Rare earth element diffusion in a natural pyrope single crystal at 2.8 GPa

Volume diffusion rates of Ce, Sm, Dy, and Yb have been measured in a natural pyrope-rich garnet single crystal (Py₇₁Alm₁₆Gr₁₃) at a pressure of 2.8 GPa and temperatures of 1,200-1,450 °C. Pieces of a single gem-quality pyrope megacryst were polished, coated with a thin layer of polycrystalline REE oxide, then annealed in a piston cylinder device for times between 2.6 and 90 h. Diffusion profiles in the annealed samples were measured by SIMS depth profiling. The dependence of diffusion rates on temperature can be described by the following Arrhenius equations (diffusion coefficients in m²/s): % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2DaeHbuLwB % Lnhiov2DGi1BTfMBaebbfv3ySLgzGueE0jxyaibaieYlf9irVeeu0d % Xdh9vqqj-hEeeu0xXdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9 % pgea0dXdar-Jb9hs0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaaca % qabeaadaabauaaaOqaauaabeqaeeaaaaqaaiGbcYgaSjabc+gaVjab % cEgaNnaaBaaaleaacqaIXaqmcqaIWaamaeqaaOGaemiraq0aaSbaaS % qaaiabbMfazjabbkgaIbqabaGccqGH9aqpcqGGOaakcqGHsislcqaI % 3aWncqGGUaGlcqaI3aWncqaIZaWmcqGHXcqScqaIWaamcqGGUaGlcq % aI5aqocqaI3aWncqGGPaqkcqGHsisldaqadaqaaiabiodaZiabisda % 0iabiodaZiabgglaXkabiodaZiabicdaWiaaysW7cqqGRbWAcqqGkb % GscaaMe8UaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqqGTaql % cqqGXaqmaaGccqGGVaWlcqaIYaGmcqGGUaGlcqaIZaWmcqaIWaamcq % aIZaWmcqWGsbGucqWGubavaiaawIcacaGLPaaaaeaacyGGSbaBcqGG % VbWBcqGGNbWzdaWgaaWcbaGaeGymaeJaeGimaadabeaakiabdseaen % aaBaaaleaacqqGebarcqqG5bqEaeqaaOGaeyypa0JaeiikaGIaeyOe % I0IaeGyoaKJaeiOla4IaeGimaaJaeGinaqJaeyySaeRaeGimaaJaei % Ola4IaeGyoaKJaeG4naCJaeiykaKIaeyOeI0YaaeWaaeaacqaIZaWm % cqaIWaamcqaIYaGmcqGHXcqScqaIZaWmcqaIWaamcaaMe8Uaee4AaS % MaeeOsaOKaaGjbVlabb2gaTjabb+gaVjabbYgaSnaaCaaaleqabaGa % eeyla0IaeeymaedaaOGaei4la8IaeGOmaiJaeiOla4IaeG4mamJaeG % imaaJaeG4mamJaemOuaiLaemivaqfacaGLOaGaayzkaaaabaGagiiB % aWMaei4Ba8Maei4zaC2aaSbaaSqaaiabigdaXiabicdaWaqabaGccq % WGebardaWgaaWcbaGaee4uamLaeeyBa0gabeaakiabg2da9iabcIca % OiabgkHiTiabiMda5iabc6caUiabikdaYiabigdaXiabgglaXkabic % daWiabc6caUiabiMda5iabiEda3iabcMcaPiabgkHiTmaabmaabaGa % eG4mamJaeGimaaJaeGimaaJaeyySaeRaeG4mamJaeGimaaJaaGjbVl % abbUgaRjabbQeakjaaysW7cqqGTbqBcqqGVbWBcqqGSbaBdaahaaWc % beqaaiabb2caTiabbgdaXaaakiabc+caViabikdaYiabc6caUiabio % daZiabicdaWiabiodaZiabdkfasjabdsfaubGaayjkaiaawMcaaaqa % aiGbcYgaSjabc+gaVjabcEgaNnaaBaaaleaacqaIXaqmcqaIWaamae % qaaOGaemiraq0aaSbaaSqaaiabboeadjabbwgaLbqabaGccqGH9aqp % cqGGOaakcqGHsislcqaI5aqocqGGUaGlcqaI3aWncqaI0aancqGHXc % qScqaIYaGmcqGGUaGlcqaI4aaocqaI0aancqGGPaqkcqGHsisldaqa % daqaaiabikdaYiabiIda4iabisda0iabgglaXkabiMda5iabigdaXi % aaysW7cqqGRbWAcqqGkbGscaaMe8UaeeyBa0Maee4Ba8MaeeiBaW2a % aWbaaSqabeaacqqGTaqlcqqGXaqmaaGccqGGVaWlcqaIYaGmcqGGUa % GlcqaIZaWmcqaIWaamcqaIZaWmcqWGsbGucqWGubavaiaawIcacaGL % Paaaaaaaaa!0C76!

