High-pressure behaviour of germanate olivines studied by X-ray diffraction and X-ray absorption spectroscopy

Germanate olivines Mg₂GeO₄, Ca₂GeO₄ and CaMgGeO₄ have been studied by high-pressure X-ray Diffraction and high-pressure X-ray Absorption Spectroscopy. The three compounds were compressed, in the 0–30 GPa pressure range, at room temperature in a diamond-anvil cell, silicon oil being used as the pressure transmitting medium. Values of K₀ are 166 ± 15, 117 ± 15 and 152 ± 14 GPa for Mg₂GeO₄, Ca₂GeO₄ and CaMgGeO₄ respectively. These olivines all exhibit compression anisotropy, the a axis being the least compressible. Crystal to crystal phase transitions have been observed in Mg₂GeO₄ and Ca₂GeO₄ above 12 GPa and 6 Gpa respectively. The nature of these structural changes remains unclear yet. The onset of amorphization has been observed in Mg₂GeO₄ and Ca₂GeO₄ at pressures above about 22 and 11 GPa respectively. These phase transitions and amorphization processes do not involve any detectable increase in the coordination number of germanium atoms. At higher pressure (P >23 GPa), we report the onset of a transition from a phase with fourfold coordinated germanium to a phase with higher germanium coordination number in CaMgGeO₄.     

The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities (fO₂) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO₂ < −9) or oxidised (log fO₂ > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S²⁻. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV.The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO₄²⁻. Sulfite (SO₃²⁻) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S⁶⁺). S⁴⁺ does, however, occur unambiguously with S⁶⁺ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO₄ at 4-16 kbar, and when buffered with Re/ReO₂ at 10 kbar. Solubility of S⁴⁺ thus requires partial pressures of SO₂ considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO₂s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S²⁻ and S⁶⁺ were found to coexist in some samples that were not in equilibrium with the imposed fO₂.The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S²⁻, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S²⁻ + 8Fe³⁺ = S⁶⁺ + 8Fe²⁺, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S²⁻ and S⁶⁺ are frequently found together despite the very limited fO₂ range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.     

电感耦合等离子体发射光谱法测定高铁三水铝土矿中的主量和次量元素

采用电感耦合等离子体发射光谱法,同时测定高铁三水铝土矿中的Si、Fe、Al、Ti、Mn、V、As、P等元素。对影响其光谱测量的各种因素进行了较为详细的研究,确定了最佳的试验测定条件。结果表明,该方法的检出限为0.0012-0.061μg/mL,回收率为95.4%-107.4%,主量元素相对标准偏差在1%-3%之间,次量元素相对标准偏差在2%-6%之间。该方法准确、快速、简便,应用于高铁三水铝土矿的测定,结果令人满意。     

The distribution of some trace elements in iron meteorites,as determined by neutron activation

The ten trace elements germanium, arsenic, antimony, copper, chromium molybdenum, silver, indium, zinc and palladium have been determined in sixty-seven different meteorites, using neutron activation and radiochemical separations. In addition the meteorites have been analysed for gallium using either neutron activation or colorimetric methods. The sulphur content of twenty-five of the meteorites has also been measured, using an evolution and colorimetric method. The meteorites analysed consist of a reasonably representative selection of all the structural types of irons.The distribution of the determined trace elements is discussed, in relation to the structural classifications of the iron meteorites. It is shown that a number of meteorites belonging to specific structural classes have the same or closely similar trace element composition. Thus, the following five groups can be specified: seven hexahedrites, three coarsest octahedrites, seven coarse octahedrites, twelve medium octahedrites and six fine octahedrites. Particular attention is paid to the behaviour of germanium and gallium following the widely accepted division of iron meteorites into four distinct GaGe “quantized” groups.It is also shown that arsenic, antimony, silver, indium and zinc are generally concentrated in the coarse and coarsest octahedrite groups, compared with the remaining structural groups. In the case of indium this behaviour is observed even at the 0·0005–0·01 ppm levels. It is also seen that the distribution of zinc does not appear to be related to that of sulphur.Finally, the five structural groups are discussed in relation to the evolution of iron meteorites, and to possible correlations with cosmic-ray exposure ages.     

Quantitative microautoradiography by X-ray emission micro-analysis

Silver concentration in developed photographic emulsions exposed by β-emission may be measured on spots with a minimum diameter of about 10μm using an electron microprobe or a scanning electron microscope. Silver concentration is directly proportional to the integrated flux of β-particles bombarding the emulsion. Thus analysis for silver provides a method for quantitative microautoradiography which is comparable in accuracy and precision to other available methods and which can be performed on readily available equipment.     

