Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer

The Al-in-hornblende barometer, which correlates Al^tot content of magmatic hornblende linearly with crystallization pressure of intrusion (Hammarstrom and Zen 1986), has been calibrated experimentally under water-saturated conditions at pressures of 2.5–13 kbar and temperatures of 700–655°C. Equilibration of the assemblage hornlende-biotite-plagioclase-orthoclasequartz-sphene-Fe-Ti-oxide-melt-vapor from a natural tonalite 15–20° above its wet solidus results in hornblende compositions which can be fit by the equation: P(±0.6 kbar) = –3.01 + 4.76 Al _hbl ^tot r ²=0.99, where Al^tot is the total Al content of hornblende in atoms per formula unit (apfu). Al^tot increase with pressure can be ascribed mainly to a tschermak-exchange ( ) accompanied by minor plagioclase-substitution ( ). This experimental calibration agrees well with empirical field calibrations, wherein pressures are estimated by contact-aureole barometry, confirming that contact-aureole pressures and pressures calculated by the Al-in-hornblende barometer are essentially identical. This calibration is also consistent with the previous experimental calibration by Johnson and Rutherford (1989b) which was accomplished at higher temperatures, stabilizing the required buffer assemblage by use of mixed H₂O-CO₂ fluids. The latter calibration yields higher Al^tot content in hornblendes at corresponding pressures, this can be ascribed to increased edenite-exchange ( ) at elevated temperatures. The comparison of both experimental calibrations shows the important influence of the fluid composition, which affects the solidus temperature, on equilibration of hornblende in the buffering phase assemblage.     

Clinoeulite (magnesian clinoferrosilite) in a eulysite of a metamorphosed iron formation in the vredefort structure,South Africa

A unique clinopyroxene (En₁₉Fs₇₈Wo₃), clinoeulite, space group P2₁/c, $${\text{(Fe}}_{{\text{1}}{\text{.48}}} {\text{Mg}}_{{\text{0}}{\text{.37}}} {\text{Mn}}_{{\text{0}}{\text{.08}}}^{{\text{2 + }}} {\text{Ca}}_{{\text{0}}{\text{.05}}} {\text{Al}}_{{\text{0}}{\text{.01}}} {\text{)}}_{{\text{1}}{\text{.99}}} {\text{ [Si}}_{{\text{2}}{\text{.01}}} {\text{O6],}}$$ contains sharp exsolution lamellae of ferroaugite (En₁₇Fs₄₃Wo₄₀) from which the former presence of a ferropigeonite near En₁₇Fs₇₀Wo₁₃ can be calculated. This two-pyroxene intergrowth is the main component of a eulysite containing also magnetite, olivine (Fo₉Fa₈₆Te₅), quartz, oligoclase-K feldspar inter-growth, and retrograde cummingtonite with about 76 % grunerite end member. The occurrence of this most unusual rock type in the center of the Vredefort structure is attributed to a period of high-temperature metamorphism (at least 800 °–850 °C) which was followed by hot deformation of the rock during the Vredefort event thus probably preventing the common formation of orthopyroxene through pigeonite exsolution and inversion upon cooling. After this tectonic deformation, the rock recrystallized within the low-temperature stability range of clinoeulite to yield fine annealing textures. Late-stage equilibria at temperatures well below 500 °C include the complete unmixing of a former high-temperature anorthoclase, a Mg/Fe redistribution in the clinoeulite and olivine and, with the introduction of water, the partial formation of cummingtonite through reaction of clinoeulite, olivine, and quartz. During weathering the olivine was transformed to a nearly opaque, anhydrous ferrisilicate which, except for the change of Fe²⁺ to Fe³⁺ and the oxygen introduction, largely retained its original chemistry.     

