Oxidation of Sb(III) to Sb(V) by O2 and H2O2 in aqueous solutions

The rates of Sb(III) oxidation by O₂ and H₂O₂ were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O₂ was first order with respect to the Sb(III) concentration and inversely proportional to the H⁺ concentrations at a constant O₂ content of 0.22 × 10⁻³ M. Pseudo-first-order rate coefficients, k_obs, ranged from 3.5 × 10⁻⁸ s⁻¹ to 2.5 × 10⁻⁶ s⁻¹ at pH values between 10.9 and 12.9. The relationship between k_obs and pH was:

     

Stability of YREE complexes with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength

Organic complexation of yttrium and the rare earth elements (YREEs), although generally believed to be important, is an understudied aspect of YREE solution speciation in the open ocean. We report the first series of stability constants for complexes of YREEs (except Ce and Pm) with the trihydroxamate siderophore desferrioxamine B (DFOB), representing a class of small organic ligands that have an extraordinary selectivity for Fe(III) and are found in surface seawater at low-picomolar concentrations. Constants were measured by potentiometric titration of DFOB (pH 3-10) in the presence of single YREEs, in simple media at seawater ionic strength (NaClO₄ or NaCl, I = 0.7 M). Under these circumstances, the terminal amine of DFOB does not deprotonate. The four acid dissociation constants of the siderophore were determined separately by potentiometric titration of DFOB alone.Values for the bidentate (log β₁), tetradentate (log β₂), and hexadentate (log β₃) complexes of La-Lu range from 4.88 to 6.53, 7.70 to 11.27, and 10.09 to 15.19, respectively, while Y falls between Gd and Tb in each case. Linear free-energy relations of the three stability constants with the first YREE hydrolysis constant, log , yield regression coefficients of >0.97. On the other hand, plots of the constants vs. the radius of the inner hydration sphere display an increasing deviation from linearity for the lightest REEs (La > Pr > Nd). This may signify steric constraints in DFOB folding around bulkier cations, a larger mismatch in coordination number, or a substantial degree of covalence in the YREE-hydroxamate bond.Complexes of the YREEs with DFOB are many orders of magnitude more stable than those with carbonate, the dominant inorganic YREE ligand in seawater. Speciation modeling with MINEQL indicates that, for an average seawater composition, the hexadentate complex could constitute as much as 28% of dissolved Lu at free DFOB concentrations as low as 10⁻¹³ M. Such conditions might occur when DFOB or other siderophores are present in excess over metals for which they have high affinity, like Fe(III) and Co(III), for example during plankton blooms. Even if it turns out that trihydroxamate siderophores are not the dominant organic YREE ligand in seawater, our results establish a benchmark for producing effects on YREE solution speciation comparable to that of DFOB: the free concentration of any weaker organic ligand L must exceed that of DFOB by a factor β₃/_Lβ₁, assuming its first order complex is formed in greatest abundance.     

Oxidative dissolution potential of biogenic and abiogenic TcO2 in subsurface sediments

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.     

Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model

A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, M_max, the attachment constant, K_P, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, , on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.     

Calcite dissolution kinetics in the system CaCO3-H2O-CO2 at high undersaturation

Dissolution rates of limestone covered by a water film open to a CO₂-containing atmosphere are controlled by the chemical composition of the CaCO₃-H₂O-CO₂ solution at the water-mineral interface. This composition is determined by the Ca²⁺-concentration at this boundary, conversion of CO₂ into H⁺ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca²⁺, , and CO₂ is derived. The Ca²⁺ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO₂ across the air-water interface. In the solution, CO₂ is converted into H⁺ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = α_i(m_ic_eq − c), where c is the calcium concentration in the water film, c_eq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α₀ = 3 × 10⁻⁶ m s⁻¹ and m₀ = 0.3. For c > m₀c_eq, a slow rate law is valid with α₁ = 3 × 10⁻⁷ m  s⁻¹ and m₁ = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.     