Selected elements in major minerals from bituminous coal as determined by INAA: implications for removing environmentally sensitive elements from coal

The four most abundant minerals generally found in Euramerican bituminous coals are quartz, kaolinite, illite and pyrite. These four minerals were isolated by density separation and handpicking from bituminous coal samples collected in the Ruhr Basin, Germany and the Appalachian basin, U.S.A. Trace-element concentrations of relatively pure ( 99⁺%) separates of major minerals from these coals were determined directly by using instrumental neutron activation analysis (INAA). As expected, quartz contributes little to the trace-element mass balance. Illite generally has higher trace-element concentrations than kaolinite, but, for the concentrates analyzed in this study, Hf, Ta, W, Th and U are in lower concentrations in illite than in kaolinite. Pyrite has higher concentrations of chalcophile elements (e.g., As and Se) and is considerably lower in lithophile elements as compared to kaolinite and illite. Our study provides a direct and sensitive method of determining trace-element relationships with minerals in coal.Mass-balance calculations suggest that the trace-element content of coal can be explained mainly by three major minerals: pyrite, kaolinite and illite. This conclusion indicates that the size and textural relationships of these major coal minerals may be a more important consideration as to whether coal cleaning can effectively remove the most environmentally sensitive trace elements in coal than what trace minerals are present.     

The determination of trace elements in whole coal by rhodium tube X-ray fluorescence spectrometry: a rock-based synthetic coal calibration

A method is presented for the determination of 15 trace and minor elements (Fe, Ti, V, Cr, Mn, Ni, Cu, Zn, Pb, Sr, Rb, Ba, Zr, Y, Nb) in whole coal, by X-ray fluorescence spectrometry. A Rhanode X-ray tube is used and matrix corrections are derived from the intensity of the rhodium Kα Compton scattered tube line. The calibration is based on synthetic coals made from mixtures of standard rocks with graphite and cellulose, emulating the range of compositions likely to be encountered in bituminous coals. Robust pellets are made from 9 g of coal blended with a powdered binder. Results are presented for a number of standard coals.     

用X射线荧光光谱法测定Cl、S等31个元素

采用硼酸镶边垫底的粉末样品压片制样,用ARL ADVANT′XP＋型X射线荧光光谱仪对土壤和水系沉积物样品中Na、Mg、Al、Si、P、S、Cl等31个组分进行测定。重点研究了Cl和S等元素的测定条件、痕量元素的背景选择和谱线重叠校正问题。使用经验系数法和康普敦散射作内标校正基体效应。经标准物质校验,结果与标准值吻合。方法的检出限、精密度和准确度能满足多目标地球化学调查样品的分析要求。     

Proton-induced X-ray emission measurements of trace elements in water samples collected from an Indiana coal mining locality

A new method of simultaneous multi-elemental analysis, Proton Induced X-ray Emission (PIXE), was used to detect trace elements in waters associated with a coal strip-mining operation in southern Indiana. Stream, pond, and ground water samples were collected and analyzed monthly from, or near, Sulphur Creek in Sullivan County. The concentrations of 26 major and trace elements were determined in samples from eleven locations: K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Cd, Sn, Sb, I, Ba, Hg, Pb, and U. Elemental concentrations fluctuated considerably throughout the 13-month sampling period and also among sampling sites. Nickel, Zn, As, Cd, Mn, Fe, and Ca were highest in the upstream water which was most acidic (pH = 2.9–4.0) because of old unreclaimed mining operations. The highest values recorded were Ni = 1662 ppb, Zn = 4953 ppb, As = 26 ppb, Cd = 93 ppb, Mn = 5063 ppb, Fe = 63 ppm, and Ca = 325 ppm. The concentrations of these elements decreased downstream as the pH of Sulphur Creek increased which was likely due to the influence of the calcareous glacial till cover in the area and the recent mining activity which disturbed overburden containing a high percentage of calcareous materials. Lead, I, Br, and Ti values were highest (661 ppb, 86 ppb, 70 ppb, and 45 ppb, respectively) in the ground water from the coal seam (pH approximately 7). Other elements which were relatively high in the pH 7 waters closest to the current mining operations (pond, stream, and groundwater) included K (17 ppm), Sr (3408 ppb), Ba (173 ppb), As (14 ppb), Rb (16 ppb), Sn (14 ppb), and Cu (3840 ppb). The highest Cu concentration was recorded at the point where drainage water from the mine entered Sulphur Creek. Gallium, U, Hg, and Mo were found in low (< 13 ppb for Ga and Hg; < 205 ppb for Mo and U) concentrations and only in the ponds within the mine.     

