Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS

The distribution of Fe atoms within the octahedral sheet of a series of trioctahedral micas has been investigated by polarized Fe K-edge EXAFS spectroscopy. Single crystals have been oriented in the X-ray beam with the layer plane at 35° with respect to the electric field vector. At this “magic angle”, contributions to the EXAFS spectrum of nearest cation shells are equal to those recorded on a completely disoriented powder. The average number of Fe and Mg cations surrounding each Fe atom has been determined and compared with those deduced from NMR spectra. It is shown that the distribution of Fe atoms is not random, the deviation from this distribution depending on the fluorine content. The agreement between these independent results proves the reliability of the structural information deduced from EXAFS and NMR spectra as well as the usefulness of these two methods in analyzing the local distribution of cations in minerals.     

Spectroscopic standard for tetrahedrally coordinated ferric iron: γ LiAlO2:Fe3+

γ LiAlO₂ doped with Fe³⁺ in the tetrahedral site has been examined by extended X-ray absorption fine structure (EXAFS) analysis, and Mössbauer and optical spectroscopy. The isomer shift (IS) is ?0.026 mm/s (Fe-Pd); the quadrupole splitting (QS) is 0.62 mm/s. Anisotropic optical absorption is prominent at ～391, 452, and 463 nm. The K-edge absorption spectrum shows a prominent absorption near 7,113 ev typical of tetrahedrally coordinated Fe³⁺.     

Polarized EXAFS of biotite and chlorite

Polarized Fe K-edge EXAFS spectra of biotite and chlorite monocrystals have been recorded using the Synchrotron radiation at LURE, Orsay. The anisotropic contribution of the nearest cation shell is clearly brought to evidence. In the limit case in which the electric field vector would be disposed normal to the layer plane, the contribution of cations belonging to octahedral sheets would not be sampled. At this orientation, the Fe-(Si, Al) contribution is selected and it is then possible by extrapolation of spectra taken at lower angles to extract phase and amplitude functions associated with this atomic pair. Two applications of this experiment are presented, (i) In chlorite, the amplitude of the Fe-(Si, Al) contribution is directly proportional to the distribution of Fe atoms between the TOT layer and the interlayer. It is found that about 25 percent of the iron is located in the interlayer. (ii) In the biotite structure, the contribution of the (Si, Al) shell is almost constant for a wide range of Fe-containing phyllosilicates and can be subtracted from their EXAFS spectrum. Such an operation will permit a more accurate analysis of the reality of solid solutions.     

Bonding of methyl mercury to reduced sulfur groups in soil and stream organic matter as determined by x-ray absorption spectroscopy and binding affinity studies

We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH₃Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-S_RED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-S_RED varied between 27% and 64% of total S in our samples. Hg L_III-edge EXAFS analysis were determined on samples added CH₃Hg (II) to yield CH₃Hg (II)/Org-S_RED ratios in the range 0.01-1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 Å and to one S atom at an average distance of 2.34 ± 0.03 Å, in the first coordination shell. At calculated CH₃Hg(II)/Org-S_RED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH₃Hg⁺, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 Å. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH₃Hg⁺, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH₃Hg⁺ by halide ions was used to determine the average binding strength of native concentrations of CH₃Hg (II) in the OS sample. Using data for Org-S_RED, calculated surface complexation constants were in the range from 10^16.3 to 10^16.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K₁) for the binding of methyl mercury to thiol groups in well-defined organic compounds.     

Insights into oxygen-cation bonding in fresnoite-type structures from O <Emphasis Type="Italic">K</Emphasis>- and Ti <Emphasis Type="Italic">L</Emphasis><Subscript>23</Subscript>-electron energy-loss spectra and ab initio calculations of the electronic structure