Optical absorption and mössbauer spectra of purple and green yoderite,a kyanite-related mineral

Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe³⁺ in both varieties, with Fe²⁺/(Fe²⁺+Fe³⁺) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s^?1, respectively. These values correspond to Fe³⁺ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe³⁺ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm^?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm^?1 (PY) and a medium strong band at around 13,800 cm^?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn²⁺(A1) Mn³⁺(A1′) ? Mn³⁺(A1) Mn²⁺(A1′) and Mn²⁺(A1) Mn³⁺(A2 ? Mn³⁺(A1) Mn²⁺(A2) in PY and Fe²⁺(A1) Fe³⁺(A1′) ? Fe³⁺(A1) Fe²⁺(A1′) in GY. The evidence for homonuclear Mn²⁺ Mn³⁺ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm^?1 and assigned to Mn³⁺ in two positions. Weak bands around 10,000 cm^?1 in both varieties are assigned to Fe²⁺ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm^?1 are identified in GY and assigned to Fe³⁺ spin-forbiddendd-transitions.     

Comparative study of dissolution rate-determining mechanisms of limestone and dolomite

The dissolution rate-determining processes of carbonate rocks include: (1) heterogeneous reactions on rock surfaces; (2) mass transport of ions into solution from rock surfaces via diffusion; and (3) the conversion reaction of CO₂ into H⁺ and HCO ₃ ⁻ . Generally, it is the slowest of these three processes that limits the dissolution rate of carbonate rock. However, from experiment and theoretical analysis under similar conditions not only were the initial dissolution rates of dolomite lower by a factor of 3–60 than those of limestone, but also there are different dissolution rate-determining mechanisms between limestone and dolomite. For example, for limestone under the condition of CO₂ partial pressures dissolution rates increased significantly by a factor of about ten after addition of carbonic anhydrase (CA) into solution, which catalysed the conversation reaction of CO₂, whereas CA had little influence on dolomite dissolution. For dolomite, the increase of dissolution rate after addition of CA into solution appeared at Moreover, the enhancement factor of CA on dolomite dissolution rate was much lower (by a factor of about 3). In addition, when dissolution of both limestone and dolomite was determined by hydrodynamics (rotation speed or flow speed), especially under the dissolution of limestone was more sensitive to hydrodynamic change than that of dolomite. These findings are of significance in understanding the differences in karstification and relevant problems of resource and environment in dolomite and limestone areas.     

Garnet-clinopyroxene geothermometer

A garnet-clinopyroxene geothermometer based on the available experimental data on compositions of coexisting phases in the system MgO-FeO-MnO-Al₂O₃-Na₂O-SiO₂ is as follows: $$T({\text{}}K) = \frac{{8288 + 0.0276 P {\text{(bar)}} + Q1 - Q2}}{{1.987 \ln K_{\text{D}} + 2.4083}}$$ where P is pressure, and Q1, Q2, and K _D are given by the following equations $$Q1 = 2,710{\text{(}}X_{{\text{Fe}}} - X_{{\text{Mg}}} {\text{)}} + 3,150{\text{ }}X_{{\text{Ca}}} + 2,600{\text{ }}X_{{\text{Mn}}} $$ (mole fractions in garnet) $$\begin{gathered}Q2 = - 6,594[X_{{\text{Fe}}} {\text{(}}X_{{\text{Fe}}} - 2X_{{\text{Mg}}} {\text{)]}} \hfill \\{\text{ }} - 12762{\text{ [}}X_{{\text{Fe}}} - X_{{\text{Mg}}} (1 - X_{{\text{Fe}}} {\text{)]}} \hfill \\{\text{ }} - 11,281[X_{{\text{Ca}}} (1 - X_{{\text{Al}}} ) - 2X_{{\text{Mg}}} 2X_{{\text{Ca}}} ] \hfill \\{\text{ + 6137[}}X_{{\text{Ca}}} (2X_{{\text{Mg}}} + X_{{\text{Al}}} )] \hfill \\{\text{ + 35,791[}}X_{{\text{Al}}} (1 - 2X_{{\text{Mg}}} )] \hfill \\{\text{ + 25,409[(}}X_{{\text{Ca}}} )^2 ] - 55,137[X_{{\text{Ca}}} (X_{{\text{Mg}}} - X_{{\text{Fe}}} )] \hfill \\{\text{ }} - 11,338[X_{{\text{Al}}} (X_{{\text{Fe}}} - X_{{\text{Mg}}} )] \hfill \\\end{gathered} $$ [mole fractions in clinopyroxene Mg = MgSiO₃, Fe = FeSiO₃, Ca = CaSiO₃, Al = (Al₂O₃-Na₂O)] K _D = (Fe/Mg) in garnet/(Fe/Mg) in clinopyroxene. Mn and Cr in clinopyroxene, when present in small concentrations are added to Fe and Al respectively. Fe is total Fe²⁺+Fe³⁺.     

