercury oxidization was observed which was controlled by the competition between two reaction pathways. O2 weakly promotes homogeneous Hg oxidation, especially under the condition of high temperature. 1.1, 2.6 and 3.1 % of mercury was oxidized in the presence of 0, 4 and 16 % O2 at 600 K, respectively. However, 12.5, 22.5 and 26.0 % of Hg oxidation has been obtained at 1,200 K.  相似文献   

12.
We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.  相似文献   

13.
In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS2) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS2) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS2 clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.  相似文献   

14.
Capture of Mo by FeS2 is an important sink for marine Mo. X-ray spectroscopy has shown that Mo forms Mo-Fe-S cuboidal clusters on pyrite. Reduction of MoVI must occur to stabilize these structures. Sulfide alone is a poor reductant for Mo, producing instead a series of MoVI thioanions (MoOxS4−x2−, x = 0-3). In solutions that contain both H2S and S0-donors (i.e. polysulfides; dissolved S8), Mo is transformed to MoIV or MoV2 polysulfide/sulfide anions. This intramolecular reduction requires no external reducing agent. Remarkably, an oxidizing agent (S0 donor), rather than a reducing agent, stabilizes the reducible MoVI complex. Thiomolybdates and their reduction products do not precipitate spontaneously; solutions supersaturated by 109 with respect to molybdenite, MoS2, produce no precipitate in 40 days. In 10-minute exposures, pyrite can scavenge MoOS32− and MoS42− weakly at mildly alkaline pH but can scavenge an unidentified product of the S0-induced reduction of MoOS32− very strongly. On the basis of these observations, a reaction pathway for Mo capture by pyrite is proposed. Conditions that favor Mo capture by this pathway also favor pyrite growth. Ascribing Mo capture simply to low redox potential is too simplistic and neglects the likely role of oxidizing S0-donors. The aqueous speciation of Mo in anoxic environments will be a function of the activity of zero-valent sulfur as well as the activity of H2S(aq).  相似文献   

15.
The oxidation of carbonate green rust, GR(CO32−), in NaHCO3 solutions at T = 25°C has been investigated through electrochemical techniques, FTIR, XRD, TEM and SEM. The used GR(CO32−) samples were made of either suspended solid in solution or a thin electrochemically formed layer on the surface of an iron disc. Depending on experimental conditions, oxidation occurs, with or without major modifications of the GR(CO32−) structure, suggesting the existence of two pathways: solid-state oxidation (SSO) leading to a ferric oxyhydroxycarbonate as the end product, and a dissolution-oxidation-precipitation (DOP) mechanism leading to ferric oxihydroxides such as lepidocrocite, goethite, or ferrihydrite. A formula was proposed for this ferric oxyhydroxycarbonate, Fe6IIIO(2+x)(OH)(12-2x)(H2O)x(CO3), assuming that the solid-state oxidation reaction is associated to a deprotonation of the water molecules within the interlayers, or of the hydroxyl groups in the Fe(O,H) octahedra layers. The DOP mechanism involves transformation via solution with the occurrence of soluble ferrous-ferric intermediate species. A discussion about factors influencing the oxidation of carbonate green rust is provided hereafter. The ferric oxyhydroxycarbonate can be reduced back to GR(CO32−) by a reverse solid-state reduction reaction. The potentiality for a solid-state redox cycling of iron to occur may be considered. The stability of the ferric oxyhydroxycarbonate towards thermodynamically stable ferric phases, such as goethite and hematite, was also studied.  相似文献   

16.
《Applied Geochemistry》2006,21(8):1259-1273
Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe–As–O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu2S] and (or) djurleite [Cu31S16], occur as a layer (generally <500 nm thick) along the arsenopyrite grain boundary, and also within the coating as aggregates, and as layers that parallel the grain boundary. Although the precipitation of secondary Cu minerals along the grain boundary is a nanoscale feature, the process of formation is thought to be analogous to the supergene enrichment that occurs in weathered sulfide deposits. As the oxidation of arsenopyrite proceeds, layers and clusters of secondary Cu sulfides become isolated in the Fe–As–O coating. Secondary wulfenite [PbMoO4] and an unidentified crystalline Bi–Pb–As–O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi–Pb–As–O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS2], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources and sinks at this location. The results of this study indicate that the mineralogical controls on aqueous elemental concentrations at this tailings site are complex and are not predicted by thermodynamic calculations.  相似文献   

17.
《Geochimica et cosmochimica acta》1999,63(19-20):3301-3310
The weathering rate of sedimentary organic matter in the continental surficial environment is poorly constrained despite its importance to the geochemical carbon cycle. During this weathering, complete oxidation to carbon dioxide is normally assumed, but there is little proof that this actually occurs. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time.We have determined the aqueous oxidation rates of pyrite-free bituminous coal at 24° and 50°C by using a dual-cell flow-through method. Coal was used as an example of sedimentary organic matter because of the difficulty in obtaining pyrite-free kerogen for laboratory study. The aqueous oxidation rate obtained in the present study for air-saturated water (270 μM O2) was found to be on the order of 2 × 10−12 mol O2/m2/s at 25°C, which is fast compared to other geologic processes such as tectonic uplift and exposure through erosion. The reaction order with respect to oxygen level is 0.5 on a several thousand hour time scale for both 24° and 50°C experiments. Activation energies, determined under 24° and 50°C conditions, were ≈40 kJ/mol O2 indicating that the oxidation reaction is surface reaction controlled.The oxygen consumption rate obtained in this study is two to three orders of magnitude smaller than that for pyrite oxidation in water, but still rapid on a geologic time scale. Aqueous coal oxidation results in the formation of dissolved CO2, dissolved organic carbon (DOC), and solid oxidation products, which are all quantitatively significant reaction products.  相似文献   

