Determination of the oxidation state of radiogenic Pb in natural zircon using X-ray absorption near-edge structure

We examined the L_III-edge Pb X-ray absorption near-edge structure (XANES) of three natural zircon samples with different amounts of radiation doses (1.9 × 10¹⁵ to 6.8 × 10¹⁵ α-decay events/mg). The results suggest that the oxidation state of radiogenic Pb in the zircon sample with the highest radiation dose is divalent. The XANES spectra of the two other samples with lower radiation doses suggest that radiogenic Pb(II) is present, and further that some Pb may be tetravalent. This is the first work on the determination of the oxidation state of radiogenic Pb in natural zircon using XANES.     

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.     

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

Estimation of Fe³⁺/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe³⁺/ΣFe ratio in silicates using Fe L_2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe³⁺/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe³⁺ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L₃-edge. This method allows mapping of Fe³⁺/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L₂ maximum for Fe³⁺, which is compared to the total integral intensity of the Fe L₂-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe³⁺/ΣFe ratios at the submicrometre scale in geological samples.     

An atomic level study of rhenium and radiogenic osmium in molybdenite

Local atomic structures of Re and radiogenic Os in molybdenite from the Onganja mine, Namibia, were examined using X-ray absorption fine structure (XAFS). Rhenium L_III-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) show that the oxidation state of Re, the interatomic distances between Re and the neighboring atoms, and the coordination number of Re to S are very similar to those of Mo in molybdenite. The results confirm that Re is present as Re(IV) in the Mo site in molybdenite.Measurement of L_III-edge XANES and EXAFS of a minor concentration (8.55 ppm) of radiogenic Os was accomplished in fluorescence mode by removing the interfering X-rays from Re and other elements using a crystal analyzer system. The data indicate that the oxidation state of radiogenic Os is Os(III) and Os(IV) and clearly different from Os(II) in natural sulfide minerals, such as OsS₂ (erlichmanite). XANES data also suggest that radiogenic Os does not form a secondary Os phase, such as OsS₂ or Os metal, in molybdenite.EXAFS of radiogenic Os was successfully simulated assuming that Os is present in the Mo site in molybdenite. The data are consistent with the XANES data; Os does not form Os phases in molybdenite. The EXAFS simulation showed that the interatomic distance between Os and S is 2.27 Å, which is 0.12 Å smaller than the distances of Re-S and Mo-S (2.39 Å) in molybdenite. Similar valences and ionic sizes of Re and Mo in molybdenite support the fact that large amounts of Re can be incorporated into the Mo site as has been observed in previous studies, whereas the different properties of Os compared to Mo and Re suggested here support much lower abundance of common Os in molybdenite. This makes molybdenite an ideal mineral for the Re-Os geochronometer as shown in many studies. However, the shorter distance between radiogenic Os and S compared to those of Re-S and Mo-S in molybdenite suggests that the radiogenic Os has a smaller ionic size than Re(IV) and Mo(IV). Furthermore, Os may be partly present as Os(III). Smaller and lower charge Os can diffuse faster than larger and higher charge Re in molybdenite at a given set of conditions. Hence, our study provides an atomic-level explanation for the high mobility of Os compared to Re, which has been suggested by earlier workers using laser ablation ICP-MS.     

Speciation of Cr and V within BOF steel slag reused in road constructions

Basic Oxygen Furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, which is partially reused as an aggregate for road constructions. It is essentially composed of calcium, silicon and iron but also contains potential toxic elements present as traces, like chromium (Cr, 2600 mg kg^− 1) and vanadium (V, 690 mg kg^− 1), which can be released. The linked results of chemical analysis, XRD and SEM-EDX enabled to identify the main mineral phases composing BOF slag and EDX micro-analyses indicated that V and Cr were associated to dicalciumferrite. A 47-days static leaching test at a laboratory scale with a controlled pH of 5 (pH_stat leaching test) showed that Cr was little released, while V was significantly released. Finally, X-ray absorption near-edge structure (XANES) spectra of 3 BOF slag samples were recorded (“raw”, leached 47 days at pH 5 and aged 2 years in a lysimeter). XANES spectra showed that Cr is present at octahedral coordination in the trivalent form, the less mobile and less toxic one, and that its speciation does not evolve during natural ageing and leaching at pH 5. They also indicated that V is predominantly present in the + 4 oxidation state and seems to become oxidized to the pentavalent form (the most toxic form) during natural ageing.     