Grain boundary diffusion of Si, Mg, and O in enstatite reaction rims: a SIMS study using isotopically doped reactants

Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in ¹⁸O and ²⁹Si were used as reactants. The relative mobility of ¹⁸O and ²⁹Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg₂SiO₄=0.5 Mg₂Si₂O₆+MgO at the forsterite-enstatite, and MgO+SiO₂=0.5 Mg₂Si₂O₆ at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiramaaDa % aaleaacaWGtbGaamyAaiaacYcacaWGfbGaamOBaaqaaiaadAfacaWG % VbGaamiBaaaaaaa!3DD2! D_Si,En^VolD_{Si,En}^{Vol} at dry conditions from the literature, results a % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmirayaafa % Waa0baaSqaaiaadofacaWGPbGaaiilaiaadweacaWGUbaabaaaaOGa % eqiTdqgaaa!3CCD! D￠_Si,En dD'_{Si,En}^{} \delta value of 3᎒^-24 m³ s^-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to ¹⁸O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and D´_Ox,En' cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity D´_MgO' of MgO in iron-free enstatite is 8᎒^-22 m³ s^-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo₉₂) as reactant reveal lower rates by a factor of about 4. Our results show that isotope tracers in rim growth experiments allow identification of the actual interface reactions, recognition of the rate-controlling component and further calculation of D´' values for specific components.     

Diffusion of lead in plagioclase and K-feldspar: an investigation using Rutherford Backscattering and Resonant Nuclear Reaction Analysis

Chemical diffusion of Pb has been measured in K-feldspar (Or₉₃) and plagioclase of 4 compositions ranging from An₂₃ to An₉₃ under anhydrous, 0.101 MPa conditions. The source of diffusant for the experiments was a mixture of PbS powder and ground feldspar of the same composition as the sample. Rutherford Backscattering (RBS) was used to measure Pb diffusion profiles. Over the temperature range 700–1050°C, the following Arrhenius relations were obtained (diffusivities in m²s^-1):Oligoclase (An₂₃): Diffusion normal to (001): log D = ( – 6.84 ± 0.59) – [(261 ± 13 kJ mol ^–1)/2.303RT]Diffusion normal to (010): log D = ( – 3.40 ± 0.50) – [(335 ± 11 kJ mol ^–1)/2.303RT]Andesine (An₄₃): Diffusion normal to (001): log D = ( – 6.73 ± 0.54) – [(266 ± 12 kJ mol ^–1)/2.303RT] Diffusion normal to (010) appears to be only slightly slower than diffusion normal to (001) in andesine.Labradorite (An₆₇): Diffusion normal to (001): log D = ( – 7.16 ± 0.61) – [(267 ± 13 kJ mol ^–1)/2.303RT] Diffusion normal to (010) is slower by 0.7 log units on average.Anorthite Diffusion normal to (010): log D = ( – 5.43 ± 0.48) – [(327 ± 11 kJ mol ^–1)/2.303RT]K-feldspar (Or₉₃): Diffusion normal to (001): log D = ( – 4.74 ± 0.52) – [(309 ± 16 kJ mol ^–1)/2.303RT] Diffusion normal to (010): log D = ( – 5.99 ± 0.51) – [(302 ± 11 kJ mol ^–1)/2.303RT]In calcic plagioclase, Pb uptake is correlated with a reduction of Ca, indicating the involvement of PbCa exchange in chemical diffusion. Decreases of Na and K concentrations in sodic plagioclase and K-feldspar, respectively, are correlated with Pb uptake and increase in Al concentration (measured by resonant nuclear reaction analysis), suggesting a coupled process for Pb exchange in these feldspars. These results have important implications for common Pb corrections and Pb isotope systematics. Pb diffusion in apatite is faster than in the investigated feldspar compositions, and Pb diffusion rates in titanite are comparable to both K-feldspar and labradorite. Given these diffusion data and typical effective diffusion radii for feldspars and accessory minerals, we may conclude that feldspars used in common Pb corrections are in general less inclined to experience diffusion-controlled Pb isotope exchange than minerals used in U-Pb dating that require a common Pb correction.     