18.
A detailed experimental study was conducted to investigate mechanisms of pyrite oxidation by determining product yields and oxygen isotopic fractionation during reactions between powdered pyrite (FeS2) with aqueous hydrogen peroxide (H2O2). Sealed silica-tube experiments utilized aliquots of pyrite that were reacted with 0.2 M H2O2 for 7 to 14 days at 4 to 150 °C. No volatile sulfur species were detected in any experiment. The only gaseous product recovered was elemental oxygen inferred to result from decomposition of H2O2. Aqueous sulfate (Saq) was the only sulfur product recovered from solution. Solid hydrated ferric iron sulfates (i.e., water-soluble sulfate fraction, Sws) were recovered from all experiments. Ferric oxide (hematite) was detected only in high temperature experiments.Reactants were selected with large differences in initial δ18O values. The oxygen isotopic compositions of oxygen-bearing reactants and products were analyzed for each experiment. Subsequent isotopic mass-balances were used to identify sources of oxygen for reaction products and to implicate specific chemical reaction mechanisms. δ18O of water did not show detectable change during any experiment. δ18O of sulfate was similar for Saq and Sws and indicated that both H2O and H2O2 were sources of oxygen in sulfate. Low-temperature experiments suggest that H2O-derived oxygen was incorporated into sulfate via Fe3+ oxidation, whereas H2O2-derived oxygen was incorporated into sulfate via oxidation by hydroxyl radicals (HO). These two competing mechanisms for oxygen incorporation into sulfate express comparable influences at 25 °C. With increasing reaction temperatures from 4 to 100 °C, it appears that accelerated thermal decomposition and diminished residence time of H2O2 limit the oxygen transfer from H2O2 into sulfate and enhance the relative importance of H2O-derived oxygen for incorporation into sulfate. Notably, at temperatures between 100 and 150 °C there is a reversal in the lower temperature trend resulting in dominance of H2O2-derived oxygen over H2O-derived oxygen. At such high temperatures, complete thermal decomposition of H2O2 to water and molecular oxygen (O2) occurs within minutes in mineral-blank experiments and suggests little possibility for direct oxidation of pyrite by H2O2 above 100 °C. We hypothesize that a Fe-O2 mechanism is responsible for oxygenating pyrite to sulfate using O2 from the preceding thermal decomposition of H2O2.  相似文献   

19.
The sediments of the Madeira Abyssal Plain, east of Great Meteor Seamount, are dominated by distal turbidite deposition. While the turbidites exhibit a wide compositional range (25–80% CaCO3), individual examples can be correlated over a wide area and are relatively homogenous. Organic C oxidation, by bottom water oxygen, proceeds from the turbidite tops downwards after emplacement in pelagic conditions, and the progress of this oxidation front is marked by a sharp colour contrast in the sediments (Wilsonet al., 1985). In turbidites with Corg ? 0.5%, redistribution of authigenic U occurs to form a concentration peak (4–9 ppm U), just below the oxidation front or colour change. Several tens μg U/cm2 may be mobilised, and in all examples studied ?60% of the remobilised U is relocated into the peak. Following burial by subsequent turbidites, such U concentration peaks are persistent as relict indicators of their extinct oxidation fronts for at least 2 × 105 years. In the case of thin turbidites where labile Corg is almost exhausted, the U peaks may be located in underlying sedimentary units because of their relationship to the oxidation front. A redox mechanism for U peak formation is suggested from these data rather than a complexation with organic matter.  相似文献   

20.
The geochemistry of Se is largely controlled by that of iron, with which Se is closely affiliated in both oxidizing and reducing environments. In aerated waters the Se(IV) oxyanions, HSeO?3 and SeO2?3, are strongly adsorbed by hydrated surfaces of ferric oxides over the pH range 2–8; above pH8 adsorption decreases to complete desorption at pH 11. This adsorption immobilizes Se(IV) in neutral-to-acid waters and increases the range of oxidation potential over which Se(IV) is stable. During experimental aeration of aqueous Fe-S-Se systems, the stability field of Se(IV) is attained and elemental Se is slowly oxidized to this higher valence; oxidation potentials of the Se(VI) stability field were never reached, however, even by continued aeration of an alkaline system. Under reducing conditions, elemental Se either is incorporated within pyrite or forms the mineral ferroselite (FeSe2.Selenium geochemistry is summarized on an Eh-pH diagram, synthesized from equilibrium calculations, experimental work and reported geologic occurrences. A stability field for ferroselite, constructed for a Gibbs free-energy value of ?23.2 kcal/mole, is in accord both with its geologic occurrence and behavior and with conditions under which ferroselite has been synthesized. Traces on this diagram of Eh-pH variation show the behavior of selenium during oxidation of associated iron-sulfide minerals. Such considerations also demonstrate the manner in which selenium migrates, is deposited and is increasingly concentrated in roll-type sandstone uranium deposits, as well as the relative positions of the several forms of selenium within the deposit.  相似文献   

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