Determination of some trace elements in geochemical standards by X-ray fluorescence

The following trace elements Cr, Cu, Nb, Ni, Pb, Rb, Sr, Y, Zn, and Zr were determined by X-ray fluorescence in some geochemical standards from Japan and France. The internal standard method was applied using a Philips PW 1410 X-ray spectrometer. The results were compared with the published data.     

The quiescent X-ray emission of X-ray novae and the coronal emission of late-type stars

The X-ray luminosities and spectra of F-M stars of luminosity classes IV–V are analyzed. In dwarfs with rotational velocities of about 100 km/s, such as the optical components of low-mass X-ray novae with black holes, hot plasma can be confined in coronal loops even in the presence of fairly weak magnetic fields. Thus, the soft X-ray emission of such systems in their quiescent state (to 10³¹ erg/s) could be associated with the coronal emission of the optical component/dwarf. Two systems studied with subgiants (V1033 Sco and V404 Cyg) have X-ray luminosities 2×10³²–2×10³³ erg/s. The X-ray emission of a solar-type corona cannot provide such luminosities. However, a transition to a non-solar corona is possible in rapidly rotating subgiants—a dynamical corona whose X-ray emission can be one to two orders of magnitude higher than observed for more slowly rotating late-type subgiants in the solar neighborhood. This suggests that the quiescent X-ray emission of these two systems is provided by emission from the corona of the subgiant optical component.     

The X-ray emission of magnetars

It is shown that cyclotron radiation by electrons near the surface of a neutron star with a magnetic field of ～10¹² G can easily provide the observed quiescent radiation of magnetars (Anomalous X-ray Pulsars and Soft Gamma-ray Repeaters). Pulsed emission is generated by the synchrotron mechanism at the periphery of the magnetosphere. Short-time-scale cataclysms on the neutron star could lead to flares of gamma-ray radiation with powers exceeding the power of the X-ray emission by a factor of 2γ², where γ is the Lorentz factor of the radiating particles. It is shown that an electron cyclotron line with an energy of roughly 1 MeV should be generated in the magnetar model. The detection of this line would serve as confirmation of the correctness of this model.     

Pressure and composition dependence of the electrical conductivity of iron-rich synthetic olivines to 200 kbar

The objectives of this study of olivines are, to calibrate the variation of electrical conductivity with pressure, up to 200 kbar in a diamond-anvil cell, and to determine how this is influenced by chemical composition. Experimentally, we have found that the variation of the electrical conductivity of three synthetic olivines containing 50, 75 and 100 mole percent of fayalite, is an exponential function of pressure P, closely represented at room temperature by:σ_xP=σ_x·exp ·(B _x·P) where x is the iron content of the olivine, σ _x the extrapolated value of conductivity at normal pressure and B _x the slope of the regression line in semi-logarithmic coordinates. It is thus possible to express the temperature dependence of conductivity through the Boltzmann relationship:σ_xPT= σ_αT· exp ·(-H*/RT)=σ_xT·exp ·[-(E*+PV _* ^x )/RT] where H* is the activation enthalpy, E* the activation energy and V _x ^* the activation volume. At constant temperature V _* ^x =B _x·RT and is approximately equal to 0,6 cm³/mole at 295 K. On the other hand, we have found that σ_xT is an exponential function of x and thus, B _x and of course V _x ^* are linear functions. The experimental procedure is described and the results discussed.     

Structure and specification of iron complexes in aqueous solutions determined by X-ray absorption spectroscopy