Solubility of Ca and Al in orthopyroxene from spinel peridotite: an improved version of an empirical geothermometer

Geothermometric equations for spinel peridotites by Fujii (1976), Gasparik and Newton (1984), and Chatterjee, and Terhart (1985) based on the reaction enstatite (en)+spinel (sp)Mg–Tschermaks (mats)+forsterite (fo) were tested using a nearly isothermal suite of mantle xenoliths from the Eifel, West Germany. In spite of using activities of MgAl₂O₄, en, and mats to allow for the non-ideal solution behaviour of the constituent phases, temperatures calculated from these equations systematically change as a function of Cr/(Cr+AL+Fe³⁺) in spinel. We propose an improved version of the empirical geothermometer for spinel peridotites of Sachtleben and Seck (1981) derived from the evaluation of the solubilities of Ca and Al in orthopyroxene from more than 100 spinel peridotites from the Rhenish Volcanic Province. A least squares regression yielded a smooth correlation between

The system Fe-Si-O: Oxygen buffer calibrations to 1,500K

The five solid-phase oxygen buffers of the system Fe-Si-O, iron-wuestite (IW), wuestite-magnetite (WM), magnetite-hematite (MH), quartz-iron-fayalite (QIF) and fayalite-magnetite-quartz (FMQ) have been recalibrated at 1 atm pressure and temperatures from 800°–1,300° C, using a thermogravimetric gas mixing furnace. The oxygen fugacity, \(f_{{\text{O}}_{\text{2}} }\) was measured with a CaO-doped ZrO₂ electrode. Measurements were made also for wuestite solid solutions in order to determine the redox behavior of wuestites with O/Fe ratios varying from 1.05 to 1.17. For FMQ, additional determinations were carried out at 1 kb over a temperature range of 600° to 800° C, using a modified Shaw membrane. Results agree reasonably well with published data and extrapolations. The reaction parameters K, ΔG _r ^o , ΔH _r ^o , and ΔS _r ^o were calculated from the following log \(f_{{\text{O}}_{\text{2}} }\) /T relations (T in K): $$\begin{gathered} {\text{IW }}\log f_{{\text{O}}_{\text{2}} } = - 26,834.7/T + 6.471\left( { \pm 0.058} \right) \hfill \\ {\text{ }}\left( {{\text{800}} - 1,260{\text{ C}}} \right), \hfill \\ {\text{WM }}\log f_{{\text{O}}_{\text{2}} } = - 36,951.3/T + 16.092\left( { \pm 0.045} \right) \hfill \\ {\text{ }}\left( {{\text{1,000}} - 1,300{\text{ C}}} \right), \hfill \\ {\text{MH }}\log f_{{\text{O}}_{\text{2}} } = - 23,847.6/T + 13.480\left( { \pm 0.055} \right) \hfill \\ {\text{ }}\left( {{\text{1,040}} - 1,270{\text{ C}}} \right), \hfill \\ {\text{QIF }}\log f_{{\text{O}}_{\text{2}} } = - 27,517.5/T + 6.396\left( { \pm 0.049} \right) \hfill \\ {\text{ }}\left( {{\text{960}} - 1,140{\text{ C}}} \right), \hfill \\ {\text{FMQ }}\log f_{{\text{O}}_{\text{2}} } = - 24,441.9/T + 8.290\left( { \pm 0.167} \right) \hfill \\ {\text{ }}\left( {{\text{600}} - 1,140{\text{ C}}} \right). \hfill \\ \end{gathered}$$ These experimentally determined reaction parameters were combined with published 298 K data to determine the parameters G_f, H_f, and S_f for the phases wuestite, magnetite, hematite, and fayalite from 298 K to the temperatures of the experiments. The T? \(f_{{\text{O}}_{\text{2}} }\) data for wuestite solid solutions were used to obtain activities, excess free energies and Margules mixing parameters. The new data provide a more reliable, consistent and complete reference set for the interpretation of redox reactions at elevated temperatures in experiments and field settings encompassing the crust, mantle and core as well as extraterrestrial environments.     