O K- and Ti L₂₃-core-loss spectra of fresnoite Ba₂TiSi₂O₈ (BTS) and Sr₂TiSi₂O₈ (STS), which is isotypic to BTS, have been measured by electron energy-loss spectroscopy (EELS). The energy-loss near-edge structures (ELNES) of the O K edge have been identified on the basis of theoretical simulations and interpretations of the X-ray absorption near-edge structures (XANES), which have been modelled in the framework of self-consistent full multiple-scattering (FMS) theory using FEFF8. Herewith, the K-absorption spectra of oxygen (E) and the local partial electron density of states (DOS) of all atoms have been calculated. For BTS, the observed spectral features in the O K-edge spectra are interpreted in terms of mixing between the central O p and neighbouring Ba 5d and 4f, Si 3p and 3d, and Ti 3d orbitals. The observed differences in the O K-edge spectra for STS and BTS can mainly be attributed to three properties: (1) The lack of high local partial Sr unoccupied DOS with 4f symmetry near the Fermi level compared to the high Ba 4f unoccupied DOS results in differences of overlapping O 2p – cation orbitals. (2) The differences in the ionic radii of Sr and Ba result in a larger unit cell for BTS and, thus, in larger oxygen-cation bonding distances. (3) In comparison to STS, the strength of the incommensurate 2-D structural modulation is significantly weaker in BTS, i.e. distortions of coordination polyhedra occur to a much lesser extent. All these effects alter the oxygen-cation hybridization and, hence, result in a variation of the O 1s p transition and consequently of the O K-edge spectral shape. The observed peak broadening in Ti L₂₃ ELNES of STS compared to BTS is correlated with strong displacive modulations hosted in STS.     

硫脲络合-火焰原子吸收光谱法同时测定银精矿中的铜和银

在高氯酸-硫脲介质中用原子吸收光谱法同时测定地质及选冶样品中银和铜已有文献报道;但在王水-硫脲介质中存在铜对银的测定干扰.本文采用盐酸-氢氟酸-硝酸-高氯酸四酸溶矿,王水提取、硫脲络合,用火焰原子吸收光谱法对银精矿中铜、银进行连续测定.通过筛选不同的样品消解方法,试验了硫脲介质浓度的影响,对共存元素的干扰进行消除.结果表明:四酸溶矿效果最好;通过加入过量的硫脲并控制其浓度在20 g/L以内,使溶液中银的白色沉淀与硫脲生成可溶的Ag[SC(NH2)2]3+配离子,消除了铜对银测定的干扰.该方法用于样品分析,相对标准偏差RSD(n =6)铜为1.20％～2.11％,银为0.61％ ～1.18％;加标回收率铜为96.5％ ～ 107.0％,银为97.3％ ～ 104.7％.测定值与碘量法、火试金法结果相符.本法具有简单、实用、成本低等优点,可满足银精矿选矿工艺生产的需要.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Structural relaxation in the MnCO3–CaCO3 solid solution: a Mn K-edge EXAFS study

Mn K-edge EXAFS spectroscopy of solid-solution samples encompassing the complete MnCO₃–CaCO₃ series shows that first-shell Mn–O distances deviate little from the 2.19-Å distance observed in pure MnCO₃. Very slight lengthening is observed only in the limiting case of dilute Mn(II) calcite solid solutions, where the Mn–O distance is 2.21 Å. The observed nearly complete structural relaxation and the composition independence of the Mn–O distance are consistent with the Pauling model behavior of solid solutions, and agree with previous studies showing a high degree of relaxation around hetero-sized substituents in the calcite structure. Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite. Observed distances from Mn to more distant neighbors show significant variation across the solid-solution series that resembles Vegard's law-type behavior but reflects averaging. The high degree of relaxation suggests modest enthalpies of mixing in the solution, consistent with calorimetric studies.     

Geochemical Characteristics and Zonation of Primary Halos of Pulang Porphyry Copper Deposit,Northwestern Yunnan Province,Southwestern China

The Pulang (普朗) porphyry copper deposit, located in the southern segment of the Yidun-Zhongdian (义敦-为中甸) island arc ore-forming belt of the Tethys-Himalaya ore-forming domain, is a recently discovered large copper deposit. Compared with the composition of granodiorite in China, the porphyry rocks in this area are enriched in W, Mo, Cu, Au, As, Sb, F, V, and Na2O (K1≥1.2). Compared with the composition of fresh porphyry rocks in this district, the mineralized rocks are enriched in Cn, Au, Ag, Mo, Pb, Zn, W, As, Sb, and K2O (K≥1.2). Some elements show clear anomalies, such as Zn, Ag, Cu, Au, W, and Mo, and can be regarded as pathfinders for prospecting new ore bodies in depth. It has been inferred from factor analysis that the Pulang porphyry copper deposit may have undergone the multiple stages of alteration and mineralization: (a) Cu-Au mineralization; (b) W-Mo mineralization; and (c) silicification and potassic metasomatism in the whole ore-forming process. A detailed zonation sequence of indicator elements is obtained using the variability index of indicator elements as follows: Zn→Ag→Cu→Au→W→Mo. According to this zonation, an index such as (Ag×Zn) D/(Mo×W) D can be constructed and regarded as a significant criterion for predicting the Cu potential at a particular depth.     

Preparation and characterization of antibacterial silver/vermiculites and silver/montmorillonites

The reason for the preparation and characterization of the novel antibacterial silver/vermiculites (Ag/V) together with the silver/montmorillonites (Ag/M) was that the information on the vermiculite structure change and stability of Ag/V in water as well as its effect on bacteria are sporadic. The vermiculite (V), (Si_3.02Al_0.98)^IV (Mg_2.27Al_0.12Ti_0.07)^VI O₁₀(OH)₂ Ca_0.09Na_0.21K_0.50 from West China and montmorillonite (M), (Si_3.96Al_0.04)^IV (Al_1.20Mg_0.42Ti_0.02)^VI O₁₀ (OH)₂Ca_0.15Na_0.14K_0.08 from Ivan?ice (Czech Republic), fraction <0.4 μm were the starting clay materials for sample preparation. The samples V1 and M1 were prepared via reaction of the V and M with the 0.01 mol L⁻¹ AgNO₃ aqueous solution. The samples V2 and M2 were treated with the aqueous solution of AgNO₃ for two times. The cation exchange and reduced metallic silver on M1 and V1 evoked the specific surface area (SSA) diminution, the mean particle-size diameter extension and appearance of micropores with radius (<0.4 nm). Repeated silver cation exchange in M2 and V2 reduced particle size, increased slightly SSA and micropores with radius of 0.4-0.5 nm. Samples Ag/V and Ag/M showed higher content of pores with radius 0.5-1.0 nm than original V and M. The Ag concentration was found higher in Ag/V than in Ag/M and higher in repeatedly treated samples: 0.9 wt.% Ag in V1, 1.4 wt.% Ag in V2, 0.6 wt.% Ag in M1 and 1.0 wt.% Ag in M2. Vermiculite structure consisting of the hydrated interstratified phases and the mica-like phase changed to the cation-one-zero layer hydrate interstratification structure in V1 and to the random of two-one layer hydrate interstratifications in V2. Infrared and Mössbauer spectroscopy revealed no changes in the structure of the clay minerals that could be related directly to the sorption and crystallization of silver. Transmission electron microscopy showed that the silver nanoparticles size distribution was much narrower for the samples Ag/M than for Ag/V. The mean size of the Ag particles was between 40 and 50 nm. Although the Ag nanoparticles did not adhere sufficiently at the clay minerals surface and migrated moderately into water, all samples under study were approved to be effective inhibitors of the bacterial growth persisting for the whole testing period of 6 days. Silver/vermiculite was antimicrobial more efficient against Klebsiella pneumoniae and Pseudomonas aeruginosa than silver/montmorillonite.     

Regularities in the impurity element content of minerals during hydrothermal ore formation

Many goldfields host scores of discovered gold ore occurrences with unclear prospects because of their insufficient geologic exploration. Since exploration is expensive, the occurrences should be first appraised by low-cost methods. Studying the typomorphic features of minerals from the goldfields of the Upper Yana–Kolyma region, we have established a relationship between the contents of isomorphic impurity elements (IIE) and the degree of solution supersaturation (DSS). Preliminary studies show that, based on this relationship, criteria can be developed for revealing “concealed” mineralogical–geochemical zonation and predicting mineralization to depth. The determining factor for the behavior of IIE, depending on the DSS, is their distribution coefficient (K) with respect to the host element. If K > 1, the content of these elements decreases with increasing DSS during ore deposition; if K < 1, it increases. When a solution contains IIE with K > 1 and K < 1, they behave according to their distribution coefficients. In other words, when the DSS increases during ore deposition, IIE with K > 1 will be typical of early mineral segregations, and IIE with K < 1, of late ones. If the crystallization front migrates, this must give rise to a vertical zonation in the content of both groups of elements. The content of elements with K > 1 will decrease upsection, and that of elements with K < 1 will increase (“concealed” mineralogical–geochemical zonation). In connection with this subject, the paper reports data using native gold as an example. The behavior of Ag, Sb, Hg, Cu, Ni, and Co is discussed depending on the depth of deposit formation from the paleosurface (deep-seated → shallow); in the vertical section of individual deposits; depending on mineralization stages; in the cross-section of individual crystals with a zonal structure. The behavior of Ag, Sb, and Hg has been shown to be opposite to that of Cu, Ni, and Co in all these aspects. With respect to Au, the first group of elements has K < 1, and the second one, K > 1. Copper and antimony are of particular interest. In the vertical section of individual deposits, the Cu content of gold increases with depth and the Sb content decreases. The Cu/Sb ratio can be used to estimate the erosional truncation level of deposits and thus predict their extension to depth. Examples of well-explored deposits are given.     

The tetrahedrite-freibergite series,with reference to the Mount Isa Pb-Zn-Ag orebody

Twenty eight electron microprobe analyses of freibergite from the Mount Isa (Queensland) Pb-Zn-Ag stratiform orebody, range in silver content from 18.4 to 42.5 wt. % Ag. These values significantly extend the tetrahedrite-freibergite series. The compositional range based on twenty-one complete analyses is indicated by the formula (Ag,Cu)_9.21–11.44(Fe,Zn)_1.59–2.31(Sb,As)_3.87–4.43S_13.0. As far as could be determined, Mount Isa freibergite is homogeneous and no marked compositional changes were detected either across individual grains, or in different grains of the same electron microprobe sample. The linear, atom for atom, replacement of copper by silver reported for lower silver bearing tetrahedrites continues in Mount Isa freibergite. A maximum silver content of about 51 wt. % Ag is predicted. X-ray investigations indicate however that in contrast to the structural expansion with increasing silver content reported for argentian tetrahedrite, Mount Isa freibergite contracts with increase in silver. The extrapolated lattice parameter for the theoretical freibergite (Ag₁₀(Fe,Zn)₂Sb₄S₁₃) end member is of the same order as tetrahedrite.     

Pressure-induced coordination change of Ti in silicate glass: a XANES study

The effect of pressure on titanium coordination in glasses, with composition K₂TiSi₄O₁₁, quenched isobarically from liquids equilibrated at high pressure (5, 10, 15, 20, 25, 30 kbar respectively) and T=1600° C has been investigated by X-ray absorption spectroscopy (XAS). The XANES spectra collected at the Ti K-edge clearly show a variation with pressure that is related to changes in the geometrical environment around the Ti atoms. By comparison with spectra of standard materials, the XANES spectra of the glasses suggest a relatively low average coordination number (near 5) in samples quenched at low pressure and a higher coordination number (near 6) in samples quenched from the highest pressure. The combination of XANES data with density and compressibility measurements supports the idea that a mixture of 6- and lower coordinated (4- and/ or 5-coordinated) Ti geometries are present in the 1 bar glass, and an increasing proportion of 6-coordinated Ti occurs in the glasses synthesized at progressively higher pressures.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

Core level electron energy-loss spectra of minerals: pre-edge fine structures at the oxygen K-edge

In a recent paper entitled “Water in minerals detectable by electron energy-loss spectroscopy EELS” by R. Wirth, it has been claimed that OH^–- and H₂O-bearing minerals exhibit a characteristic peak in the ELNES spectra at about 528 eV prior to the onset of the O K-edge at 532 eV, which could be used for (semi-)quantitative determination of water- or OH-contents on a nanometer scale. It is shown here by parallel electron energy-loss spectroscopy (PEELS) recorded in a transmission electron microscope (TEM) that O K-pre-edge peaks with very high intensities may also exist in water-free compounds and minerals, in particular when they contain transition metals. These spectral features arise from covalent mixing of the metal and oxygen states, which introduces oxygen p character in unoccupied states of mainly metal character. The point is illustrated by the comparison of hematite (α-Fe₂O₃) and lepidocrocite (γ-FeOOH) O K-edge PEELS spectra which exhibit similar intensities of the pre-edge peak, despite of their grossly different OH^– contents. As a consequence, the general validity of the method proposed by Wirth is questioned. Received: 4 December 1997 / Revised, accepted: 22 April 1998     