Diffusion of tetravalent cations in zircon

Diffusion rates for the three tetravalent cations U, Th and Hf have been measured in synthetic zircon. Diffusant sources included oxide powders and ground pre-synthesized silicates. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles. Over the temperature range 1400–1650 °C, the following Arrhenius relations were obtained (diffusion coefficients in m²sec⁻¹): log D _Th = (1.936 ± 0.9820) + (− 792 ± 34 kJ mol⁻¹ /2.303 RT) log D _U = (0.212 ± 2.440) + (− 726 ± 83 kJ mol⁻¹ /2.303 RT) log D _Hf = (3.206 ± 1.592) + (− 812 ± 54 kJ mol⁻¹ /2.303 RT) The data show a systematic increase in diffusivity with decreasing ionic radius (i.e., faster diffusion rates for Hf than for U or Th), a trend also observed in our earlier study of rare earth diffusion in zircon. Diffusive fractionation may be a factor in the Lu-Hf system given the much slower diffusion rates of tetravalent cations when compared with the trivalent rare earths. The very slow diffusion rates measured for these tetravalent cations suggest that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores. Received: 12 July 1996 / Accepted: 2 December 1996     

Thermodynamic data of lawsonite and zoisite in the system CaO–Al2O3–SiO2–H2O based on experimental phase equilibria and calorimetric work

The enthalpy of drop-solution in molten 2PbO·B₂O₃ of synthetic and natural lawsonite, CaAl₂(Si₂O₇)(OH)₂·H₂O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (_fH^Oxides=-168.7Dž.4 kJ mol^-1, or (_fH⁰₂₉₈=-4,872.5dž.0 kJ mol^-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca₂Al₃(SiO₄)(Si₂O₇)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al₂O₃-SiO₂-H₂O (CASH). The following data for lawsonite and zoisite were obtained: (_fH⁰₂₉₈ (lawsonite)=-4,865.68 kJ mol^-1 , S⁰₂₉₈ (lawsonite)=229.27 J K^-1 mol^-1 , (_fH⁰₂₉₈ (zoisite)=-6,888.99 kJ mol^-1 , S⁰₂₉₈ (zoisite)=297.71 J K^-1 mol^-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.     

Cr and Al diffusion in chromite spinel: experimental determination and its implication for diffusion creep

Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl₂O₄ spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D _Cr–Al = D ₀ exp {−(Q′ + PV*)/RT}, where D ₀ = exp{(10.3 ± 0.08) × Cr#^0.54±0.02} + (1170 ± 31.2) cm²/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm³/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.     

Enthalpies in (Na,Ca)- and (K,Ca)-feldspar binaries: a high-temperature solution calorimetric study

A series of high structural state plagioclases (Ab-An) was crystallized from glasses. By exchanging Na for K in KCl melts, metastable K-plagioclases (Or-An) were prepared which possess the same structural state as the starting plagioclases. Both series were investigated at 980 K by lead borate solution calorimetry. Continuing the ideas of Carpenter and McConnell (1984) and Carpenter (1992a), the results can be interpreted as follows. In the high plagioclase series, the enthalpies of solution, jH_sol, reflect the schemes of Al,Si ordering: (1) analbite-like (C2/m) ordering in the An-poor region 0hX_AnА.2, (2) high albite-like (C1¥) ordering in intermediate plagioclases, and (3) anorthite-like (I1¥) ordering in the An-rich region 0.7AnБ. In regions 1 and 2, jH_sol decreases as a function of X_An, but increases in region 3 as a consequence of the C1¥MI1¥ ordering reaction. Therefore, it is not a mixing effect but a compositionally restricted ordering effect which causes the excess enthalpies, jH^ex, to be positive in the plagioclase binary as a whole. Neglecting the existence of phase transitions at X_An=0.2 and X_An=0.7, jH^ex can be approximated by a two-parameter Margules model yielding W^H_AnAb=14Dž kJ/mol and W^H_AbAn=40Dž kJ/mol. jH_sol values of I1¥ plagioclases (X_An>0.7) can be "corrected" for the C1¥MI1¥ ordering effect (Carpenter 1992a). When combining the corrected values with the jH_sol data which were actually measured on the C1¥ plagioclases (X_An<0.7), negative excess enthalpies are generated in the plagioclase binary. This may be expected when C1¥ ordering occurs relative to topochemically monoclinic reference states of analbite and hypothetical anorthite devoid of I1¥ order. The solution experiments on the K-plagioclases resulted in similar characteristics as those found for the plagioclases. However, in addition to the ordering effects observed in the plagioclase binary, volume mismatch effects contribute to jH^ex in the K-plagioclase series. jH^ex can be represented by a Margules model with W^H_AnOr=60ᆞ kJ/mol and W^H_OrAn=91ᆢ kJ/mol when the phase transitions at X_An=0.2 and X_An=0.7 are again neglected. The contribution of the volume mismatch effect to jH^ex is considerable, as appears from the large difference between the K-plagioclase and the plagioclase Margules parameters. Their difference corresponds to a practically symmetrical dependence of jH^ex_volmism on composition, with W^H_volmism=48ᆡ kJ/mol.     