Copper-gold endoskarns and high-Mg monzodiorite–tonalite intrusions at Mt. Shea,Kalgoorlie, Australia: implications for the origin of gold–pyrite–tennantite mineralization in the Golden Mile

Five Cu–Au epidote skarns are associated with the Mt. Shea intrusive complex, located in the 2.7–2.6 Ga Eastern Goldfields Province of the Archean Yilgarn craton, in greenstones bounded by the Boulder Lefroy and Golden Mile strike-slip faults, which control the Golden Mile (1,435 t Au) at Kalgoorlie and smaller “orogenic” gold deposits at Kambalda. The Cu–Au deposits studied are oxidized endoskarns replacing faulted and fractured quartz monzodiorite–granodiorite. The orebodies are up to 140 m long and 40 m thick. Typical grades are 0.5% Cu and 0.3 g/t Au although parts are richer in gold (1.5–4.5 g/t). At the Hannan South mine, the skarns consist of epidote, calcite, chlorite, magnetite (5–15%), and minor quartz, muscovite, and microcline. Gangue and magnetite are in equilibrium contact with pyrite and chalcopyrite. The As–Co–Ni-bearing pyrite contains inclusions of hematite, gold, and electrum and is intergrown with cobaltite and Cu–Pb–Bi sulfides. At the Shea prospect, massive, net-textured, and breccia skarns are composed of multistage epidote, actinolite, albite, magnetite (5%), and minor biotite, calcite, and quartz. Gangue and magnetite are in equilibrium with Co–Ni pyrite and chalcopyrite. Mineral-pair thermometry, mass-balance calculations, and stable-isotope data (pyrite δ³⁴S_CDT = 2.5‰, calcite δ¹³C_PDB = −5.3‰, and δ¹⁸O_SMOW = 12.9‰) indicate that the Cu–Au skarns formed at 500 ± 50°C by intense Ca–Fe–CO₂–S metasomatism from fluids marked by an igneous isotope signature. The Mt. Shea stock–dike–sill complex postdates the regional D1 folding and metamorphism and the main phase of D2 strike-slip faulting. The suite is calc-akaline and comprises hornblende–plagioclase monzodiorite, quartz monzodiorite, granodiorite, and quartz–plagioclase tonalite porphyry. The intrusions display a wide range in silica content (53–73 wt% SiO₂), in ratio (0.37–0.89), and in ratio (0.02–0.31). Chromium (62–345 ppm), Ni (23–158), Sr (311–1361 ppm), and Ba (250–2,581 ppm) contents are high, Sr/Y ratios are high (24–278, mostly >50), and the rare earth element patterns are fractionated . These features and a negative niobium anomaly relative to the normal mid-ocean ridge basalt indicate that the suite formed by hornblende fractionation from a subduction-related monzodiorite magma sourced from metasomatized peridotite in the upper mantle. The magnesian composition of many intrusions was enhanced due to hornblende crystallization under oxidizing hydrous conditions and during the subsequent destruction of igneous magnetite by subsolidus actinolite–albite alteration. At the Shea prospect, main-stage Cu–Au epidote skarn is cut by biotite–albite–dolomite schist and by red biotite–albite replacement bands. Post-skarn alteration includes 20-m-thick zones of sericite–chlorite–ankerite schist confined to two D3 reverse faults. The schists are mineralized with magnetite + pyrite + chalcopyrite (up to 0.62% Cu, 1.6 g/t Au) and are linked to skarn formation by shared Ca–Fe–CO₂ metasomatism. Red sericitic alteration, marked by magnetite + hematite + pyrite, occurs in fractured porphyry. The biotite/sericite alteration and oxidized ore assemblages at the Shea prospect are mineralogically identical to magnetite–hematite-bearing gold lodes at Kambalda and in the Golden Mile. Published fluid inclusion data suggest that a “high-pressure”, oxidized magmatic fluid (2–9 wt% NaCl equivalent, , 200–400 MPa) was responsible for gold mineralization in structural sites of the Boulder Lefroy and Golden Mile faults. The sericite–alkerite lodes in the Golden Mile share the assemblages pyrite + tennantite + chalcopyrite and bornite + pyrite, and accessory high-sulfidation enargite with late-stage sericitic alteration zones developed above porphyry copper deposits.     