A cervelleite-like mineral and other Ag-Cu-Te-S minerals [Ag2CuTeS and (Ag,Cu)2TeS] in gold-bearing veins in metamorphic rocks of the Cycladic Blueschist Unit, Kallianou, Evia Island, Greece

A cervelleite-like mineral, two unnamed silver sulfotellurides in the system Ag-Cu-Te-S [Ag₂CuTeS, (Ag,Cu)₂TeS], Te-rich polybasite and cadmian tetrahedrite occur in gold-bearing quartz veins in metapelites and faults within brecciated marbles of the Cycladic Blueschist Unit in the Kallianou area (southern Evia Island, Greece). The quartz veins and faults are discordant to syn-metamorphic structures and formed during ductile to brittle deformation in the final stages of exhumation of the Styra Nappe extrusion wedge (~21?Ma). Te-rich polybasite (up to 7.4 wt. % Te), cadmian tetrahedrite (up to 12.4 wt. % Cd), together with electrum (23?C54 wt. % Ag) and the sulfotellurides, are the main silver carriers in the mineralization. The two unnamed sulfotellurides, Ag₂CuTeS and (Ag,Cu)₂TeS are believed to be new quaternary minerals in the system Ag-Cu-Te-S. These minerals and the cervelleite-like phase could have exsolved from galena during cooling (below 200°C). Initial temperatures for the formation of the sulfotellurides, in the form of hessite-intermediate solid solution, at Kallianou may be up to 300°C under logfS₂ values between?~ ?11.5 to ?8.3, and logfTe₂ from?~ ?14.8 to ?7.8. The values of logfTe₂ and logfS₂ during re-equilibration (at ~200°C) were constrained to ?19.5 to ?15.2 and to ?15.8 to ?11.5 respectively.     

Use of L-edge X-ray absorption spectroscopy to characterize multiple valence states of 3d transition metals; a new probe for mineralogical and geochemical research

2p (L _2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3d ⁿ → 2p ⁵ 3d ⁿ⁺¹ transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu₃ VS₄) indicates the presence of both Cu⁺ and Cu²⁺; the V L-edge spectrum of the same sample shows that both V²⁺ and V⁵⁺ are present. Spectral simulations representing mixtures of Fe d ⁵ and Fe d ⁶ states are used to quantify Fe³⁺/∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2p XAS in a dilute system, the Fe L-edge spectrum of amethyst (α-SiO₂: Fe) has been recorded; this spectrum shows that ～68% of the Fe in amethyst is Fe²⁺, and ～32% is Fe³⁺. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe⁴⁺, there is no indication in the L-edge spectrum for Fe⁴⁺ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.     

Impact of amide–amide hydrogen bonding on the stability of two nicotinamide complexes of silver(I)

The nicotinamide (pyridine-3-carboxamide, nia) complexes of silver(I), [Ag(nia)₂(NO₃)]·H₂O (1), [Ag(nia)₂(NO₃)] (2), and {K[Ag(nia)₂](NO₃)₂} _n (3), were prepared and characterised by IR spectroscopy and TG/DTA thermal methods. The solid state structures of 2 and 3 were determined by single-crystal X-ray diffraction analysis. In both complexes two nicotinamide ligands are coordinated to silver(I) through the nitrogen atom of the pyridine ring in a near-linear fashion. In 2, additional coordination by two oxygen atoms of one nitrate group leads to the distorted tetrahedral coordination environment of silver(I). In 3, nitrate ions bridge potassium cations giving rise to a 2D coordination network which is further stabilised by cross-bridging of each two potassium atoms in [1 0 0] direction by complex cations, [Ag(nia)₂]⁺. Despite different aggregation of 2 and 3 in the solid state, both complexes demonstrate quite similar thermal stability. The amide self-complementary hydrogen bonds appear to be the main driving force for establishing the crystal structures of both 2 and 3.     

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si−O bond distances, coordination numbers and Debye-Waller factors). The mean Si−O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R≈0.172 nm and N≈5) to R≈0.167 nm and N≈4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced. Received: 18 December 1996 / Revised, accepted: 20 June 1997     

Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength (I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.