Measurement of the effects of temperature and partial pressure of oxygen on the oxidation states of europium in silicate glasses

The techniques of electron paramagnetic resonance (EPR) were used to measure the concentration ratio of Eu²⁺ to Eu³⁺ in quenched CaMgSi₂O₆, Ca₃Si₃O₁₂, and CaAl₂Si₂O₈ liquids as functions of partial pressure of oxygen and temperature. The redox equilibrium of the Eu ions was described by the reaction 4Eu³⁺ + 20^2? = 4Eu²⁺ + O₂. The reduction of Eu³⁺ to Eu²⁺ was endothermic, and for CaMgSi₂O₆ and Ca₃Al₂Si₃O₁₂ liquids the mean value of ΔH⁰ and the standard deviation from that mean were 25 ± 7 kcal/mole.The magnitude of the Eu anomaly in the distribution coefficients is discussed in terms of the compositions of the solid and liquid phases.     

The oxidation state of europium as an indicator of oxygen fugacity

The distribution of Eu between plagioclase feldspar and magmatic liquid has been determined experimentally for basaltic and andesitic systems as a function of temperature and oxygen fugacity at one atmosphere total pressure. Using the approach of Philpotts the ratios $\text{Eu}{}^{\mathrm{2+}}\text{Eu}{}^{\mathrm{3+}}$ in plagioclase and coexisting magmatic liquid have been calculated. These ratios appear to be simply related to oxygen fugacity for the bulk compositions studied here. Using published trace element distribution data for natural rocks oxygen fugacities may be calculated from these experimental results. For terrestrial basalts calculated oxygen fugacities average 10^?7 with little dispersion from this value. Andesites average 10^?8.1 with considerable dispersion, while dacites and rhyodacites average 10^?9.1, also with considerable dispersion. Oxygen fugacities for lunar ferrobasalts cluster tightly around 10^?12.7. Data on achondritic meteorites are limited, but calculations indicate oxygen fugacities of two-to-five orders of magnitude lower than lunar ferrobasalts.     

Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation

A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using ¹H, ²⁹Si, and ²⁷Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as ¹H-²⁹Si and ¹H-²⁷Al cross-polarization (CP) MAS NMR, ¹H double quantum (DQ) MAS NMR and ²⁷Al multiple quantum (MQ) MAS NMR. Under acidic conditions, ²⁹Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the ²⁹Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From ¹H DQ and ¹H-²⁹Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q²), Si (Q³), and Si (Q⁴) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. ²⁷Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO₄]⁻ groups during glass alteration. ¹H-²⁷Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.     

孔道结构化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4]的钒氧化态与热稳定性关系研究

热处理脱除有机模板易导致VPO体系孔道结构化合物结构破坏,从而阻碍此类材料的实际应用。以孔道结构化合物(H3NCH2CH2NH3)3[(VO)4 (PO4 )2 (HPO4 )4 ](简称V2P3 en)为研究对象,利用热分析(DSC TG)、动态原位高温X 射线衍射(XRD)及多功能X 射线光电子能谱(XPS)等方法,研究了该化合物在不同气氛热处理过程中模板脱除及结构演化规律,重点探讨了钒氧化态的变化对结构稳定性的影响。结果表明,加热过程中随着有机模板的分解脱除,形成较强的还原环境,骨架中的部分钒被还原(V4+→V3+),使原有的配位环境([VⅣO5]三角双锥、[VⅣO6]畸变八面体)与钒的氧化态不符而导致结构重组。因此,钒氧化态的变化是影响热稳定性的重要因素之一。     

Influence of glass polymerisation and oxidation on micro-Raman water analysis in alumino-silicate glasses