Reduction of uranium(VI) under sulfate-reducing conditions in the presence of Fe(III)-(hydr)oxides

Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(III)-(hydr)oxide mineral was varied to give equivalent Fe(III)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 growth, along with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and, to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L₃-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)-(hydr)oxides are incompletely reduced.     

Heat-induced changes in speciation and extraction of uranium associated with sheet silicate minerals

Three samples of gouge from a U-mineralised fault, and two model samples, montmorillonite and muscovite, spiked with U, were heat-treated at a range of temperatures up to 1100 °C. Mineralogical changes were followed by thermal analysis, powder XRD and electron microscopy, and U extractability was measured by extraction with NH₄⁺. Changes in U speciation in the montmorillonite sample were followed using EXAFS spectroscopy. On heating, the minerals progressively dehydrate, dehydroxylate and eventually decompose to form new phases in a glassy matrix. In the case of montmorillonite (90% of U extractable from unheated material), U extractability increased slightly on heating to temperatures around 400 °C. Almost 50% of U was extracted from unheated muscovite, and this increased slightly by 450 °C. Above 500–600 °C, U extractability from both montmorillonite and muscovite declined to very low levels, reflecting dehydration of the uranyl ion and trapping in the new phases and glassy matrix. Uranium extractability from the natural samples was much lower in all cases (0.25–5% of the total before heating). In 2 samples, a significant increase in U extraction was associated with dehydroxylation at around 600 °C, followed by a decrease to very low levels at higher temperatures. Uranium extraction from the third natural sample, which contained X-ray amorphous U minerals, decreased steadily on heating. The results show that changes in U extraction can be related to structural and morphological changes in sheet silicate minerals. Heat treatment has potential to fix U but only if temperatures above 800 °C are reached. If only lower temperatures, in the range 400–600 °C, are used, then U extraction may increase.     

Uranyl acetate speciation in aqueous solutions—an XAS study between 25°C and 250°C

Speciation of uranium (VI) in acetate solutions between 25 and 250°C, at pH values between 1.8 and 3.8 and acetate/uranium (Ac/U) ratios of 0.5 to 100 has been investigated using uranium L_III-edge X-ray absorption spectroscopy. With increasing pH the UO₂(Ac)₂⁰ species becomes more important than UO₂(Ac)⁺ species, which is predominant below pH 2. It remains the dominant species as pH is further increased to 3.8 at an Ac/U ratio of 20. Decrease in U-O_eq bond distance and coordination number with increasing solution age indicates that steric/kinetic factors are important and that equilibrium is attained slowly in this system with initial acetate coordination to the uranyl ion being monodentate or pseudo-bridging before slow conversion to bidentate chelation. Acetate coordination to the uranyl ion appears to decrease as temperature is increased from room temperature to ∼100°C before increasing in solutions of Ac/U > 2. For solutions where Ac/U ≤ 2 at pH 2.1, there is no evidence for uranyl acetate speciation at low temperatures, but at elevated temperature bidentate uranyl-acetate ion-pairing is evident. The existence of the uranyl acetate species in the temperature range 200 to 240°C demonstrates the importance of including acetate and other organic ligands in models of uranium transport at elevated temperatures.     

Correlation between local structure and molar ratio of Au (III) complexes in aqueous solution: An XAS investigation

The local and geometrical structure around gold (III) e.g., Au³⁺ ions in aqueous solution with different OH⁻/Cl⁻ molar ratios, has been investigated by X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure (XANES) spectra of [AuCl_n(OH)_4−n]⁻ solutions have been calculated and the multiple-scattering spectral features have been attributed to Cl d-states, axial water molecules and the replacement of Cl⁻ ligands by OH⁻ ligands. A square–planar geometry for [AuCl_n(OH)_4−n]⁻ with two axial water molecules has been identified. Moreover, a spectral correlation between XANES features and the type of planar atoms has been identified. By extended X-ray absorption fine structure spectra (EXAFS), the planar Au bond distances in the solutions have also been determined, e.g., 2.28 Å for Au–Cl and 1.98 Å for Au–O, respectively. The same EXAFS analysis provides evidence that the peak at about 4.0 Å in solutions with the lowest OH⁻/Cl⁻ molar ratio arises from collinear Cl–Au–Cl multiple-scattering contributions. For the first time, a complete detailed reconstruction of the hydration structure of an Au ion at different pH values has been achieved.     