Experimental investigation of zoisite–clinozoisite phase equilibria in the system CaO–Fe2O3–Al2O3–SiO2–H2O

The system Ca₂Al₃Si₃O₁₁(O/OH)-Ca₂Al₂FeSi₃O₁₁(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-X_ps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-X_ps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by X_ps^zo (max) = 1.9*10 ^{- 4} T+ 3.1*10 ^{- 2} P - 5.36*10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and X_ps^czo (min) = (4.6 * 10 ^{- 4} - 4 * 10 ^{- 5} P)T + 3.82 * 10 ^{- 2} P - 8.76 * 10 ^{- 2}{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (H_r⁰=2.8ǃ.3 kJ/mol and (S_r⁰=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 X_ps and clinozoisite II >0.55 X_ps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al₂O₃-Fe₂O₃-SiO₂-H₂O are shown.     

Geochemistry of Mesozoic plutons, southern Death Valley region, California: Insights into the origin of Cordilleran interior magmatism

Mesozoic granitoid plutons in the southern Death Valley region of southeastern California reveal substantial compositional and isotopic diversity for Mesozoic magmatism in the southwestern US Cordillera. Jurassic plutons of the region are mainly calc-alkaline mafic granodiorites with )_Ndi of -5 to -16, ⁸⁷Sr/⁸⁶Sr_i of 0.707-0.726, and ²⁰⁶Pb/²⁰⁴Pb_i of 17.5-20.0. Cretaceous granitoids of the region are mainly monzogranites with )_Ndi of -6 to -19, ⁸⁷Sr/⁸⁶Sr_i of 0.707-0.723, and ²⁰⁶Pb/²⁰⁴Pb_i of 17.4-18.6. The granitoids were generated by mixing of mantle-derived mafic melts and pre-existing crust - some of the Cretaceous plutons represent melting of Paleoproterozoic crust that, in the southern Death Valley region, is exceptionally heterogeneous. A Cretaceous gabbro on the southern flank of the region has an unusually juvenile composition ()_Ndi -3.2, ⁸⁷Sr/⁸⁶Sr_i 0.7060). Geographic position of the Mesozoic plutons and comparison with Cordilleran plutonism in the Mojave Desert show that the Precambrian lithosphere (craton margin) in the eastern Mojave Desert region may consists of two crustal blocks separated by a more juvenile terrane.     

The effect of halogens on Zr diffusion and zircon dissolution in hydrous metaluminous granitic melts

Diffusion of Zr and zircon solubility in hydrous, containing approximately 4.5 wt% H₂O, metaluminous granitic melts with halogens, either 0.35 wt% Cl (LCl) or 1.2 wt% F (MRF), and in a halogen-free melt (LCO) were measured at 1.0 GPa and temperatures between 1,050 and 1,400 °C in a piston-cylinder apparatus using the zircon dissolution technique. Arrhenius equations for Zr diffusion in each hydrous melt composition are, for LCO with 4.4ǂ.4 wt% H₂O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaI4aaocqaI4aaocqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaIZaWmcqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabiIda4aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIXaqmcqaI0aancqaIWaamcqGGUaGlcqaIXa % qmcqGHXcqScqaIZaWmcqaIZaWmcqGGUaGlcqaI5aqoaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!571F! D = 2.88 ±0.03x10 ^{- 8} exp( [( - 140.1 ±33.9)/(RT)] )D = 2.88 \pm 0.03x10^{ - 8} \exp \left( {{{ - 140.1 \pm 33.9} \over {RT}}} \right) , for LCl with 4.5ǂ.5 wt% H₂O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaIZaWmcqaIZaWmcqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaI1aqncqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabisda0aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIYaGmcqaI1aqncqaI0aancqGGUaGlcqaI4a % aocqGHXcqScqaI2aGncqaI0aancqGGUaGlcqaIXaqmaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!5719! D = 2.33 ±0.05x10 ^{- 4} exp( [( - 254.8 ±64.1)/(RT)] )D = 2.33 \pm 0.05x10^{ - 4} \exp \left( {{{ - 254.8 \pm 64.1} \over {RT}}} \right) and for MRF with 4.9ǂ.3 wt% H₂O: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacqWGebarcqGH9aqpcq % aIYaGmcqGGUaGlcqaI1aqncqaI0aancqGHXcqScqaIWaamcqGGUaGl % cqaIWaamcqaIZaWmcqWG4baEcqaIXaqmcqaIWaamdaahaaWcbeqaai % abgkHiTiabiwda1aaakiGbcwgaLjabcIha4jabcchaWnaabmaabaWa % aSaaaeaacqGHsislcqaIYaGmcqaIYaGmcqaIZaWmcqGGUaGlcqaI4a % aocqGHXcqScqaIXaqmcqaI1aqncqGGUaGlcqaI1aqnaeaacqWGsbGu % cqWGubavaaaacaGLOaGaayzkaaaaaa!5715! D = 2.54 ±0.03x10 ^{- 5} exp( [( - 223.8 ±15.5)/(RT)] )D = 2.54 \pm 0.03x10^{ - 5} \exp \left( {{{ - 223.8 \pm 15.5} \over {RT}}} \right) . Solubilities determined by the dissolution technique were reversed for LCO +4.5ǂ.5 wt% H₂O by crystallization of a Zr-enriched glass of LCO composition at 1,200 and 1,050 °C at 1.0 GPa. The solubility data were used to calculate partition coefficients of Zr between zircon and hydrous melt, which are given by the following expressions: for LCO % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGOnayJa % eG4mamZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 1aqncqGGUaGlcqaI4aaocqaI3aWnaaa!5924! lnD_Zr^zircon/melt = 1.63( [10000/(T)] ) - 5.87\ln D_{Zr}^{zircon/melt} = 1.63\left( {{{10000} \over T}} \right) - 5.87 , for LCl % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGinaqJa % eG4naCZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 0aancqGGUaGlcqaI3aWncqaI1aqnaaa!5920! lnD_Zr^zircon/melt = 1.47( [10000/(T)] ) - 4.75\ln D_{Zr}^{zircon/melt} = 1.47\left( {{{10000} \over T}} \right) - 4.75 and, for MRF by % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavP1wzZbItLDhis9wBH5garm % Wu51MyVXgaruWqVvNCPvMCG4uz3bqee0evGueE0jxyaibaieYlf9ir % Veeu0dXdh9vqqj-hEeeu0xXdbba9ev6pc9fs0-rqaqpepmKs4qpepe % I8kaL8kuc9pgc9q8qqaq-dhH6hb9hs0dXdHu6deP0u0-vr0-vr0db8 % meaabaqaciGacaGaaeaabaWaaeaaeaaakeaacyGGSbaBcqGGUbGBcq % WGebardaqhaaWcbaGaemOwaOLaemOCaihabaGaemOEaONaemyAaKMa % emOCaiNaem4yamMaem4Ba8MaemOBa4Maei4la8IaemyBa0Maemyzau % MaemiBaWMaemiDaqhaaOGaeyypa0JaeGymaeJaeiOla4IaeGinaqJa % eG4naCZaaeWaaeaadaWcaaqaaiabigdaXiabicdaWiabicdaWiabic % daWiabicdaWaqaaiabdsfaubaaaiaawIcacaGLPaaacqGHsislcqaI % 0aancqGGUaGlcqaI5aqocqaIXaqmaaa!591C! lnD_Zr^zircon/melt = 1.47( [10000/(T)] ) - 4.91\ln D_{Zr}^{zircon/melt} = 1.47\left( {{{10000} \over T}} \right) - 4.91 . Experiments on the same compositions, but with water contents down to 0.5 wt%, demonstrated reductions in both the diffusion coefficient of Zr and zircon solubility in the melt. The addition of halogens at the concentration levels studied to metaluminous melts has a small effect on either the diffusion of Zr in the melt, or the solubility of zircon at all water concentrations and temperatures investigated. At 800 °C, the calculated diffusion coefficient of Zr is lowest in LCl, 9᎒^-17 m² s^-1, and is highest in LCO, 4᎒^-15 m² s^-1. Extrapolation of the halogen-free solubility data to a magmatic temperature of 800 °C yields solubilities of approximately one-third of those directly measured in similar compositions, predicted by earlier studies of zircon dissolution and based upon analyses of natural rocks. This discrepancy is attributed to the higher oxygen fugacity of the experiments of this study compared with previous studies and nature, and the effect of oxygen fugacity on the structural role of iron in the melt, which, in turn, affects zircon solubility, but does not significantly affect Zr diffusion.     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).     

