Octahedral-site Fe2+ quadrupole splitting distributions from Mössbauer spectroscopy along the (OH, F)-annite join

We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe²⁺ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QS_HH2.55 mm/s for Fe²⁺O₄(OH)₂ octahedra (cis and trans not resolved), QS_HF 2.35 mm/s for Fe²⁺O₄(OH)F octahedra (cis and trans not resolved), QS_cFF2.15 mm/s for cis-Fe²⁺O₄F₂ octahedra, and QS_tFF 1.5 mm/s for trans-Fe²⁺O₄F₂ octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe²⁺O₅(OH) and Fe²⁺O₅F octahedra probably also contribute to the overall Fe²⁺ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe³⁺ contributions are seen and interpreted as being due mainly to Fe³⁺O₅OH and Fe³⁺O₅F octahedra, respectively. Tetrahedral Fe³⁺ is seen only in the OH-annite end-member and the total Fe³⁺ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China     

Density calculations for silicate liquids. I. Revised method for aluminosilicate compositions

Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature T_r, is given by $\text{V}{}_{\mathrm{r}}\text{= ∑X}{}_{\mathrm{i}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{+ X}{}_{\mathrm{A}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$, where the summation is taken over all oxide components except A1₂O₃, X stands for mole fraction, terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is the composition-dependent apparent partial molar volume of Al₂O₃. The thermal expansion coefficient of aluminosilicate liquids is given by $\text{α = ∑X}{}_{\mathrm{i}}\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}\text{+ X}{}_{\mathrm{A}}\text{}\text{?}\text{ga}{}_{\mathrm{A}}{}^{\mathrm{o}}$, where $\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}$ terms are constants independent of temperature and composition, and $\text{}\text{?}\text{ga}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is a composition-dependent term representing the effect of Al₂O₃ on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = V_rexp[α(T-T_r)], where T_r = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 $\text{cc}\text{mole}$ and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is discussed in terms of several possible interpretations of the structural role of Al³⁺ in aluminosilicate melts.     

Tellurides from Sunrise Dam gold deposit, Yilgarn Craton, Western Australia: a new occurrence of nagyágite

Summary The Cu–Fe–Au–Mo (W) deposits in southeastern Hubei are an important component of the Middle–Lower Yangtze River metallogenic belt. Molybdenite from the Fengshandong Cu- (Mo), Ruanjiawan W–Cu- (Mo), Qianjiawan Cu–Au, Tongshankou Cu–Mo and Tonglüshan Cu- (Fe) deposits yielded Re–Os ages of 144.0 ± 2.1 Ma, 143.6 ± 1.7 Ma, 137.7 ± 1.7 Ma, 142.3 ± 1.8–143.7 ± 1.8 Ma and 137.8 ± 1.7–138.1 ± 1.8 Ma, respectively. Phlogopite from the Tieshan Fe- (Cu) deposit yielded an Ar–Ar age of 140.9 ± 1.2 Ma. These data and other published isotopic ages (Re–Os molybdenite and Ar–Ar mica ages) for the Cu–Fe–Au–Mo (W) deposits in the Middle–Lower Yangtze River metallogenic belt show that Cu–Fe–Au–Mo (W) mineralisation in the Tongling, Anqing, Jiurui and Edong ore districts developed in a narrow time span between 135.5 and 144.9 Ma, reflecting an important regional metallogenic event. An integrated study of available petrological and geochronological data, together with relationships to magmatism and the regional geodynamic framework, indicate that the Cu–Fe–Au–Mo (W) mineralisation in the Middle–Lower Yangtze River belt occurred during a regime of lithospheric extension. This extension is probably related to Late Mesozoic processes of lower crustal delamination and lithospheric thinning in East China.     

Wet and Dry Basalt Magma Evolution at Torishima Volcano, Izu Bonin Arc, Japan: the Possible Role of Phengite in the Downgoing Slab

The arc-front volcanoes of Sumisu (31·5°N, 140°E)and Torishima (30·5°N, 140·3°E) in thecentral Izu–Bonin arc are similar in size and rise asrelatively isolated edifices from the seafloor. Together theyprovide valuable along-arc information about magma generationprocesses. The volcanoes have erupted low-K basalts originatingfrom both wet and dry parental basaltic magmas (low-Zr basaltsand high-Zr basalts, respectively). Based on models involvingfluid-immobile incompatible element ratios (La/Sm), the parentalbasalts appear to result from different degrees of partial meltingof the same source mantle (20% and 10% for wet and dry basaltmagmas, respectively). Assuming that the wet basalts containgreater abundances of slab-derived components than their drycounterparts, geochemical comparison of these two basalt typespermits the identification of the specific elements involvedin fluid transport from the subducting slab. Using an extensiveset of new geochemical data from Torishima, where the top ofthe downgoing slab is about 100 km deep, we find that Cs, Pb,and Sr are variably enriched in the low-Zr basalts, which cannotbe accounted for by fractional crystallization or by differencesin the degree of mantle melting. These elements are interpretedto be selectively concentrated in slab-derived metasomatic fluids.Variations in K, high field strength element and rare earthelement concentrations are readily explained by variations inthe degree of melting between the low- and high-Zr basalts;these elements are not contained in the slab-derived fluids.Rb and Ba exhibit variable behaviour in the low-Zr basalts,ranging from immobile, similar to K, to mildly enriched in somelow-Zr basalts. We suggest that the K-rich mica, phengite, playsan important role in determining the composition of fluids releasedfrom the downgoing slab. In arc-front settings, where slab depthis 100 km, phengite is stable, and the fluids released fromthe slab contain little K. In back-arc settings, however, wherethe slab is at 100–140 km depth, phengite is unstable,and K-rich fluids are released. We conclude that cross-arc variationsin the K content of arc basalts are probably related to differingcompositions of released fluids or melts rather than the widelyheld view that such variations are controlled by the degreeof partial melting. KEY WORDS: arc volcano; degrees of melting; mantle wedge; water; wet and dry basalts     