The development of an accurate analytical procedure for determination of dissolved water in complex alumino-silicate glasses via micro-Raman analysis requires the assessment of the spectra topology dependence on glass composition. We report here a detailed study of the respective influence of bulk composition, iron oxidation state and total water content on the absolute and relative intensities of the main Raman bands related to glass network vibrations (LF: ∼490 cm⁻¹; HF: ∼960 cm⁻¹) and total water stretching (H₂O_T: ∼3550 cm⁻¹) in natural glasses. The evolution of spectra topology was examined in (i) 33 anhydrous glasses produced by the re-melting of natural rock samples, which span a very large range of polymerisation degree (NBO/T from 0.00 to 1.16), (ii) 2 sets of synthetic anhydrous basaltic glasses with variable iron oxidation state (Fe³⁺/Fe_T from 0.05 to 0.87), and (iii) 6 sets of natural hydrous glasses (C_H2OT from 0.4 to 7.0 wt%) with NBO/T varying from 0.01 to 0.76.In the explored domain of water concentration, external calibration procedure based on the H₂O_T band height is matrix-independent but its accuracy relies on precise control of the focusing depth and beam energy on the sample. Matrix-dependence strongly affects the internal calibrations based on H₂O_T height scaled to that of LF or HF bands but its effect decreases from acid (low NBO/T, SM) to basic (high NBO/T, SM) glasses. Structural parameters such as NBO/T (non-bridging oxygen per tetrahedron) and SM (sum of structural modifiers) describe the matrix-dependence better than simple compositional parameters (e.g. SiO₂, Na₂O + K₂O). Iron oxidation state has only a minor influence on band topology in basalts and is thus not expected to significantly affect the Raman determinations of water in mafic (e.g. low SiO₂, iron-rich) glasses. Modelling the evolution of the relative band height with polymerisation degree allows us to propose a general equation to predict the dissolved water content in natural glasses:

     

High-sensitive measurement of uranium LIII-edge X-ray absorption near-edge structure (XANES) for the determination of the oxidation states of uranium in crustal materials

The uranium L_III-edge XANES spectra for natural rocks at the concentration range of 0.96–124 mg kg⁻¹ were measured using a log spiral bent crystal Laue analyzer (BCLA) combined with a multi-element Ge detector. It was found that the quality of the XANES spectra using the BCLA was greatly improved due to a reduction of interfering fluorescence from major components such as Rb and Sr. The ratio of signal to background intensities in the U L_III-edge XANES spectra increased by a factor of 2.9–17 with the use of the BCLA, which greatly enhanced the detection limit for the speciation of the oxidation states of U or the U(IV)/U(VI) ratio of natural samples. In addition, it was demonstrated that the fluorescence XANES method coupled with the BCLA enable determination of the speciation of U for various natural samples such as acidic igneous rocks, ferromanganese nodules, sediments, and some sedimentary rocks such as shale and limestone.     

Changing grading of soil: effect on critical states

Examples of situations are presented where the grading of a soil changes during its lifetime either by crushing of particles leading to an increase of fine material or by slow transport of fine particles with seepage leading to a decrease of fine material. Such grading changes influence the basic constitutive properties of the soil, in particular properties such as critical states which are dependent on the available range of densities of packing. Discrete element modelling is used to show the dependence of critical state conditions on grading and the way in which the particle assembly seeks out new critical state conditions as the grading changes.     

The effect of net-transfer reactions on the isotopic composition of minerals

To interpret correctly the isotopic composition of metmorphic rocks and minerals, the effect of nettransfer reactions must be quantitatively evaluated. Such evaluation requires a complete set of linearly independent, net-transfer reactions that fully describe the reacting system. The set of net-transfer reactions is then coupled with mass-balance equations for stable isotopes. Reaction spaces can be contoured with isopleths of °¹⁸O, °¹³C, and D of minerals which allows evaluation of the effect of different reactions and bulk compositions on the stable isotopic composition of minerals and rocks. Using this approach, we examined the effect of fractionation of isotopes due to net-transfer reactions at the biotite and second-sillimanite isograds in northern New England. Our analysis shows that the shift in °¹³C and °¹⁸O at an isograd depends strongly upon the overall net-transfer reaction at the isograd and the bulk composition of the rock. The use of model isograd reactions to determine isotopic shifts, therefore, can lead to serious errors in the interpretation of isotopic data. At the second-sillimanite isograd °¹⁸O _qtz (quartz), °¹⁸O _kspar (K feldsdpar), and °¹⁸O _wr (whole rock) decrease by 0.5, 1.0, and 0.8 per mil, respectively. Quantitative evaluation of the effect of fractionation of isotopes by net-transfer reactions shows that: (1) the relative changes in oxygen isotopes across the isograd could be caused by distillation of fluids during develatilization reactions; (2) the magnitude of the observed isotopic shifts often differs by a factor of 2 from the calculated shifts due to reaction progress alone. The difference between observed and calculated shifts is attributed to either, differences in bulk composition between individual rocks, or, to isotopic exchange between minerals after peak metamorphism. At the biotite isograd the shifts in carbon and oxygen isotope values are different from predicted shifts caused by net-transfer reactions alone. This discrepancy suggests that fluids infiltrated the rocks during the formation of the biotite isograd.     

高精度磁测预测砂岩铀矿氧化带前锋线

通过伊犁盆地南缘地面高精度磁测的开展、航空高精度磁测资料的应用以及钻孔岩心的磁化率测量,对层间氧化带型砂岩铀矿各地球化学分带的铁磁矿物分布特征、磁化率变化特征和磁场特征以及与铀矿化的关系进行了系统地研究,探讨了利用高精度磁测确定氧化—还原过渡带的位置的可行性、机理和方法,对砂岩型铀矿氧化带前锋线位置和铀成矿远景靶区的预测具有重要作用.     

The compressibility of silicate liquids containing Fe2O3 and the effect of composition,temperature, oxygen fugacity and pressure on their redox states

Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe₂O₃ is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na₂O−Al₂O₃ mixing. Partial-molar properties for FeO and Fe₂O₃ components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo₂ and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo₂ of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log₁₀ units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.     

The chemical composition of medieval wood ash glass from Central Europe

Medieval wood ash glass classified as 6 early medieval wood ash glasses, 17 wood ash glasses, 5 early wood ash lime glasses, 7 wood ash lime glasses and 9 mixed alkali glasses has been analyzed by microprobe and ICP-mass spectrometry on 61 elements. Their calcium oxide to potassium oxide ratio (CaO/K₂O) increases from early to late medieval glasses according to an increase of the proportion of twigs in the bulk amount of wood (logs plus twigs). Twigs because of their relatively large proportion of bark contain more calcium than wood logs. The ratio CaO/K₂O of the glasses from not yet evaluated excavations can be used for dating. The observation that the 25 minor elements Be, Sc, V, Cr, Ge, Y, Nb, REE (La to Lu), Ta, W and Bi occur in almost equal concentrations in the five subtypes of wood ash glass makes it highly probable that these elements were introduced into the starting mixtures of the glasses by means of quartz from quartz-rich sand with heavy minerals. The majorities of the wood ash glasses contain so-called europium anomalies within the group of rare-earth elements (REE). Their Eu concentrations normalized to those of the Continental Earth's Crust are lower than the normalized samarium and gadolinium concentrations. These Eu anomalies are apparently inherited from the granitic source of quartz in the upper Continental Earth's Crust. Soda ash and soda lime glass as the other major types in the history of glass contain no Eu anomaly. Therefore a different source of quartz has caused this important element constellation for these glass types. The elements K, Cu, Rb and S are physiologically separated from Ca, P, Mn, Sr and B during the growth of the wood and bark, respectively, in the trees. Different sources of the metals Cu and Co were used for colouring the glasses of our report.     

The effect of ionic interactions on the oxidation of metals in natural waters

The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation

$\text{-d in [Fe(II)]/dt = k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{] + k}{}_2\text{β}{}_2\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{]}{}^2$

where k₁ and k₂ are the pseudo first order rate constants, β₁ and β₂ are the hydrolysis constants for Fe(OH)⁺ and Fe(OH)⁰. The value of α_FE is the fraction of free Fe²⁺. The value of k₁ (2.0 ±0.5 min^?1) in water and seawater are similar within experimental error. The value of k₂ (1.2 × 10⁵ min^?1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model.For the oxidation of Cu(I) a rate equation of the form

$\text{?d ln [Cu(I)]/dt = k}{}_0\text{α}{}_{\mathrm{Cu}}\text{+ k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Cu}}\text{[Cl]}$

was found where k₀ (14.1 sec^?1) and k₁ (3.9 sec^?1) are the pseudo first order rate constants for the oxidation of Cu⁺ and CuCl⁰, β₁ is the formation constant for CuCl⁰ and α_Cu is the fraction of free Cu⁺. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.     

The oxidation states of cobalt and selected metals in Pacific ferromanganese nodules

A study of the oxidation states of metals in selected Pacific ferromanganese nodules by x-ray photoelectron spectroscopy (XPS) indicates the presence of Co(III), Pb(II), Pb(IV), Fe(III) and Ti(IV). These findings are based on measurements of core electron binding energies and an evaluation of the core electron shake-up satellite features.     

pH值对红土粒度成分影响的分形几何研究

红土是一种特殊土,其成分和结构决定了红土本身具有不同于一般粘性土的工程地质性质。红土中游离氧化铁的存在使土颗粒之间产生胶结,是土具有“假粉性”和“假砂性”特征的主要原因。研究发现,游离氧化铁含量和形态的改变,将直接影响红土颗粒的粒度分布。通过对不同pH值红土试样的颗粒成分进行测试,借助分形理论得到不同pH值红土粒度成分分维值。计算发现,不管是否在测试过程中采用分散剂,土粒度分维曲线上都存在两个无标度区。pH值的改变引起了土粒度分维的变化,随pH值的增大,土粒度分维值也变大,反应出土的细颗粒含量增加,土颗粒所形成的集合体越分散。土pH值的大小与粒度成分分维、游离氧化铁含量之间的内在联系,揭示出了红土中游离氧化铁对土颗粒胶结的本质。     

The effect of adsorbed lipid on pyrite oxidation under biotic conditions

The chemolithoautotrophic bacterium, Acidithiobacillus ferrooxidans, commonly occurs in acid mine drainage (AMD) environments where it is responsible for catalyzing the oxidation of pyrite and concomitant development of acidic conditions. This investigation reports on the growth of this bacterial species on the pyrite surface and in the aqueous phase at a pH close to 2 as well as the role of adsorbed lipid in preventing pyrite dissolution. Both acid washed pyrite and acid-washed pyrite coated with lipids were used as substrates in the studies. The choice of lipid, 1,2-bis(10,12-tricosadiynoyl)-sn-Glycero-3-Phosphocholine lipid (23:2 Diyne PC), a phosphocholine lipid, was based on earlier work that showed that this lipid inhibits the abiotic oxidation rate of pyrite. Atomic force microscopy showed that under the experimental conditions used in this study, the lipid formed ~4–20 nm layers on the mineral surface. Surface-bound lipid greatly suppresses the oxidation process catalyzed by A. ferrooxidans. This suppression continued for the duration of the experiments (25 days maximum). Analysis of the bacterial population on the pyrite surface and in solution over the course of the experiments suggested that the pyrite oxidation was dependent in large part on the fraction of bacteria bound to the pyrite surface.     

The effect of dissolved water on the oxidation state of iron in natural silicate liquids

Ferric-ferrous ratios have been measured in 22 experiments on three natural compositions equilibrated at known temperature (950°–1100° C) and oxygen fugacity, and at water-saturated conditions over a pressure range from 0.05 to 0.2 GPa. There does not appear to be any reaction between the melt and the capsule material that affects the redox state of the iron in the melt. An empirical expression for the anhydrous behavior of the redox state of iron in each of these compositions has also been determined at 1 bar as a function of temperature and oxygen fugacity. A direct comparison of the hydrous ferric-ferrous values with the calculated anhydrous values shows that the dissolution of water in a per-alkaline rhyolite, andesite, and an augite minette has no effect on the redox state of the iron in these melts. This result parallels the effect of water on sulfide speciation in basaltic melts, and confirms published results on experimental hydrous basalts.