Primary fluids entrapped at blueschist to eclogite transition: evidence from the Tianshan meta-subduction complex in northwestern China

Orthopyroxene and olivine exposed along the rim of a harzburgite xenolith from La Palma (Canary Islands) show polycrystalline selvages and diffusion zones that result from contact with mafic, alkaline, silica-undersaturated melts during at least 10-100 years before eruption. The zoned selvages consist of a fine-grained reaction rim towards the xenolith and a coarser grained, cumulate-like layer towards the melt contact. The diffusion zones are characterized by decreasing magnesium number from about 89-91 in the xenolith interior to 79-85 at the rims, and clearly result from Fe-Mg exchange with surrounding mafic melt. The width of the diffusion zones is 80-200 µm in orthopyroxene and 1,020-1,730 µm in olivine. Orthopyroxene also shows decreasing Al₂O₃ and Cr₂O₃ and increasing MnO and TiO₂ towards the reaction rims. Textural relations and comparisons with dissolution experiments suggest that orthopyroxene dissolution by silica-undersaturated melt essentially ceased after days to weeks of melt contact, possibly because of decreasing temperature and formation of the reaction rims. The short dissolution phase was followed by prolonged growth of diffusion zones through cation exchange between xenolith minerals and melt across the reaction rims, and by the growth of cumulus crystals. The observations indicate that orthopyroxene xenocrysts and harzburgite xenoliths can survive in mafic, silica-undersaturated, subliquidus magmas at 1,050-1,200 °C and 200-800 MPa for tens of years. Modeling and comparison of the diffusion zones indicate that the average Fe-Mg interdiffusion coefficient D_FeMg in orthopyroxene is 2 log units lower than that in olivine; at 1,130 °C and QFM-buffered oxygen fugacity, D_FeMg^opx = 3 ×10 ^{- 19}  m²  s^{- 1}D_{FeMg}^{opx} = 3 \times 10^{ - 19} \,{\rm m}^2 \,{\rm s}^{{\rm - 1}} . The new data overlap well with recently published data for D_FeMg in diopside, and indicate that D_FeMg ^opxD_{FeMg\,}^{opx} (as predicted by previous authors) may be extrapolated to higher temperatures and oxygen fugacities. It is suggested that D_FeMg ^opx D_{FeMg\,}^{opx} and D_FeMg in Mn-poor ferromagnesian garnet are similar within 0.5 log units at temperatures between 1,050 and 1,200 °C.     

Experimental partitioning of Be,Cs, and other trace elements between cordierite and felsic melt,and the chemical signature of S-type granite

The trace-element signature that cordierite (Crd) imparts to silicic magmas was evaluated by experiment using metapelite mineral mixtures to produce cordierite-bearing peraluminous granitic melts at 200 MPa (P_H2O), from 700 to 850 °C. Most elemental partition coefficients vary with T. Beryllium is strongly compatible, with D_Be^Crd/melt values decreasing linearly from 202.0 to 6.7 as T rises from 700 to 850 °C. Manganese is compatible (D_Mn^Crd/melt=7.67 to 1.92 over the same range of T), and shows similar values to those reported for biotite in silicic melts. Incompatible components include Li, Rb, B, F and P, although Cs is nearly compatible in cordierite, especially at higher T (D_Cs^Crd/melt=~0.19 to 0.60) where the large alkalis are better accommodated structurally. Cordierite appears to be the most effective crystalline reservoir of Be and Cs in metapelites and their anatectic melts. Natural data support the hypothesis that Crd, when present in granitic melts, sequesters Be, Cs and, in the absence of garnet, Mn. S-type granitic rocks containing Crd show consistently low Be contents (mean=0.8 ppm Be with an average range of <1 to 1.20) whereas Crd-free granites (e.g., containing accessory garnet) exhibit distinctly higher Be contents (mean=6 ppm Be with an average range of 3 to 12). These values increase further in evolved facies (mean=69 ppm Be with a an average range of 11 to 145) which commonly give rise to beryl-bearing pegmatites. Whole-rock signatures of Be discriminate source environments of silicic magmas at a resolution equal to the boundaries of the cordierite stability field - e.g., at the P-T-X conditions where cordierite gives rise to garnet+aluminum silicate. Cordierite-bearing granitic rocks contain low Cs contents (mean=1.8 ppm Cs) compared to the Crd-free equivalents (mean=18 ppm Cs). Mn contents also correlate with the presence (mean=0.01 wt% MnO) or absence of Crd (mean=0.09 wt% MnO). Depending on its contribution to anatexis, cordierite may either give or take S-type chemical character from granitic liquids, resulting in a distinctive Crd-associated group of S-type elements. This signature is different from that of micas (high Li, F and, to a lesser degree, Be and Mn). Whole-rock compositions of granites, coupled with notable absences of beryl in their associated pegmatites, indicate that a sizable population of S-type granites originated from Crd-bearing sources. The normative Crd component of silicic peraluminous melts is Д wt% to 850 °C. Higher modal contents of cordierite reflect either restite entrainment or peritectic reactions which produce Crd after magma ascent to shallow depths. The distinctive trace-element signature of cordierite now provides improved resolution of the source mineralogy for S-type magmas.     