Kanonaite, (Mn 0.76 3+ Al0.23Fe 0.02 3+ )[6]Al[5][O¦SiO4], a new mineral isotypic with andalusite

Kanonaite forms rare porphyroblasts up to 12mm long in a gahnite— Mg-chlorite — coronadite — quartz schist occurring near Kanona, Zambia. The composition is (microprobe analysis): SiO₂ 32.2, Al₂O₃ 33.9, Mn as Mn₂O₃ 32.2, Fe₂O₃ 0.66, ZnO 0.13, MgO 0.04, BaO 0.04, TiO₂ 0.01, CaO 0.01, PbO 0.01, CuO 0.01, total 99.21, corresponding to $$\left( {{\text{Mn}}_{{\text{0}}{\text{.76}}}^{{\text{3 + }}} {\text{Al}}_{{\text{0}}{\text{.23}}} {\text{Fe}}_{{\text{0}}{\text{.015}}}^{{\text{3 + }}} } \right)_{1.005}^{\left[ 6 \right]} {\text{AL}}_{1.00}^{\left[ 5 \right]} \left[ {{\text{O}}_{{\text{1}}{\text{.00}}} |{\text{Si}}_{{\text{0}}{\text{.99}}} {\text{O}}_{{\text{4}}{\text{.00}}} } \right]$$ The mineral is greenish black, strongly pleochroic with X(∥a) yellow green, Y(∥b) bluish green, Z(∥c) deep golden yellow, biaxial positive, with 2V = 53°(3°), α = 1.702, β = 1.730, γ = 1.823. Vickers microhardness (100 gram load) ranges between 906 and 1017kp/mm². The structure is orthorhombic, isotypic with andalusite, space group Pnnm, a = 0.7953(2), b = 0.8038(2), c = 0.5619(2) nm, V = 0.3592(1) nm³, a/b = 0.9895(3), c/b = 0.6990(3), S.G.(_x) = 3.395 g/cm³, Z = 4. The strongest X-ray powder lines are (d in nm, I, hkl):0.5669, 100, 110; 0.4590, 75, 011 and 101; 0.3577, 90, 120 and 210; 0.2827, 94, 220; 0.2517, 90, 310 and 112; 0.2212, 83, 320, 122 and 212. Comparison of the intensities of 373 observed X-ray reflections with those calculated for several models of Mn³⁺-distribution indicates octahedral coordination of all or most of the manganese present. Interpretation of magnetic measurements (μ_eff = 3.15B.M. per Mn atom at 25 ° C) indirectly supports octahedral coordination of Mn³⁺. The name of the mineral is for Kanona, a town near the type locality. The name is proposed for the end member Mn^{3+ [6]}Al^[5][O¦SiO₄] and for members of the solid-solution series towards andalusite with octahedral Mn³⁺>Al. The presently described mineral may be referred to as aluminian kanonaite.     