X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques, have been used to determine the structure and speciation of complexes for Fe²⁺ and Fe³⁺ chloride solutions at a variety of pH's, ionic strengths, and chloride/iron ratios.Low intensity K-edge transition features and analysis of modified pair correlation functions, derived from Fourier transformation of EXAFS spectra, show a regular octahedral coordination of Fe(II) by water molecules with a first-shell Fe²⁺-O bond distance, closely matching octahedral Fe²⁺-O bonds obtained from solid oxide model compounds. Solution Fe²⁺-O bond distances decrease with chloride/iron ratio, pH, and total FeCl₂ concentration. A slight intensification of the $\text{1s → 3d}$ transition with increasing FeCl₂ concentration suggests that chloride may begin to mix with water as a nearest-neighbor octahedral ligand. Fe³⁺ solutions show a pronounced increase in the $\text{1s → 3d}$ transition intensities between 1.0 M FeCl₃/7.8 M Cl^? to 1.0 M FeCl₃/ 15 M Cl^?, indicating a coordination change from octahedral to tetrahedral complexes. EXAFS analyses of these solutions show an increase in first-shell Fe³⁺-ligand distances despite this apparent reduction in coordination number. This can be best explained by a change from regular octahedral complexes of ferric iron (either Fe(H₂O)₆³⁺ or trans-Fe(H₂O)₄Cl₂ or both; Fe³⁺-O bond distances of 2.10 Å) to tetra-chloro complexes [Fe³⁺-Cl bond distances of 2.25 Å].     

Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

Partition of major and minor elements and equilibration in coexisting pyroxenes

The partition of Si, Al, Ti, Fe³⁺, Mg, Fe²⁺, Mn, Ca and Na between coexisting Ca-rich and Ca-poor pyroxenes from a wide variety of igneous and metamorphic rocks have been investigated systematically. Many of the distributions, and especially those for the partition of Ti, Mg, Fe²⁺, Mn and Na, indicate characteristic trends for pyroxenes from the various petrologic groups identified. The partition of Mg, Fe²⁺ and Mn correlate with inferred cooling rates, the partition co-efficients of pyroxenes from extruded and other quickly cooled rocks most nearly approaching unity. In contrast, the partition of Si and Ti and the absolute amounts of Al may be related to the physicochemical conditions prevailing during original crystallisation; Ti being particularly relatively enriched in Ca-rich pyroxenes of ultramafic associations. The trends of the compositions of the Ca-rich pyroxenes plotted in the pyroxene quadrilateral also correlate with cooling rates and comparison with the limited data available on the phase relations of coexisting pyroxenes suggests that sub-solidus chemical readjustments have occurred in both phases.     

Nitrogen microanalysis of glass inclusions in chondritic olivines by nuclear reaction

Measured were the abundance and distribution of nitrogen in glasses of glass inclusions in olivines of CV3, CO3, CR, C4, CH3, and LL chondritic meteorites by means of the ¹⁴N(d, p)¹⁵N nuclear reaction. Similar to what was observed with carbon, nitrogen is present in low concentrations (<20 ppm) in the structure of olivines but can by stored in variable amounts in glasses of glass inclusions. These primitive glasses, characterized by a Si-Al-Ca-rich composition, have highly variable nitrogen contents (30 to 1500 ppm) and highly inhomogeneous nitrogen distribution. Nitrogen contents are independent of the chemical composition of the glasses. The heterogeneous distribution is a common feature of all studied inclusions, as is evidenced by the variable contents of nitrogen in glass inclusions occurring in the same olivine grain. Nitrogen heterogeneity is suggestive of trapping of solid nitrogen carrier phases during formation of the constituents of chondrules. However, part of the originally trapped nitrogen appears to have been lost, possibly, by ulterior oxidation and subsequent transformation into volatile species.     

A study of synthetic and natural uranium oxides by X-ray photoelectron spectroscopy

Synthetic and natural uranium oxides UO _x (2≦×≦3) have been studied with X-ray photoelectron spectroscopy (XPS) to determine the phase composition and content of uranium ions in uraninites with a varying degree of oxidation. A strong hybridization of U_6p and O_2s orbitals has been found which permits a quantitative assessment of the U-O bond lengths. The values of such bonds in some substances have been found to be smaller than those in synthetic U(VI) oxide. The oxides U₂O₅ and U₃O₈ contain two types of uranium ions with a varying degree of oxidation.     

Assessment of major and minor elements in the Northumberland Coalfield,England

Thirty-three coal samples from the Northumberland Coalfield were investigated for thirty-six major and minor elements with a view to interpreting the mode of inorganic formation or association and their enrichment or depletion in relation to the published data for other coals.It was generally observed that the interelement correlation did not confirm a total dependency of the elements either on the inorganic or organic matter. However, the association of some of the minor elements tend to constitute a more satisfactory reference to the first phase of coalification (i.e. organo-metallic complexes). Principal components and factor analyses given for the elements confirm the mode of formation and provide the basis for suggesting three significant modes of concentration and association: (a) biological fixation; (b) mineral sorption; and (c) localized concentration.Comparison of the chemical data for this coal with published data appears to show similarity with the averages quoted for a “rich coal ash”.