Proterozoic low-sulfidation epithermal Au-Ag mineralization in the Mallery Lake area, Nunavut, Canada

The Mallery Lake area contains pristine examples of ancient precious metal-bearing low-sulfidation epithermal deposits. The deposits are hosted by rhyolitic flows of the Early Proterozoic Pitz Formation, but are themselves apparently of Middle Proterozoic age. Gold mineralization occurs in stockwork quartz veins that cut the rhyolites, and highest gold grades (up to 24 g/t over 30 cm) occur in the Chalcedonic Stockwork Zone. Quartz veining occurs in two main types: barren A veins, characterized by fine- to coarse-grained comb quartz, with fluorite, calcite, and/or adularia; and mineralized B veins, characterized by banded chalcedonic silica and fine-grained quartz, locally intergrown with fine-grained gold or electrum. A third type of quartz vein (C), which crosscuts B veins at one locality, is characterized by microcrystalline quartz intergrown with fine-grained hematite and rare electrum. Fluid inclusions in the veins occur in two distinct assemblages. Assemblage 1 inclusions represent a moderate temperature (Th=150 to 220 °C), low salinity (~1 eq. wt% NaCl, with trace CO₂), locally boiling fluid; this fluid type is found in both A and B veins and is thought to have been responsible for Au-Ag transport and deposition. Assemblage 2 inclusions represent a lower temperature (Th=90 to 150 °C), high salinity calcic brine (23 to 31 wt% CaCl₂-NaCl), which occurs as primary inclusions only in the barren A veins. Assemblage 1 and 2 inclusions occur in alternating quartz growth bands in the A-type veins, where they appear to represent alternating fluxes of dilute fluid and local saline groundwater. No workable primary fluid inclusions were observed in the C veins. The A-vein quartz yields '¹⁸O values from 8.3 to 14.5‰ (average=10.9ǃ.7‰ [1C], n=30), whereas '¹⁸O values for B-vein quartz range from 11.2 to 14.0‰ (average=13.0ǂ.9‰, n=12). Calculated '¹⁸O_H2O values for the dilute mineralizing fluid from B veins range from -2.6 to 0.2‰ (average=-0.8ǂ.9‰, n=12) and are consistent with a dominantly meteoric origin. No values could be calculated for the brine, however, because all A-vein quartz samples contain mixed fluid inclusion populations. However, the fact that A-vein quartz samples extend to lower '¹⁸O values than the B veins suggests that the brine had a lighter isotopic signature relative to the dilute fluid. Hydrogen isotopic ratios of fluid inclusion waters extracted from eleven quartz samples of both vein types range from 'D_FI=-56 to -134‰, but show no particular correlation with vein type. In most respects, the mineralogical and fluid characteristics of the Mallery Lake system are comparable to those of Phanerozoic low-sulfidation deposits, and although the presence of high salinity brines is unusual in such deposits, it is not unknown (e.g., Creede, Colorado). In addition, one of the few other examples of well-preserved, Precambrian, low-sulfidation epithermal deposits, from the Central Pilbara tectonic zone, Australia, contains a similarly bimodal fluid assemblage. The significance of these saline brines is not clear, but from this study we infer that they were not directly involved with Au-Ag transport or deposition.     

He diffusion systematics in minerals: Evidence from synthetic monazite and zircon structure phosphates

Helium diffusivity was measured in synthetic rare-earth-element orthophosphates with systematically varying properties to evaluate potential controls on He transport in minerals. In the zircon structure phosphates (in this study, the phosphates of Tb, Dy, Ho, Er, Tm, Yb, and Lu as well as synthetic xenotime, YPO₄), He diffusion is strongly anisotropic. Transport apparently proceeds preferentially through channels aligned with the c-axis. The activation energy for diffusion is almost the same (122 ± 6 kJ/mol) in all members of this family, but there is a monotonic decrease in D_o with atomic number from TbPO₄ (∼10⁵ cm²/s) to LuPO₄ (∼10 cm²/s). The c-parallel channels become increasingly constricted in the same sequence, likely accounting for the systematically decreasing diffusivity. The He closure temperature (r = 1 cm, dT/dt = 10 °C/Myr) increases with atomic number from 44 °C for TbPO₄ to 88 °C for LuPO₄. Diffusion of radiogenic helium from natural zircon and xenotime is much slower than these synthetic analogs predict, suggesting that coupled substitution of REE and P for Zr and Si and/or radiation damage profoundly modify the energetics of interstitial He diffusion. In particular, α-recoil may play a key role by damaging the continuity and integrity of the channels.Monazite structure phosphates (here La, Ce, Pr, Nd, Sm, and Gd phosphate) are far more He retentive than those of the zircon structure. Activation energies increase smoothly with atomic number from LaPO₄ (183 kJ/mol) to NdPO₄ (224 kJ/mol) then decrease again to GdPO₄ (198 kJ/mol). D_o values mimic this pattern, spanning a range from ∼10⁻¹ cm²/s (GdPO₄) to 10⁴ cm²/s (NdPO₄). Nevertheless, He closure temperatures increase monotonically with atomic number, from 300 °C in LaPO₄ to 410 °C in GdPO₄. No evidence was obtained bearing on diffusion anisotropy, but the monazite structure lacks through-going channels so it is not expected. Diffusion parameters for radiogenic helium in natural monazite are similar to those obtained on the synthetic analogs.Ionic porosity is not the primary control on He diffusion in the orthophosphates. Within a given structure and with limited elemental substitution, ionic porosity and He closure temperature are negatively correlated, as predicted. However, differences between crystal structures are far more important than ion packing density: at comparable ionic porosity the monazite structure phosphates have He closure temperatures ∼300 °C higher than the xenotime structure phosphates. Modifications to the structures by radiation damage likely play a similarly significant role in controlling He diffusion.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Rare earth element and gallium diffusion in yttrium aluminum garnet

Diffusion of four rare-earth elements and gallium has been measured in yttrium aluminum garnet (YAG). Sources of diffusant were mixtures of alumina and rare-earth element oxides for REE diffusion, and mixtures of gallium and yttrium oxides for Ga diffusion. Diffusion profiles were measured with Rutherford backscattering spectrometry (RBS). For the rare-earth elements investigated, the following Arrhenius relations were obtained: D_La=6.87×10^–1 exp (–582±21 kJ mol^–1 /RT) m²s^–1 D_Nd=1.63×10^–1 exp (–567±15 kJ mol^–1 /RT) m²s^–1 D_Dy=2.70×10⁰ exp (–603±35 kJ mol^–1 /RT) m²s^–1 D_Yb=1.50×10^–2 exp (–540±26 kJ mol^–1 /RT) m²s^–1 Diffusion rates for the rare earths are quite similar, in contrast with trends noted for zircon. It is likely that these differences are a consequence of the relative ionic radii of the REE and the cations for which they substitute in the mineral lattice. For gallium, the following Arrhenius relation was determined: D_Ga=9.96×10^–6 exp (–404±19 kJ mol^–1 /RT) m²s^–1 Gallium diffuses faster than the REE in YAG and has a smaller activation energy for diffusion. These data mirror relative trends in diffusion rates for YIG, in which trivalent cations occupying tetrahedral and octahedral sites (i.e., Al, Ga, Fe) diffuse faster than trivalent cations occupying dodecahedral sites (i.e., Y and the REE), and suggest that the rate-limiting process in the diffusion-controlled regime of solid-state creep of YAG is the diffusion of yttrium. Received: 10 November 1997 / Revised; accepted: 13 March 1998     

A Method for Thermodynamical Calculation of Basicity Indicators of Rocks and Minerals

A new method has been suggested for evaluating the overall basicityof minerals and rocks by using ionization reactions involvingone proton: (sum of cations) + H₂O = mineral + H⁺, (sum of cations) + H₂O = (sum of normative minerals of a rock)+ H⁺. The basicity indicators are expressed as standard free energychanges of these reactions (). At standard water pressure (logP_H2O = 0) and chemical activity of the metal ions ( log _Mⁿ⁺= 0), the relationship between and alkalinity of solutions(pH) becomes: = –2.303 RTlog _H⁺ = 2.303 RT pH. The overall basicities of rock-forming oxides, minerals andmajor rocks were calculated from the thermodynamic data on ionsin water solutions and solid compounds.