Inter-relationships of MnO2 precipitation, siderophore-Mn complex formation, siderophore degradation, and iron limitation in Mn-oxidizing bacterial cultures

To examine the pathways that form Mn^(III) and Mn^(IV) in the Mn^(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn^(IV)O₂ formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn^(III) complex or insoluble Mn^(IV)O₂ minerals - but not both simultaneously. PVD-Mn^(III) was present, and MnO₂ precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn^(III) arose by predominantly ligand-mediated air oxidation of Mn^(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn^(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn^(III), a process linked to the production of both MnO₂ and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn^(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO₂ to appear. These results suggest that P. putida cultures produce soluble Mn^(III) or MnO₂ by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO₂ under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn^(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn^(III) versus MnO₂) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

Solubility of KFe(CrO4)2·2H2O at 4–75°C

The solubility of KFe(CrO₄)₂·2H₂O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO₄)₂·2H₂O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log K_SP for the reaction

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Acoustic velocity measurements on Na2O-TiO2-SiO2 liquids: Evidence for a highly compressible TiO2 component related to five-coordinated Ti

Longitudinal acoustic velocities were measured at 1 bar in 10 Na₂O-TiO₂-SiO₂ (NTS) liquids for which previous density and thermal expansion data are reported in the literature. Data were collected with a frequency-sweep acoustic interferometer at centered frequencies of 4.5, 5, and 6 MHz between 1233 and 1896 K; in all cases, the sound speeds decrease with increasing temperature. Six of the liquids have a similar TiO₂ concentration (∼25 mol %), so that the effect of varying Na/Si ratio on the partial molar compressibility of the TiO₂ component can be evaluated. Theoretically based models for β_T and (∂V/∂P)_T as a function of composition and temperature are presented. As found previously for the partial molar volume of TiO₂ in sodium silicate melts, values of (13.7-18.8 × 10⁻²/GPa) vary systematically with the Na/Si and Na/(Si + Ti) ratio in the liquid. In contrast values of for the SiO₂ and Na₂O components (6.6 and 8.0 × 10⁻²/GPa, respectively, at 1573 K) are independent of composition. Na₂O is the only component that contributes to the temperature dependence of the compressibility of NTS liquids (1.13 ± 0.04 × 10⁻⁴/GPa K). The results further indicate that the TiO₂ component is twice as compressible as the Na₂O and SiO₂ components. The enhanced compressibility of TiO₂ appears to be related to the abundance of five-coordinated Ti (^[5]Ti) in these liquids, but not with a change in Ti coordination. Instead, it is proposed that the asymmetric geometry of ^[5]Ti in a square pyramidal site promotes different topological rearrangements in alkali titanosilicate liquids, which lead to the enhanced compressibility of TiO₂.     

Molecular H2O in armenite, BaCa2Al6Si9O30·2H2O, and epididymite, Na2Be2Si6O15·H2O: Heat capacity, entropy and local-bonding behavior of confined H2O in microporous silicates

Armenite, ideal formula BaCa₂Al₆Si₉O₃₀·2H₂O, and its dehydrated analog BaCa₂Al₆Si₉O₃₀ and epididymite, ideal formula Na₂Be₂Si₆O₁₅·H₂O, and its dehydrated analog Na₂Be₂Si₆O₁₅ were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C_p, behavior of their confined H₂O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H₂O molecule.The determined structural formula for armenite is Ba_0.88(0.01)Ca_1.99(0.02)Na_0.04(0.01)Al_5.89(0.03)Si_9.12(0.02)O₃₀·2H₂O and for epididymite Na_1.88(0.03)K_0.05(0.004)Na_0.01(0.004)Be_2.02(0.008)Si_6.00(0.01)O₁₅·H₂O. The infrared (IR) spectra give information on the nature of the H₂O molecules in the natural phases via their H₂O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H₂O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔS^rxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔS^rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H₂O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H₂O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H₂O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H₂O phases ice, liquid water and steam, the C_p behavior of confined H₂O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C_p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H₂O at 298 K is analyzed for various microporous silicates.The entropy of confined H₂O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H₂O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H₂O. This results in increased amplitudes of external H₂O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H₂O at T < 298 K.     

Residence times for protons bound to three oxygen sites in the AlO4Al12(OH)24(H2O)12 polyoxocation

Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO₄Al₁₂(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using ¹H NMR at pH ∼ 5 in both aqueous and mixed solvents. The ¹H NMR peak for protons on bound waters (η-H₂O) lies near 8 ppm in a 2.5:1 mixture of H₂O/acetone-d₆ and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H₂O is τ²⁹⁸ ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H₂O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H₂O)₆³⁺). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al₁₃ molecule in addition to the fully protonated Al₁₃ at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ₂-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H₂O/dmso-d₆ over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ₂-OH was also measured in D₂O. The τ²⁹⁸ values are ∼0.013 and ∼0.2 s in the H₂O/dmso-d₆ solution and the τ²⁹⁸ value for the μ₂-OH detectable in D₂O is τ²⁹⁸ ∼ 0.013 s. The ¹H NMR peak for the more reactive μ₂-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.     