Controlling factors of the δ 11B-pH proxy and its research direction

Significant boron isotope fractionation occurs in nature (?70 ‰ to +75 ‰) due to the high geochemical reactivity of boron and the large relative mass difference between ¹⁰B and ¹¹B. Since the 1990s, reconstruction of ancient seawater pH using the isotopic composition of boron in bio-carbonates (δ ¹¹B_carb), and then calculation of the past pCO₂ have become important issues for the international isotope geochemistry community, and are called the δ ¹¹B-pH proxy. Although many achievements have been made by this proxy, various aspects of boron systematics require rigorous evaluation. Based on the previous researches, mechanism of boron isotope fractionation, variation of boron isotope (δ ¹¹B) in nature (especially in bio-carbonates) and controlling factors of the δ ¹¹B-pH proxy, such as the dissociation constant of B(OH)₃ in seawater (pK_a), the δ ¹¹B of seawater (δ ¹¹B_SW), the boron isotopic fractionation factor between B(OH) ₄ ^? and B(OH)₃ (α _4–3), and the incorporated species of boron into bio-carbonates, are reviewed in detail and the research directions of this proxy are proposed. Generally, the controversy about pK_a, δ ¹¹B_sw, and α _4–3 is relatively less, but whether boron incorporated into bio-carbonates only in the form of B(OH) ₄ ^? remains doubtful. In the future, it is required that the physicochemical processes that control boron incorporation into carbonates be rigorously characterized and that the related chemical and isotopic fractionation be quantified. It is also necessary and important to establish a “best-fit empirically equation” between δ ¹¹B_carb and pH of seawater based on the precipitation experiments of inorganic or culture experiments of corals or foraminifera. In addition, extended application of the δ ¹¹B-pH proxy to the earlier part of the Phanerozoic relying on the Brachiopods is worthy of studying. Like other geochemical indicators, there are limiting factors of δ ¹¹B; however, it remains a very powerful tool in the reconstruction of past seawater pH at present.     

Studies on concentration and direct reduction of the Ramim iron ore

Beneficiation and direct reduction of the Ramim iron ore was studied. Feed concentrates were obtained by gravity concentration of oolites followed by wet, high-intensity magnetic separation. Poor liberation prohibits physical concentration of goethite from oolites. These concentrates were directly reduced with different reductants at varying temperatures, followed by dry magnetic separation. Quality of concentrates depends on temperature, iron content in feed, type of coal, residence time, and composition of pellets. Conditions of optimum temperature range 1250–1275°C, unmixed pellets, high iron content in feed, dense high carbon reductant, and 15 min residence time resulted in grades and recoveries better than 90%. It is shown that segregation and growth of the metallic iron nuclii must be achieved in order to get superior yields.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

Volcanic facies and mineral chemistry of Tertiary volcanics in the northern part of the Eastern Pontides,northeast Turkey: implications for pre-eruptive crystallization conditions and magma chamber processes