Re-evaluation of lead isotopic data,southern Massif Central,France

Three independent Pb isotope homogenizing processes operating on large volumes of rock material during limited intervals in the Phanerozoic have been used to define a unique evolutionary curve for rock and ore lead isotopic compositions of the southern Massif Central, France. The model is

The magnesiowüstite: iron equilibrium and its implications for the activity-composition relations of (Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine solid solutions

The chemical potential of oxygen (µO₂) in equilibrium with magnesiowüstite solid solution (Mg, Fe)O and metallic Fe has been determined by gas-mixing experiments at 1,473 K supplemented by solid-cell EMF experiments at lower temperatures. The results give:

Genesis of secondary uranium minerals associated with jasperoid veins,El Erediya area,Eastern Desert,Egypt

Uranium mineralization in the El Erediya area, Egyptian Eastern Desert, has been affected by both high temperature and low temperature fluids. Mineralization is structurally controlled and is associated with jasperoid veins that are hosted by a granitic pluton. This granite exhibits extensive alteration, including silicification, argillization, sericitization, chloritization, carbonatization, and hematization. The primary uranium mineral is pitchblende, whereas uranpyrochlore, uranophane, kasolite, and an unidentified hydrated uranium niobate mineral are the most abundant secondary uranium minerals. Uranpyrochlore and the unidentified hydrated uranium niobate mineral are interpreted as alteration products of petscheckite. The chemical formula of the uranpyrochlore based upon the Electron Probe Micro Analyzer (EPMA) is . It is characterized by a relatively high Zr content (average ZrO₂ = 6.6 wt%). The average composition of the unidentified hydrated uranium niobate mineral is , where U and Nb represent the dominant cations in the U and Nb site, respectively. Uranophane is the dominant U⁶⁺ silicate phase in oxidized zones of the jasperoid veins. Kasolite is less abundant than uranophane and contains major U, Pb, and Si but only minor Ca, Fe, P, and Zr. A two-stage metallogenetic model is proposed for the alteration processes and uranium mineralization at El Erediya. The primary uranium minerals were formed during the first stage of the hydrothermal activity that formed jasperoid veins in El Eradiya granite (130–160 Ma). This stage is related to the Late Jurassic–Early Cretaceous phase of the final Pan-African tectono-thermal event in Egypt. After initial formation of El Erediya jasperoid veins, a late stage of hydrothermal alteration includes argillization, dissolution of iron-bearing sulfide minerals, formation of iron-oxy hydroxides, and corrosion of primary uranium minerals, resulting in enrichment of U, Ca, Pb, Zr, and Si. During this stage, petscheckite was altered to uranpyrochlore and oxy-petscheckite. Uranium was likely transported as uranyl carbonate and uranyl fluoride complexes. With change of temperature and pH, these complexes became unstable and combined with silica, calcium, and lead to form uranophane and kasolite. Finally, at a later stage of low-temperature supergene alteration, oxy-petscheckite was altered to an unidentified hydrated uranium niobate mineral by removal of Fe.     

Chemistry of Neutral and Alkaline Waters with Low Al<Superscript>3+</Superscript> Activity Against Hydroxyaluminosilicate HAS<Subscript>B</Subscript> Solubility. The Evidence from Ground and Surface Waters of the Sudetes Mts. (SW Poland)