Hydroxamate siderophore-promoted reactions between iron(II) and nitroaromatic groundwater contaminants

Recent studies show that ferrous iron (Fe^II), which is often abundant in anaerobic soil and groundwater, is capable of abiotically reducing many subsurface contaminants. However, studies also demonstrate that Fe^II redox reactivity in geochemical systems is heavily dependent upon metal speciation. This contribution examines the influence of hydroxamate ligands, including the trihydroxamate siderophore desferrioxamine B (DFOB), on Fe^II reactions with nitroaromatic groundwater contaminants (NACs). Experimental results demonstrate that ring-substituted NACs are reduced to the corresponding aniline products in aqueous solutions containing Fe^II complexes with DFOB and two monohydroxamate ligands (acetohydroxamic acid and salicylhydroxamic acid). Reaction rates are heavily dependent upon solution conditions and the identities of both the Fe^II-complexing hydroxamate ligand and the target NAC. Trends in the observed pseudo-first-order rate constants for reduction of 4-chloronitrobenzene (k_obs, s⁻¹) are quantitatively linked to the formation of Fe^II species with standard one-electron reduction potentials, (Fe^III/Fe^II), below −0.3 V. Linear free energy relationships correlate reaction rates with the (Fe^III/Fe^II) values of different electron-donating Fe^II complexes and with the apparent one-electron reduction potentials of different electron-accepting NACs, (ArNO₂). Experiments describing a redox auto-decomposition mechanism for Fe^II-DFOB complexes that occurs at neutral pH and has implications for the stability of hydroxamate siderophores in anaerobic environments are also presented. Results from this study indicate that hydroxamates and other Fe^III-stabilizing organic ligands can form highly redox-active Fe^II complexes that may contribute to the natural attenuation and remediation of subsurface contaminants.     

A general algorithm for the O abundance correction to C/C determinations from CO2 isotopologue measurements, including CO2 characterised by ‘mass-independent’ oxygen isotope distributions

It is widely recognised that a significant limitation to the ultimate precision of carbon stable isotope ratio measurements, as obtained from dual-inlet mass spectrometric measurements of CO₂ isotopologue ion abundances at m/z 44, 45, and 46, is the correction for interference from ¹⁷O-bearing molecular ions. Two long-established, alternative procedures for determining the magnitude of this correction are in widespread use (although only one has IAEA approval); their differences lead to small but potentially significant discrepancies in the magnitude of the resulting correction. Furthermore, neither approach was designed to accommodate oxygen three-isotope distributions which do not conform to terrestrial mass-dependent behaviour. Stratospheric CO₂, for example, contains a strongly ‘mass-independent’ oxygen isotope composition. A new strategy for determining the ¹⁷O-bearing ion correction is presented, for application where the oxygen three-isotope characteristics of the analyte CO₂ are accurately known (or assigned) in terms of the slope λ of the three-isotope fractionation line and the ordinate axis intercept 10³ ln(1 + k) on a 10³ ln(1 + δ¹⁷O) versus 10³ ln(1 + δ¹⁸O) plot. At the heart of the approach is the relationship between ¹⁷R, which is the ¹⁷O/¹⁶O ratio of the sample CO₂, and other assigned or empirically determined parameters needed for the δ¹³C evaluation:

     

Oxidation of aqueous Cr(III) at birnessite surfaces: constraints on reaction mechanism

X-ray Photoelectron Spectroscopy (XPS) was used to investigate oxidation of aqueous Cr(III) at the surface of 7 Å-birnessite [MnO_1.75(OH)_0.25]. Special emphasis was placed on detection of intermediate oxidation states of chromium due to their critical environmental significance. No previous studies have been able to identify these intermediate oxidation states of chromium (namely, Cr[IV] and Cr[V]) on mineral surfaces or in natural solutions. Mn(2p_3/2), Cr(2p_3/2) and O(1s) spectra of the reacted surfaces reveal that Mn(IV) of synthetic birnessite undergoes reductive dissolution in two steps. The first step involves Mn(IV) reduction to Mn(III),that forms at the oxide surface probably as an oxyhydroxide (MnOOH), and in the second step Mn(III) is reduced to Mn(II) that is subsequently taken into solution. Each reductive reaction step involves transfer of only one electron to the Mn ion. After Cr(III)_aq is adsorbed onto the MnO₂ surface, it undergoes oxidation in three separate steps, each involving the loss of one electron to Mn ions, so that Cr(IV), Cr(V) and Cr(VI) are produced. The intermediate reaction products, namely Mn(III), and Cr(V) were positively identified by XPS spectral analyses. Similarity in XPS binding energy values of Cr(III) and Cr(IV) as well as that of Cr(V) and Cr(VI), however, preclude separate identification of Cr(III) from Cr(IV) and Cr(VI) from Cr(V) multiplets on the near-surface of the solid. A parallel reaction scheme (exclusive of sorption reactions) best describes the birnessite-Cr(III)_aq redox reactions. The two parallel reactions proceed by separate mechanisms with a monodentate complex formed in one mechanism and a bidentate complex in another. The bulk of Cr(IV) probably is formed via the monodentate complex and Cr(V) via the bidentate complex. The rate expressions associated with these reactions display near-perfect correlation with changing surface abundances of Cr(IV) and Cr(V) as a function of reaction time. Copyright © 1999 Elsevier Science Ltd.     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