Petrology and geochemistry of Tertiary volcanic rocks from the İkizce (Ordu) area, NE Turkey: Implications for the evolution of the eastern Pontide paleo-magmatic arc

Tertiary volcanism in the İkizce region at the western edge of the eastern Pontides paleo-magmatic arc is represented by basaltic and andesitic rocks associated with sediments deposited in a shallow basin environment. The basaltic rocks contain plagioclase (An_58–80), olivine (Fo_82–84), clinopyroxene (Wo_44–48En_35–42Fs_7–17), hornblende (Mg# = 0.68–0.76) phenocrysts, and magnetite microcrysts, whereas the andesitic rocks include plagioclase (An_25–61), clinopyroxene (Wo_46–49En_38–43Fs_11–13), hornblende (Mg# = 0.48–0.81), biotite (Mg# = 0.48–0.60) phenocrysts, titanomagnetite, apatite, and zircon microcrysts.Geochemical data indicate magmatic evolution from tholeiitic-alkaline transitional to calc-alkaline characteristics with medium-K contents. The geochemical variation in the rocks can be explained by fractionation of common mineral phases such as clinopyroxene, olivine, hornblende, plagioclase, magnetite, and apatite. The trace elements’ distributions of the volcanic rocks show similarities to those of E-Type MORB, have a shape that is typical of rocks from subduction-related tectonic setting with enrichment in LILE and to a lesser extent in LREE, but depletion in HFSE. The rocks evolved from a parental magma derived from an enriched source formed by subduction induced metasomatism of basaltic rocks, the latter formed through clinopyroxene ± olivine controlled fractionation in a high level magma chamber. The andesitic rocks developed through hornblende ± plagioclase controlled fractionation in shallow level magma chamber(s).     

Determination of the uranium valence state in the brannerite structure using EELS, XPS, and EDX

In this study, the valence states of uranium in synthetic and natural brannerite samples were studied using a combination of transmission electron microscopy-electron energy loss spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) techniques. We used a set of five (UO₂, CaUO₄, SrCa₂UO₆, UTi₂O₆, and Y_0.5U_0.5Ti₂O₆) U standard samples, including two synthetic brannerites, to calibrate the EELS branching ratio, M₅/(M₄ +M₅), against the number of f electrons. The EELS data were collected at liquid nitrogen temperature in order to minimise the effects of electron beam reduction of U⁶⁺ and U⁵⁺. Test samples consisted of three additional synthetic brannerites (Th_0.7U_0.3Ti₂O₆, Ca_0.2U_0.8Ti₂O₆, and Th_0.55U_0.3Ca_0.15Ti₂O₆) and three natural brannerites from different localities. The natural brannerite samples are all completely amorphous, due to cumulative alpha decay events over geological time periods (24–508 Ma). Our U valence calibration results are in reasonable agreement with previous work, suggesting possibly a non-linear relationship between the branching ratio and the number of f electrons (and hence the average valence state) of U in solids. We found excellent agreement between the nominal valence states of U and the average valence states determined directly by EELS and estimated by EDX analysis (with assumptions regarding stoichiometry) in two of the three synthetic brannerite test samples. The average U oxidation states of the five synthetic brannerite samples, as derived from XPS analyses, are also in good agreement with those determined by other techniques. The average valence states of U in three amorphous (metamict) natural brannerite samples with alpha decay doses ranging from 3.6×10¹⁶ to 6.9×10¹⁷ /mg were found to be 4.4, 4.7, and 4.8, consistent with the presence of U⁵⁺ and/or U⁶⁺ as well as U⁴⁺ in these samples. These results are in general agreement with previous wet chemical analyses of natural brannerite. However, the average valence states inferred by SEM-EDX for two of the natural brannerite samples do not show satisfactory agreement with the EELS determined valence. This may be due to the occurrence of OH^– groups, cation vacancies, anion vacancies, or excess oxygen in the radiation-damaged structure of natural brannerite.     

Adsorption mechanisms of trivalent gold on iron- and aluminum-(oxy)hydroxides. Part 1: X-ray absorption and Raman scattering spectroscopic studies of Au(III) adsorbed on ferrihydrite, goethite, and boehmite