A wide set of aqueous chemistry data (574 water analyses) from natural environments has been used to testify and validate of the solubility of synthetic hydroxyaluminosilicate (HAS_B)_, Al₂Si₂O₅(OH)₄. The ground and surface waters represent regolith and/or fissure aquifers in various (magmatic, sedimentary and metamorphic) bedrocks in the Sudetes Mts. (SW Poland). The solubility of HAS_B in natural waters was calculated using the method proposed by Schneider et al. (Polyhedron 23:3185–3191, 2004). Results confirm usefulness and validity of this method. The HAS_B solubility obtained from the field data (logK_sp = −44.7 ± 0.58) is lower than it was estimated (logK_sp = −40.6 ± 0.15) experimentally (Schneider et al. Polyhedron 23:3185–3191, 2004). In the waters studied the equilibrium with HAS_B is maintained at pH above 6.7 and at [Al³⁺] ≤ 10⁻¹⁰. Silicon activity (log[H₄SiO₄]) ranges between −4.2 and −3.4. Due to the calculation method used, the K_sp mentioned above cannot be considered as a classical solubility constant. However, it can be used in the interpretation of aluminium solubility in natural waters. The HAS_B has solubility lower than amorphous Al(OH)₃, and higher than proto-imogolite. From water samples that are in equilibrium with respect to HAS_B, the solubility product described by the reaction, is calculated to be logK_sp = 14.0 (±0.7) at 7°C.     

Crystal field and covalency of octahedral chromium in natural [8](Mg1?xCax) 3[6] (Al0.67Cr0.33)2Si3O12 garnets from upper mantle rocks

In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the 3d ^N -ions and the character of 3d ^N –O bonds in oxygen based minerals, 19 natural Cr³⁺-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The garnets had compositions with populations of the ^[8] X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w _Ca[8] ≤ 0.745, while the ^[6] Y-site fraction was constant with x _Cr³⁺ _[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x _Ca = 0.28), grey with 0.28 ≤ x _Ca ≤ 0.4 and green with 0.4 ≤ x _Ca. The crystal field parameter of octahedral Cr³⁺ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm⁻¹ at x _Ca[8] = 0.020 to 16,580 cm⁻¹ at x _Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity close to x _Ca[8] ≈ 0.3,

Experimental calibration of Forsterite–Anorthite–Ca-Tschermak–Enstatite (FACE) geobarometer for mantle peridotites

The crystallization of plagioclase-bearing assemblages in mantle rocks is witness of mantle exhumation at shallow depth. Previous experimental works on peridotites have found systematic compositional variations in coexisting minerals at decreasing pressure within the plagioclase stability field. In this experimental study we present new constraints on the stability of plagioclase as a function of different Na₂O/CaO bulk ratios, and we present a new geobarometer for mantle rocks. Experiments have been performed in a single-stage piston cylinder at 5–10 kbar, 1050–1150?°C at nominally anhydrous conditions using seeded gels of peridotite compositions (Na₂O/CaO?=?0.08–0.13; X _Cr = Cr/(Cr?+?Al)?=?0.07–0.10) as starting materials. As expected, the increase of the bulk Na₂O/CaO ratio extends the plagioclase stability to higher pressure; in the studied high-Na fertile lherzolite (HNa-FLZ), the plagioclase-spinel transition occurs at 1100?°C between 9 and 10 kbar; in a fertile lherzolite (FLZ) with Na₂O/CaO?=?0.08, it occurs between 8 and 9 kbar at 1100?°C. This study provides, together with previous experimental results, a consistent database, covering a wide range of P–T conditions (3–9 kbar, 1000–1150?°C) and variable bulk compositions to be used to define and calibrate a geobarometer for plagioclase-bearing mantle rocks. The pressure sensitive equilibrium:

$$\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}^{{\text{Ol}}}}\limits_{{\text{Forsterite}}} +\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{8}}}^{{\text{Pl}}}}\limits_{{\text{Anorthite}}~} =\mathop {{\text{CaA}}{{\text{l}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{6}}}^{{\text{Cpx}}}}\limits_{{\text{Ca-Tschermak}}} +{\text{ }}\mathop {{\text{M}}{{\text{g}}_{\text{2}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{\text{6}}}^{{\text{Opx}}}}\limits_{{\text{Enstatite}}} ,$$

has been empirically calibrated by least squares regression analysis of experimental data combined with Monte Carlo simulation. The result of the fit gives the following equation:

$$P=7.2( \pm 2.9)+0.0078( \pm 0.0021)T{\text{ }}+0.0022( \pm 0.0001)T{\text{ }}\ln K,$$

$${R^2}=0.93,$$

where P is expressed in kbar and T in kelvin. K is the equilibrium constant K?=?a _CaTs × a _en/a _an × a _fo, where a _CaTs, a _en, a _an and a _fo are the activities of Ca-Tschermak in clinopyroxene, enstatite in orthopyroxene, anorthite in plagioclase and forsterite in olivine. The proposed geobarometer for plagioclase peridotites, coupled to detailed microstructural and mineral chemistry investigations, represents a valuable tool to track the exhumation of the lithospheric mantle at extensional environments.

     

Daytime deposition and nighttime dissolution of calcium carbonate controlled by submerged plants in a karst spring-fed pool: insights from high time-resolution monitoring of physico-chemistry of water

Water temperature, dissolved oxygen (DO), pH, and specific conductivity (spc) were measured in a time interval of 15 min in a karst spring and the spring-fed pool with flourishing submerged plants in Guilin, SW China under dry weather for periods of 2 days. Measurements allowed calculation of calcium and bicarbonate concentrations ([Ca²⁺] and [HCO₃ ⁻]), and thus CO₂ partial pressure ( ) and saturation index of calcite (SIc). Results show that there were not any diurnal variations in the physico-chemical parameters of the water for the spring. However, during daytime periods, pool water decreased to far less than the spring water in a few hours, pH and SIc increased to greater than the spring, and [Ca²⁺] and [HCO₃ ⁻] decreased to less than the spring. During nighttime periods, pool water returned to or even increased to greater than the spring, pH and SIc decreased to less than the spring, and [Ca²⁺] and [HCO₃ ⁻] increased to greater than the spring. The decrease in [Ca²⁺] and [HCO₃ ⁻] to less than the spring during daytime periods implies daytime deposition of calcium carbonate, while the increase in [Ca²⁺] and [HCO₃ ⁻] to greater than the spring during nighttime periods implies nighttime dissolution of calcium carbonate. The direction of the observed changes depended essentially on the illumination, indicating that daytime photosynthetic and nighttime respiratory activities in the pool aquatic plant ecosystem, which were further evidenced by the increase and decrease in DO during daytime and nighttime periods respectively, were the main processes involved. The large variations of the components of the carbonate system imply considerable changes of the capacities of CO₂ and O₂ in water. The finding has implications for water sampling strategy in slow-flowing karst streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, and wetlands, where aquatic plant ecosystem may flourish.     

The origin of the high-K latites from Camp Creek,Arizona: constraints from experiments with variable fO2 and a_{{\text{H}}_{\text{2}} {\text{O}}}

Near-liquidus melting experiments were performed on a high-K latite at fO₂'s ranging from iron-wustite-graphite (IWG) to nickel-nickel oxide (NNO) in the presence of a C-O-H fluid phase. Clinopyroxene is a liquidus phase under all conditions. At IWG , the liquidus at 10 kb is about 1,150° C but is depressed to 1,025° C at NNO and . Phlogopite and apatite are near-liquidus phases, with apatite crystallizing first at pressures below 10 kb. Phlogopite is a liquidus phase only at NNO and high . Under all conditions the high-K latites show a large crystallization interval with phlogopite becoming the dominant crystalline phase with decreasing temperature. Increasing fO₂ affects phlogopite crystallization but the liquidus temperature is essentially a function of . The chemical compositions of the near-liquidus phases support formation of the high-K latites under oxidizing conditions (NNO or higher) and high . It is concluded from the temperature of the H₂O-saturated liquidus at 10 kb, the groundmass: crystal ratio and presence of chilled latite margins around some xenoliths that the Camp Creek high-K latite magma passed thru the lower crust at temperatures of 1,000° C or more.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting: