Zircon U-Pb and Hf isotope constraints on crustal melting associated with the Emeishan mantle plume

SHRIMP zircon U-Pb dates, combined with in-situ Hf isotopic data, provide new constraints on the petrogenesis and protolith of peralkaline, metaluminous and peraluminous intrusions and rhyolitic tuffs in the Emeishan large igneous province, with significant bearing on crustal melting associated with mantle plumes. Syenite and A-type granitic intrusions from Huili, Miyi and Taihe in the center of this large igneous province yield U-Pb dates at ∼260 Ma, consistent with the ages obtained for mafic layered intrusions in the same province. Zircon from these rocks exhibits a wide range of initial Hf isotope ratios (ε_Hf(t) = −1.4 to +13.4), with corresponding T_DM1 of 400-900 Ma. The highest ε_Hf(t) value is only marginally lower than that of depleted mantle reservoir at 260 Ma, suggesting that their source is primarily juvenile crust added during Emeishan volcanism, with incorporation of variable amounts of Neoproterozoic crust. The trigger of crustal melting is most likely related to advective heating associated with magmatic underplating. In contrast, the 255-251 Ma peraluminous granites from Ailanghe and 238 Ma rhyolitic tuff from Binchuan, have negative initial ε_Hf values of −1.3 to −4.4, and of −7.7 to −14, respectively. Hf isotopic model ages and presence of inherited zircons indicate their derivation from Mesoproterozoic and Paleoproterozoic crust, respectively. Given the time lag relative to the plume impact (∼260 Ma) and insignificant mantle contribution to 255-238 Ma magmatism, conductive heating is suggested as the trigger of crustal melting that resulted in formation of delayed felsic magmas. The involvement of older crust in younger felsic magmas is consistent with upward heat transfer to the lithosphere during plume impregnation, if the age of crust is inversely stratified, i.e., changes from Paleoproterozoic to Mesoproterozoic to Neoproterozoic to Permian with increasing depth. Such crust may have resulted from episodic, downward crustal growth during the evolution of the western Yangtze Craton.     

Synthesis, characterization and thermochemistry of a Pb-jarosite

The enthalpy of formation from the elements of a well-characterized synthetic Pb-jarosite sample corresponding to the chemical formula (H₃O)_0.74Pb_0.13Fe_2.92(SO₄)₂(OH)_5.76(H₂O)_0.24 was measured by high temperature oxide melt solution calorimetry. This value ( = −3695.9 ± 9.7 kJ/mol) is the first direct measurement of the heat of formation for a lead-containing jarosite. Comparison to the thermochemical properties of hydronium jarosite and plumbojarosite end-members strongly suggests the existence of a negative enthalpy of mixing possibly related to the nonrandom distribution of Pb²⁺ ions within the jarosite structure. Based on these considerations, the following thermodynamic data are proposed as the recommended values for the enthalpy of formation from the elements of the ideal stoichiometric plumbojarosite Pb_0.5Fe₃(SO₄)₂(OH)₆:  = −3118.1 ± 4.6 kJ/mol,  = −3603.6 ± 4.6 kJ/mol and S° = 376.6 ± 4.5 J/(mol K). These data should prove helpful for the calculation of phase diagrams of the Pb-Fe-SO₄-H₂O system and for estimating the solubility product of pure plumbojarosite. For illustration, the evolution of the estimated solubility product of ideal plumbojarosite as a function of temperature in the range 5-45 °C was computed (Log(K_sp) ranging from −24.3 to −26.2). An Eh-pH diagram is also presented.     

Dissociation constants and speciation in aqueous Li2SO4 and K2SO4 from measurements of electrical conductance to 673 K and 29 MPa

The electrical conductivities of aqueous solutions of Li₂SO₄ and K₂SO₄ have been measured at 523-673 K at 20-29 MPa in dilute solutions for molalities up to 2 × 10⁻² mol kg⁻¹. These conductivities have been fitted to the conductance equation of Turq, Blum, Bernard, and Kunz with a consensus mixing rule and mean spherical approximation activity coefficients. In the temperature interval 523-653 K, where the dielectric constant, ε, is greater than 14, the electrical conductance data can be fitted by a solution model which includes ion association to form , , and , where M is Li or K. The adjustable parameters of this model are the first and second dissociation constants of the M₂SO₄. For the 673 K and 300 kg m⁻³ state point where the Coulomb interactions are the strongest (dielectric constant, ε = 5), models with more extensive association give good fits to the data. In the case of the Li₂SO₄ model, including the multi-ion associate, , gave an extremely good fit to the conductance data.     

Carbon solubility in core melts in a shallow magma ocean environment and distribution of carbon between the Earth’s core and the mantle

The solubility of carbon in Fe and Fe-5.2 wt.% Ni melts, saturated with graphite, determined by electron microprobe analysis of quenched metal melts was 5.8 ± 0.1 wt.% at 2000 °C, 6.7 ± 0.2 wt.% at 2200 °C, and 7.4 ± 0.2 wt.% at 2410 °C at 2 GPa, conditions relevant for core/mantle differentiation in a shallow magma ocean. These solubilities are slightly lower than low-pressure literature values and significantly beneath calculated values for even higher pressures [e.g., Wood B. J. (1993) Carbon in the core. Earth Planet. Sci. Lett.117, 593-607]. The trend of C solubility versus temperature for Fe-5.2 wt.% Ni melt, within analytical uncertainties, is similar to or slightly lower (∼0.2-0.4 wt.%) than that of pure Fe. Carbon content of core melts and residual mantle silicates derived from equilibrium batch or fractional segregation of core liquids and their comparison with our solubility data and carbon content estimate of the present day mantle, respectively, constrain the partition coefficient of carbon between silicate and metallic melts, in a magma ocean. For the entire range of possible bulk Earth carbon content from chondritic to subchondritic values, of 10⁻⁴ to 1 is derived. But for ∼1000 ppm bulk Earth carbon, is between 10⁻² and 1. Using the complete range of possible for a magma ocean at ∼2200 °C, we predict maximum carbon content of the Earth’s core to be ∼6-7 wt.% and a preferred value of 0.25 ± 0.15 wt.% for a bulk Earth carbon concentration of ∼1000 ppm.     

Thermodynamic properties of H4SiO4 in the ideal gas state as evaluated from experimental data

Solid phases of silicon dioxide react with water vapor with the formation of hydroxides and oxyhydroxides of silica. Recent transpiration and mass-spectrometric studies convincingly demonstrate that H₄SiO₄ is the predominant form of silica in vapor phase at water pressure in excess of 10⁻² MPa. Available literature transpiration and solubility data for the reactions of solid SiO₂ phases and low-density water, extending from 424 to 1661 K, are employed for the determination of Δ_fG⁰, Δ_fH⁰ and S⁰ of H₄SiO₄ in the ideal gas state at 298.15 K, 0.1 MPa. In total, there are 102 data points from seven literature sources. The resulting values of the thermodynamic functions of H₄SiO₄(g) are: Δ_fG⁰ = −1238.51 ± 3.0 kJ mol⁻¹, Δ_fH⁰ = −1340.68 ± 3.5 kJ mol⁻¹ and S⁰ = 347.78 ± 6.2 J K⁻¹ mol⁻¹. These values agree quantitatively with one set of ab initio calculations. The relatively large uncertainties are mainly due to conflicting data for H₄SiO₄(g) from various sources, and new determinations of would be helpful. The thermodynamic properties of this species, H₄SiO₄(g), are necessary for realistic modeling of silica transport in a low-density water phase. Applications of this analysis may include the processes of silicates condensation in the primordial solar nebula, the precipitation of silica in steam-rich geothermal systems and the corrosion of SiO₂-containing alloys and ceramics in moist environments.     

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I⁻) and molecular iodine (I₂) oxidation by the manganese oxide mineral birnessite (δ-MnO₂) was investigated over the pH range 4.5-6.25. I⁻ oxidation to iodate proceeded as a two-step reaction through an I₂ intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I⁻ from solution was first order with respect to I⁻ concentration, pH, and birnessite concentration, such that −d[I⁻]/dt = k[I⁻][H⁺][MnO₂], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 10⁷ M⁻² h⁻¹. The data are consistent with the formation of an inner sphere I⁻ surface complex as the first step of the reaction, and the adsorption of I⁻ exhibited significant pH dependence. Both I₂, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I₂ and , as well as the biophilic nature of I₂, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.     

Copper partitioning in a melt-vapor-brine-magnetite-pyrrhotite assemblage

The effect of sulfur on the partitioning of Cu in a melt-vapor-brine ± magnetite ± pyrrhotite assemblage has been quantified at 800 °C, 140 MPa, f_O2 = nickel-nickel oxide (NNO), logf_S2=-3.0 (i.e., on the magnetite-pyrrhotite curve at NNO), logf_H2S=-1.3 and logf_SO2=-1. All experiments were vapor + brine saturated. Vapor and brine fluid inclusions were trapped in silicate glass and self-healed quartz fractures. Vapor and brine are dominated by NaCl, KCl and HCl in the S-free runs and NaCl, KCl and FeCl₂ in S-bearing runs. Pyrrhotite served as the source of sulfur in S-bearing experiments. The composition of fluid inclusions, glass and crystals were quantified by laser-ablation inductively coupled plasma mass spectrometry. Major element, chlorine and sulfur concentrations in glass were quantified by using electron probe microanalysis. Calculated Nernst-type partition coefficients (±2σ) for Cu between melt-vapor, melt-brine and vapor-brine are , , and , respectively, in the S-free system. The partition coefficients (±2σ) for Cu between melt-vapor, melt-brine and vapor-brine are , , and , respectively, in the S-bearing system. Apparent equilibrium constants (±1σ) describing Cu and Na exchange between vapor and melt and brine and melt were also calculated. The values of are 34 ± 21 and 128 ± 29 in the S-free and S-bearing runs, respectively. The values of are 33 ± 22 and60 ± 5 in the S-free and S-bearing runs, respectively. The data presented here indicate that the presence of sulfur increases the mass transfer of Cu into vapor from silicate melt. Further, the nearly threefold increase in suggests that Cu may be transported as both a chloride and sulfide complex in magmatic vapor, in agreement with hypotheses based on data from natural systems. Most significantly, the data demonstrate that the presence of sulfur enhances the partitioning of Cu from melt into magmatic volatile phases.     

The partitioning behavior of silver in a vapor-brine-rhyolite melt assemblage

The partitioning of silver in a sulfur-free rhyolite melt-vapor-brine assemblage has been quantified at 800 °C, pressures of 100 and 140 MPa and f_O2≈NNO (nickel-nickel oxide). Silver solubility (±2σ) in rhyolite increases 5-fold from 105 ± 21 to 675 ± 98 μg/g as pressure increases from 100 to 140 MPa. Nernst-type partition coefficients describing the mass transfer of silver at 100 MPa between vapor and melt, brine and melt and vapor and brine are 32 ± 30, 1151 ± 238 and 0.026 ± 0.004, respectively. At 140 MPa, values for for vapor and melt, brine and melt, and vapor and brine are 32 ± 10, 413 ± 172 and 0.06 ± 0.03, respectively. Apparent equilibrium constant values (±2σ) describing the exchange of silver and sodium between vapor and melt, , at 100 and 140 MPa are 105 ± 68 and 14 ± 6. The average values (±2σ) for silver and sodium exchange between brine and melt, , at 100 and 140 MPa are 313 ± 288 and 65 ± 12. These data indicate that the mass transfer of silver from rhyolite melt to an exsolved volatile phase(s) is enhanced at 100 MPa relative to 140 MPa, suggesting that decompression increases the silver ore-generative potential of an evolving silicate magma. Model calculations using the new data suggest that the evolution of low-density, aqueous fluid (i.e., vapor) may be responsible for the the silver tonnage of many porphyry-type and perhaps epithermal-type ore deposits. For example, Halter et al. (Halter W. E., Pettke T. and Heinrich C. A. (2002) The origin of Cu/Au ratios in porphyry-type ore deposits. Science296, 1842-1844) used detailed silicate and sulfide melt inclusion and vapor and brine fluid inclusions analyses to estimate a melt volume on the order of 15 km³ to satisfy the copper budget at the Bajo de la Alumbrera copper-, gold-, silver-ore deposit. Using their melt volume estimate with the data presented here, model calculations for a 15-km³ felsic melt, saturated with pyrrhotite and magnetite, suggest that a low-salinity magmatic vapor may scavenge on the order of 7 × 10¹² g of silver from the melt. This quantity of silver exceeds the discovered 2 × 10⁹ g of Ag at Alumbrera. Calculated tonnages for numerous other deposits yield similar results. The excess silver in the vapor, remaining after porphyry formation, is then available to precipitate at lower PTconditions in the stratigraphically higher epithermal environment. These data suggest that silver, and perhaps other ore metals, in the porphyry-epithermal continuum may be derived solely from the time-integrated flux of dominantly low-salinity vapor exsolved from a series of sequential magma batches.     

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al₂O₃-TiO₂-SiO₂ system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D_Ta/D_Nb and D_Hf/D_Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D_Hf/D_W = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO₂ contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.     

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide

The quantification of silicon isotopic fractionation by biotic and abiotic processes contributes to the understanding of the Si continental cycle. In soils, light Si isotopes are selectively taken up by plants, and concentrate in secondary clay-sized minerals. Si can readily be retrieved from soil solution through the specific adsorption of monosilicic acid () by iron oxides. Here, we report on the Si-isotopic fractionation during adsorption on synthesized ferrihydrite and goethite in batch experiment series designed as function of time (0-504 h) and initial concentration (ic) of Si in solution (0.21-1.80 mM), at 20 °C, constant pH (5.5) and ionic strength (1 mM). At various contact times, the δ²⁹Si vs. NBS28 compositions were determined in selected solutions (ic = 0.64 and 1.06 mM Si) by MC-ICP-MS in dry plasma mode with external Mg doping with an average precision of ±0.08‰ (±2σ_SEM). Per oxide mass, ferrihydrite (74-86% of initial Si loading) adsorbed more Si than goethite (37-69%) after 504 h of contact over the range of initial Si concentration 0.42-1.80 mM. Measured against its initial composition (δ²⁹Si = +0.01 ± 0.04‰ (±2σ_SD)), the remaining solution was systematically enriched in ²⁹Si, reaching maximum δ²⁹Si values of +0.70 ± 0.07‰ for ferrihydrite and +0.50 ± 0.08‰ for goethite for ic 1.06 mM. The progressive ²⁹Si enrichment of the solution fitted better a Rayleigh distillation path than a steady state model. The fractionation factor ²⁹ε (±1σ_SD) was estimated at −0.54 ± 0.03‰ for ferrihydrite and −0.81 ± 0.12‰ for goethite. Our data imply that the sorption of onto synthetic iron oxides produced a distinct Si-isotopic fractionation for the two types of oxide but in the same order than that generated by Si uptake by plants and diatoms. They further suggest that the concentration of light Si isotopes in the clay fraction of soils is partly due to sorption onto secondary clay-sized iron oxides.     

Porphyry and skarn Au–Cu deposits in the Shizishan orefield, Tongling, East China: U–Pb dating and in-situ Hf isotope analysis of zircons and petrogenesis of associated granitoids

The magnetite-series (I-type) calc-alkaline granitoid suit, ranging from pyroxene monzodiorite to granodiorite, is associated with the porphyry and skarn gold–copper deposits at the Shizishan orefield in Tongling district, Anhui Province. In-situ U–Pb dating and Hf isotope analysis of magmatic and inherited zircons are combined with whole rock Sr–Nd–Pb isotopic data and mineral thermobarometry to interpret the petrogenesis. The magmatic zircons from the quartz monzodiorites yield weighted average ²⁰⁶Pb/²³⁸U ages of ca. 139 Ma and mean ε_Hf(t) value of −19.8 ± 3.9 (1σ), while those from the pyroxene monzodiorite show a similar mean age but notably higher mean ε_Hf(t) value (−8.5 ± 1.4). The inherited zircons from the quartz monzodiorite yield ages of 0.8, 2.0 and 2.4 Ga with mean ε_Hf(t) value of −2.9 ± 1.4, while those from the pyroxene monzodiorite show younger ages (165 to 245 Ma) but similar mean ε_Hf(t) value (−5.6 ± 4.5). Whole rock Sr–Nd–Pb isotope data indicate that crustal material significantly contributed to the magma. Mineral thermobarometry results reveal that the depths of the discrete magma chambers were about 23 km, and 10 to 2 km deep.The data above combined with previous studies suggest that: 1) The magma emplacement and crystallization (typically for zircons) mainly occurred at about 139 Ma, consistent with the age of mineralization; 2) The primary pyroxene monzodioritic magma might have mixed with the magma produced by partial melting of the Yangtze lower crust, and accumulated in the magma chamber at ca. 23 km deep in the lower crust level; 3) AFC and magma mixing were the dominate processes for the magmatic evolutions at shallow level (2 to 10 km), where the circumstances were favorable for mineralization.     

Carbon isotope fractionation in synthetic magnesian calcite

Mg-calcite was precipitated at 25 °C in closed system, free-drift experiments, from solutions containing NaHCO₃, CaCl₂ and MgCl₂. The carbon stable isotope composition of bulk solid and solution were analyzed from subsamples collected during time course experiments of 24 h duration. Considering only the Mg-content and δ¹³C values for the bulk solid, the carbon isotope fractionation factor for the Mg-calcite-HCO_3(aq)⁻ system (as ) increased with average mol percentage of Mg (X_Mg) in the solid at a rate of (0.024 ± 0.011) per mol% MgCO₃. Extrapolation of this relationship to the pure calcite end member yields a value of 0.82 ± 0.09, which is similar to published values for the calcite-HCO_3(aq)⁻ system. Although did not vary for precipitation rates that ranged from 10^3.21 to 10^4.60 μmol m⁻² h⁻¹, it was not possible to hold Mg-content of the solid constant, so kinetic effect on 10³ ln α could not be evaluated from these experiments.     