Pyrite (FeS2) oxidation: A sub-micron synchrotron investigation of the initial steps

Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS₂) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process.Four different S species are found to be present on fresh fractured pyrite surfaces: S₂²⁻_(bulk) (4-fold coordination), S₂²⁻_(surface) (3-fold coordination), S²⁻ and S⁰/S_n²⁻ (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O₂ and H₂O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O₂ dissociatively and H₂O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H₂O may then dissociate to produce OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of OH radicals formed at the Fe sites, with formation of SO₄²⁻ occurring via S₂O₃²⁻/SO₃²⁻ intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O₂ and H₂O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO₄²⁻ arises largely from H₂O; however, depending on the surface history, SO₄²⁻ formed early in the oxidation process may also contain O from O₂.     

H2O diffusion in dacitic and andesitic melts

The diffusion of water in dacitic and andesitic melts was investigated at temperatures of 1458 to 1858 K and pressures between 0.5 and 1.5 GPa using the diffusion couple technique. Pairs of nominally dry glasses and hydrous glasses containing between 1.5 and 6.3 wt.% dissolved H₂O were heated for 60 to 480 s in a piston cylinder apparatus. Concentration profiles of hydrous species (OH groups and H₂O molecules) and total water (C_H2Ot = sum of OH and H₂O) were measured along the cylindrical axis of the diffusion sample using IR microspectroscopy. Electron microprobe traverses show no significant change in relative proportions of anhydrous components along H₂O profiles, indicating that our data can be treated as effective binary interdiffusion between H₂O and the rest of the silicate melt. Bulk water diffusivity (D_H2Ot) was derived from profiles of total water using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between D_H2Ot and C_H2Ot. In dacitic melts D_H2Ot is proportional to C_H2Ot up to 6 wt.%. In andesitic melts the dependence of D_H2Ot on C_H2Ot is less pronounced. A pressure effect on water diffusivity could not be resolved for either dacitic or andesitic melt in the range 0.5 to 1.5 GPa. Combining our results with previous studies on water diffusion in rhyolite and basalt show that for a given water content D_H2Ot increases monotonically with increasing melt depolymerization at temperatures >1500 K. Assuming an Arrhenian behavior in the whole compositional range, the following formulation was derived to estimate D_H2Ot (m²/s) at 1 wt.% H₂O_t in melts with rhyolitic to andesitic composition as a function of T (K), P (MPa) and S (wt.% SiO₂):

     

Shear viscosities of CaO-Al2O3-SiO2 and MgO-Al2O3-SiO2 liquids: Implications for the structural role of aluminium and the degree of polymerisation of synthetic and natural aluminosilicate melts

The shear viscosity of 66 liquids in the systems CaO-Al₂O₃-SiO₂ (CAS) and MgO-Al₂O₃-SiO₂ (MAS) have been measured in the ranges 1-10⁴ Pa s and 10⁸-10¹² Pa s. Liquids belong to series, nominally at 50, 67, and 75 mol.% SiO₂, with atomic M²⁺/(M²⁺+2Al) typically in the range 0.60 to 0.40 for each isopleth. In the system CAS at 1600°C, viscosity passes through a maximum at all silica contents. The maxima are clearly centered in the peraluminous field, but the exact composition at which viscosity is a maximum is poorly defined. Similar features are observed at 900°C. In contrast, data for the system MAS at 1600°C show that viscosity decreases with decreasing Mg/(Mg + 2Al) at all silica contents, but that a maximum in viscosity must occur in the field where Mg/2Al >1. On the other hand, the viscosity at 850°C increases with decreasing Mg/(Mg + 2Al) and shows no sign of reaching a maximum, even for the most peraluminous composition studied. The data from both systems at 1600°C have been analysed assuming that shear viscosity is proportional to average bond strength and considering the equilibrium:

Al^[4]-(Mg,Ca)_0.5⇔(Mg,Ca)_0.5-NBO+Al_XS