Gold adsorption products on powdered ferrihydrite, goethite, and boehmite samples, prepared by reacting Au(III)-Cl solutions ([Au] = 4.2 × 10⁻⁵-9.0 × 10⁻³ M; [Cl] = 0.017-0.6 M) with these adsorbents at pH values of 4 to 9 and Au adsorption densities ranging from 0.046 to 1.53 μmol/m² were characterized using Au-L_III XAFS spectroscopy. The solutions (before and after uptake) were investigated by Raman scattering to determine speciation and by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) to determine solution composition. We present an analysis of several effects that are observed in the Au L_III-edge XAFS spectra, including X-ray beam-induced photo-reduction, multi-electronic excitations, disorder effects, and multiple scattering, that would complicate interpretation of the spectra if not accounted for. A combination of methods (spectral deconvolution, principal component analysis, spectral inversion, and wavelet analysis) was used to identify and quantify these effects, to characterize the nature of mixed ligands around gold, and to distinguish between multiple-scattering features and features due to next-nearest neighbors in the XAFS spectra.Analysis of the Au-L_III XAFS spectra showed that Au(III) is present as square-planar Au(III)(O,Cl)₄ complexes in the aqueous solutions and on the surfaces of the Al/Fe-(oxy)hydroxide adsorption samples with dominantly O ligands at pH > 6 and mixed O/Cl ligands at lower pH values. The EXAFS-derived Au-O and Au-Cl distances are 2.00(2) and 2.28(2) Å, respectively, and the magnitudes of the Debye-Waller factors and third cumulants from anharmonic analyses indicate very little thermal or positional disorder around Au(III) in the adsorption samples. Iron second neighbors are present around Au in the Au(III)/ferrihydrite and Au(III)/goethite adsorption samples, with Au-Fe distances of 3.1(1) and 3.3(1) Å. In boehmite, two sets of Au-Al distances were detected at 3.0(1) and 3.2(1) Å. A reverse Monte Carlo study of the XAFS spectroscopic data suggests the presence of a continuum of edge-shared AuO₄-FeO₆ distances, which cannot be described correctly by a classical model of these data in which only a mean distance (although severely under-estimated) is derived.     

Arsenic and iron speciation in uranium mine tailings using X-ray absorption spectroscopy

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe³⁺–As⁵⁺ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As⁵⁺ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.     

Neoproterozoic hydrothermally altered basaltic rocks from Rajasthan, northwest India: Implications for late Precambrian tectonic evolution of the Aravalli Craton

The isolated volcano-sedimentary sequences of the Punagarh and Sindreth Groups occur along the western flank of the Delhi Fold Belt in northwest India, and include mafic rocks (pillow basalts and dolerite dykes) that are dominantly olivine tholeiites with minor quartz-normative and alkali basalts. Sindreth samples appear to have higher primary TiO₂ and P₂O₅ abundances relative to those from Punagarh. Both suites of mafic rocks show variable, but profound hydrothermal alteration effects, with loss on ignition (LOI) values up to 10.3 wt.%, and extensive secondary minerals including albite, sericite, chlorite and calcite. Despite this, there is excellent preservation of magmatic textures, but there has been extensive albitization of plagioclase phenocrysts, a hallmark of hydrothermal alteration processes in oceanic crust. Supporting evidence for such hydrothermal alteration comes from correlations of LOI abundances with CaO/Na₂O, and evidence for U mobility is apparent on diagrams of Nb/Th vs. Nb/U. Felsic volcanic rocks (rhyolite, dacite) interlayered with the Sindreth basalts yield U–Pb zircon ages (TIMS method) between 761 ± 16 and 767 ± 3 Ma, which we interpret as representing the time of primary magmatic activity. We infer that the volcano-sedimentary rocks of the Punagarh also formed at this time, on the basis of similarities in lithology, stratigraphy, field relations and geochemistry. Intermediate granitoid rocks yield older U–Pb ages of 800 ± 2 and 873 ± 3 Ma, which we correlate with the post-Delhi Supergroup Erinpura Granites. Taken together, the features of the Punagarh and Sindreth Groups are consistent with their formation in a back-arc basin setting. Their coevality with other magmatic systems in NW India (Malani Igneous Suite), the Seychelles and Madagascar, for which a continental arc setting has also been proposed, supports the notion of an extensive convergent margin in western Rodinia at 750–770 Ma.     

Molecular environment of iodine in naturally iodinated humic substances: Insight from X-ray absorption spectroscopy

The molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L₃-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparables to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d (I-C) of 2.01(4)-2.04(9) Å, which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)-2.07(6) Å), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)-2.16(2) Å). These results are in agreement with previous conclusions from X-ray photoelectron spectroscopy and from electrospray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study.     