Tertiary volcanics in the northern zone of the Eastern Pontides are characterized by subaerial and shallow-subaqueous facieses, and are divided into three volcanic suites: Eocene aged (1) basalt-trachybasalt-basaltic trachyandesite (BTB) and (2) trachyte-trachyandesite (TT), and Miocene aged (3) basanite-tephrite (BT) suites. Clinopyroxene is a common phase in all three volcanic suites, and has different compositions with Mg# varying from 0.57 to 0.91 in BTB suite and 0.57–0.84 in TT suite to 0.65–0.90 in BT suite. Feldspars in all suites generally exhibit wide range of compositions from sanidine to albite or anorthite and have weak normal and reverse compositional zoning. Olivines in BTB and BT suites have Fo_60–92. Hornblendes in BTB, TT and BT suites are commonly magnesio-hastingsite and rare pargasite in composition (Mg#: 0.67–0.90). Brown mica is mainly phlogopite with Mg# ranging from 0.56 to 0.92 in the BTB suite, 0.59–0.84 in the TT suite, and 0.75–0.93 in the BT suite. Analcime is present only in the BT suite rocks. Fe–Ti oxides in all suites are mainly composed of magnetite and titanomagnetite. Textural petrographic and mineral chemical data suggest that magmas had undergone hydrous and anhydrous crystallizations in deep-, mid-, and shallow-crustal magma chambers. Clinopyroxene thermobarometric calculations show that Eocene magma chambers were characterized by temperature ranging from 1,100 to 1,244 °C and pressure ranging from 1.84 to 5.39 kbar. Similarly, the Miocene magma chambers were characterized by temperature ranging from 1,119 to 1,146 °C and pressure ranging from 4.23 to 4.93 kbar. Hornblende thermobarometry, oxygen fugacity, and hygrometer reveal that the crystallization temperature of Eocene volcanics range from 956 to 959 °C at pressure ranging from 6.49 to 6.52 kbar. Eocene volcanics were characterized by water content ranging from 7.83 to 8.57 wt.% and oxygen fugacity of 10^?9.36 to 10^?9.46 (ΔNNO+2). Miocene volcanics had crystallization temperature ranging from 970 to 978 °C at pressure ranging from 8.70 to 9.00 kbar with water content ranging from 8.04 to 8.64 wt.% and oxygen fugacity ranging from 10^?8.75 to 10^?8.87 (ΔNNO+2). Brown mica thermobarometric data show that Eocene volcanics were characterized by relatively high oxygen fugacity varying from 10^-10.32 to 10^-12.37 (HM) at temperature ranging from 858 to 953 °C and pressure ranging from 1.08 to 1.41 kbar. Miocene volcanics were crystallized at highly oxidized conditions, which are characterized by high oxygen fugacity of 10^?12.0 (HM) at temperature of 875 °C and pressure of 2.09 kbar. The wide range of obtained temperatures for clinopyroxenes of the suites denotes that the equilibration of clinopyroxene crystals initiates from depth until close to the surface before magma eruption. The compositional variations, resorbed core and reverse zoning patterns in clinopyroxene phenocrysts, as well as variable pressures of crystallization, further indicate that the magmas that formed the suites were polybaric in origins and were composite products of more than one petrogenetic stage. The observed range of phenocryst assemblage and different compositional trends possibly originated from fractionation of magmas with different initial water contents under variable pressures of crystallization. The repeated occurrence of magmas from different suites during a single period of activity suggests that the magmatic system consists of several conduit systems and that magma reservoirs are dispersed at different levels of crustal magma chambers.     

Hydrogeochemical Precursors in Kamchatka (Russia) Related to the Strongest Earthquakes in 1988–1997

The Kamchatka peninsula, located in the far east of Russia, is a geologically active margin where the Pacific plate subducts beneath the North American and Eurasia plates. This area is characterised by frequent and strong seismic activity (magnitudes up to 8.5) and epicentres are generally distributed offshore along the eastern coast of the peninsula. For many years, hydrogeochemicals have been collected with a mean sampling frequency of three days in the form of the flow rate and the most common ions and gases in the groundwater of three deep wells in the southern area of the Kamchatka peninsula, where the capital city Petropavlovsk is located. Beginning in 1988, five earthquakes with M > 6.5 occurred in this area. These earthquakes were powerful enough to be considered as potential precursor sources in the sense that the stresses and strains building up before them might be expected to cause precursory activity. In order to reveal any possible precursors of these earthquakes, we analysed the hydrogeochemical data collected. We considered any signal having an amplitude three times the standard deviation to be an irregularity and we defined as an anomaly the existence of an irregularity occurring simultaneously in more than one parameter at each well. Then, on the basis of the worldwide past results and the time recurrence of the quoted earthquakes, we chose 158 days as the maximum temporal window between a possible anomaly and the subsequent earthquake. We identified some premonitory anomalies in hydrogeochemical parameters at different wells. On the basis of these results some earthquake forecasting criteria in southern Kamchatka may be tentatively formulated     

Formation of Carbon and Hydrogen Species in Magmas at Low Oxygen Fugacity

Studies of iron-bearing silicate melt (ferrobasalt) + iron metallicphase + graphite + hydrogen equilibria show that carbon andhydrogen solubilities in melts are important for the evolutionof the upper mantle. In a series of experiments conducted at3·7 GPa and 1520–1600°C, we have characterizedthe nature (oxidized vs reduced) and quantified the abundancesof C- and H-compounds dissolved in iron-bearing silicate melts.Experiments were carried out in an anvil-with-hole apparatuspermitting the achievement of equal chemical potentials of H₂in the inner Pt capsule and outer furnace assembly. The fO₂for silicate melt–iron equilibrium was 2·32 ±0·04 log units below iron–wüstite (IW). Theferrobasalt used as starting material experienced a reductionof its iron oxides and silicate network. The counterpart wasa liberation of oxygen reacting with the hydrogen entering thecapsule. The amount of H₂O dissolved in the glasses was measuredby ion microprobe and by step-heating and was found to be between1 and 2 wt %. The dissolved carbon content was found to be 1600ppm C by step-heating. The speciation of C and H componentswas determined by IR and Raman spectroscopy. It was establishedthat the main part of the liberated oxygen was used to formOH^– and to a much lesser extent H₂O, and only traces ofH₂, CO₂ and