Proximal provenance of the western Songpan–Ganzi turbidite complex (Late Triassic, eastern Tibetan plateau): Implications for the tectonic amalgamation of China

The Late Triassic Songpan–Ganzi turbidite complex on the eastern Tibetan plateau, which covers an area of ~ 2.2 × 10⁵ km², is one of the largest flysch turbiditic basins on Earth. It is juxtaposed with major Chinese continental blocks across several outstanding Tethyan sutures, and is critical to elucidating the tectonic amalgamation of China. However, the provenance of the turbidites remains the subject of intense debate. Detrital modes and heavy-mineral spectra of sandstone samples from three turbidite profiles in the western Songpan–Ganzi complex were determined in an attempt to elucidate their provenance and the type of tectonic setting in which they were deposited. Upper Triassic turbidites in the western Songpan–Ganzi complex have an overwhelming derivation from an orogen source, as shown by the average framework compositions of the sandstones (Q₅₇F₂₁L₂₂, Qm₅₂F₂₁Lt₂₇, Qp₂₃Lvm₀Lsm₇₇). The compositional and textural immaturity of the sandstones suggests limited transport and nearby sources. Both light and heavy mineral and lithic fractions indicate dominant metamorphic source rocks and subordinate ophiolitic and sedimentary source rocks. The occurrence of C-type garnet, omphacite, rutile, and Si-rutile, and the high-silica content of phengites reveal that the source rocks underwent ultrahigh-pressure conditions. Therefore, we advocate that the western Songpan–Ganzi Late Triassic turbidites were derived from nearby central Qiangtang Triassic collisional orogen sources, rather than distant Dabie–Qinling sources eroded after North China–South China collision, as previously proposed. The analogy of the Songpan–Ganzi turbidites to the Bengal–Indus fans is not favored. The central Qiangtang metamorphic belt is unlikely to have occurred as an early Mesozoic mélange underthrust from the Jinsa suture, and is more likely to have been an in situ Triassic ultrahigh-pressure orogen. Our provenance interpretation implies that the Paleotethys, represented by the present Jinsa and Kunlun sutures, was not yet closed when central Qiangtang was being exhumed to supply the sediments of the Songpan–Ganzi basin. This challenges the conventional model for sequential amalgamation of China during the Phanerozoic.     

Selective detection of Fe and Mn species at mineral surfaces in weathered granite by conversion electron yield X-ray absorption fine structure

A new method for the speciation of Fe and Mn at mineral surfaces is proposed using X-ray absorption fine structure in conversion electron yield mode (CEY-XAFS). This method generally reflects information on the species at the sub-μm scale from the particle surface due to the limited escape depth of the inelastic Auger electron. The surface sensitivity of this method was assessed by experiments on two samples of granite showing different degrees of weathering. The XANES spectra of the Fe-K and Mn-K edge clearly gave different information for CEY and fluorescence (FL) modes. These XANES spectra of Fe and Mn show a good fit upon application of least-squares fitting using ferrihydrite/MnO₂ and biotite as the end members. The XANES spectra collected by CEY mode provided more selective information on the secondary phases which are probably present at the mineral surfaces. In particular, CEY-XANES spectra of Mn indicated the presence of Mn oxide in unweathered granite despite a very small contribution of Mn oxide being indicated by FL-XANES and selective chemical-extraction analyses. Manganese oxide could not be detected by micro-beam XANES (beam size: 5 × 5 μm²) in unweathered granite, suggesting that Mn oxide thinly and ubiquitously coats mineral surface at a sub-μm scale. This information is important, since Mn oxide can be the host for various trace elements. CEY-XAFS can prove to be a powerful tool as a highly sensitive surface speciation method. Combination of CEY and FL-XAFS will help identify minor phases that form at mineral surfaces, but identification of Fe and Mn oxides at mineral surfaces is critical to understand the migration of trace elements in water-rock interaction.     

Uranium anomalies in paleo-aquifers near sandstone-type uranium deposits in the devonian catskill formation of Pennsylvania

Background values of U and Th in 371 clastic sedimentary rocks from the Catskill Formation correlate negatively with Si and positively with Al and most other major elements because of the low content of U and Th in quartz and the relative enrichment in clays, Fe oxides, and other fine-grained components. Background U also correlates closely with Th. Similar results are obtained from 100 samples from western Colorado near the Uravan mineral belt. Weak anomalies in U are much more easily recognized by study of residuals or deviations from regressions of U against Al or Th than in the raw data.At Penn Haven Junction near Jim Thorpe, Pa., roll-type uranium deposits similar to those in Wyoming are localized around an iron-stained paleo-aquifer of conglomeratic sandstone. Twenty-four rock samples from this paleo-aquifer contain 1–12 ppm U; eight of the samples contain less than 4 ppm U, the background level for shales of the area. Uranium residuals from regressions against Al or Th are clearly anomalous for all samples. Experiments on another group of samples suggest that readily extractable U (H₂O₂-acetic acid leach) would also show the paleo-aquifer to be anomalous.Anomalies of this type in paleo-aquifers should be useful in evaluation of drill holes, outcrops, and radiometric data in prospective districts, especially when paleo-aquifers are difficult to recognize visually. The anomalies also indicate that U is added to sandstones of the paleo-aquifer rather than leached out to form the ore bodies in reduced rocks at the margins of a geochemical cell.     

Geochemical signatures of Variscan eclogites from the Saxonian Erzgebirge, central Europe

From the abundant metre to km-sized eclogite bodies in the Variscan crystalline complex of the Saxonian Erzgebirge we have investigated 19 samples from the ultrahigh pressure area at the Saidenbach reservoir. Twenty-two samples were from the south-western Erzgebirge, and from occurrences located only some km away from the reservoir. These samples were analysed for major and trace elements using X-ray fluorescence (XRF) spectrometry and inductively coupled plasma mass spectrometry (ICP-MS).The non-Saidenbach eclogites (SiO₂=49–53 wt%) can be derived from N-mid-ocean ridge basalts (MORBs) partially transitional to P-MORBs (e.g., (Nb)_N: 3–36; (Sr)_N: 4–17; (La/Sm)_N<1.5 (in most instances <0.7) and (Sm/Yb)_N around 1.2). Eclogites from the Saidenbach reservoir (SiO₂=49–61 wt%) are characterised by (Nb)_N: 20–170; (Sr)_N: 9–43; (La/Sm)_N: 1.2–3.0; (Sm/Yb)_N: 1.4–8.8, and a clear negative Eu anomaly for the Si-rich samples, thus, being significantly different from the other investigated eclogites. These signatures point to protoliths related to within plate igneous rocks. However, we also discuss the possibilities of (1) protoliths related to a magmatic arc along an active continental margin and (2) the formation by melting of crustal material in the deep mantle and final crystallisation in the lowermost continental crust similar to the adjacent diamondiferous quartzofeldspathic rocks.Due to the specific geochemical signatures of eclogites in the Saidenbach area including other facts, this ultrahigh pressure region is believed to represent a section of lowermost crust not outcropping in other portions of the Saxonian Erzgebirge.     

The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air

Metal L_2,3, sulfur K and oxygen K near-edge X-ray absorption fine structure (NEXAFS) spectra for chalcopyrite, bornite, chalcocite, covellite, pyrrhotite and pyrite have been determined from single-piece natural mineral specimens in order to assess claims that chalcopyrite should be regarded as Cu^IIFe^IIS₂ rather than Cu^IFe^IIIS₂, and that copper oxide species are the principal initial oxidation products on chalcopyrite and bornite exposed to air. Spectra were obtained using both fluorescence and electron yields to obtain information representative of the bulk as well as the surface. Where appropriate, NEXAFS spectra have been interpreted by comparison with the densities of unfilled states and simulated spectra derived from ab initio calculations using primarily the FEFF8 code and to a lesser extent WIEN2k. Metal 2p and S 2p photoelectron spectra excited by monochromatised Al K_α X-rays were determined for each of the surfaces characterised by NEXAFS spectroscopy. The X-ray excited Cu LMM Auger spectrum was also determined for each copper-containing sulfide. FEFF8 calculations were able to simulate the experimental NEXAFS spectra quite well in most cases. For covellite and chalcocite, it was found that FEFF8 did not provide a good simulation of the Cu L₃-edge spectra, but WIEN2k simulations were in close agreement with the experimental spectra. Largely on the basis of these simulations, it was concluded that there was no convincing evidence for chalcopyrite to be represented as Cu^IIFe^IIS₂, and no strong argument for some of the Cu in either bornite or covellite to be regarded as Cu(II). The ab initio calculations for chalcopyrite and bornite indicated that the density of Cu d-states immediately above the Fermi level was sufficient to account for the Cu L₃-edge absorption spectrum, however these incompletely filled Cu d-states should not be interpreted as indicating some Cu(II) in the sulfide structure. It was also concluded that the X-ray absorption spectra were quite consistent with the initial oxidation products on chalcopyrite and bornite surfaces being iron oxide species, and inconsistent with the concomitant formation of copper-oxygen species.