Zircon U-Pb and Lu-Hf isotopic systematics of the Daping plutonic rocks: Implications for the Neoproterozoic tectonic evolution of the northeastern margin of the Indochina block, Southwest China

The Daping Neoproterozoic plutonic rocks at the northeastern margin of Indochina block in southwest China provide an ideal opportunity for studying the tectonic setting and relationship between the Indochina and Yangtze Blocks. LA-ICP-MS U-Pb dating on the zircon cores and rims of a hornblende-gabbro yield ²⁰⁶Pb/²³⁸U weighted means ages of 873 ± 9.1 Ma and 769 ± 7 Ma, respectively, and that for cores, mantles and rims of a granodiorite yield ²⁰⁶Pb/²³⁸U weighted means ages of 981-987 Ma, 829 ± 10 Ma and 761 ± 11 Ma, respectively. The zircon cores and mantles are interpreted as inherited from their source region. The zircon rims are magmatic, their ages represent the emplacement timing. The zircon cores and rims from the hornblende-gabbro have ε_Hf^(t) values ranging from − 5.0 to − 5.8 and + 0.6 to + 6.4. Corresponding single-stage model ages range from 1626 to 1662 Ma and 1094 to 1311 Ma, respectively. For the granodiorite, the inherited mantles (including cores) show two groups: (1) ε_Hf^(t) values of + 3.3 to + 12.3 with single-stage Hf model ages of 897 to 1235 Ma; and (2) ε_Hf^(t) values of − 1.9 to − 7.8 with single stage model ages of 1470-1667 Ma. The zircon rims are characterized by positive ε_Hf^(t) values (+ 5.4 to + 8.2) with single-stage model ages ranging from 977 to 1108 Ma. Whole-rock geochemical data for the hornblende-gabbro, such as enrichment of LILE and LREE, negative anomaly of Nb and Ta, and high Mg^# (52.1-65.4), suggest magma generation in a subduction-related setting. An island-arc affinity is strongly supported by the features of high-alumina basalt and abundant hornblende in a large hornblende-gabbro sill. The granodiorites are characterized by high Sr contents and Sr/Y ratios, strong enrichment of LILE and LREE, and negative anomaly of Nb, Ta, P and Ti, comparable with the features of subduction-related plutonic rocks. These data show that the hornblende-gabbro was generated by the partial melting of a metasomatized mantle wedge peridotite with contribution from aqueous fluids derived from a subducted slab. The granodiorite magma is a product of the mixing of mafic magma produced by partial melting of a slab-fluid-enriched metasomatized mantle wedge peridotite and felsic magma formed by the partial melting of crustal materials. The emplacement ages and geochemical features of subduction-related Daping plutonic rocks are the same as those reported from the western margin of the Yangtze block, suggesting the presence of an oceanic crust in between, with subduction to either side generating island-arc magmatism in the Neoproterozoic.     

Early Cretaceous adakitic granites in the Northern Dabie Complex, central China: Implications for partial melting and delamination of thickened lower crust

To date, few adakitic rocks have been reported in direct association with contemporary intra-continental extensional structures, which has cast doubt on genetic models involving partial melting of the lower crust. This study presents Early Cretaceous (143-129 Ma, new Sensitive high-resolution ion microprobe (SHRIMP) zircon U-Pb ages) adakitic granites, which are directly associated with a contemporary metamorphic core complex (i.e., the Northern Dabie Complex in the Dabie area). These granites exhibit relatively high Sr contents, negligible to positive Eu and Sr anomalies, high La/Yb and Sr/Y ratios, but very low Yb and Y contents, similar to subducted oceanic crust-derived adakites. They are also characterized, however, by very low MgO or Mg^# and Ni values, and Nd-Sr isotope compositions (ε_Nd(t) = −14.6 to −19.4 and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067-0.7087) similar to Triassic continent-derived eclogites subducted in the Dabie-Sulu Orogen. Additionally, late granitic dikes in the adakitic intrusions exhibit low Sr contents, clearly negative Eu and Sr anomalies, low La/Yb and Sr/Y ratios, but relatively high Yb and Y contents, similar to 118-105 Ma granites in the Northern Dabie Complex. Based on composition and geochronology data of Neoproterozoic amphibolites and orthogneisses, Triassic high- to ultra-high pressure metamorphic rocks, and Early Cretaceous mafic-ultramafic intrusive rocks, and the constraints provided by experimental melt data for tonalites, metabasaltic rocks and eclogites, we suggest that the adakitic granites were most probably generated by partial melting of thickened amphibole or rutile-bearing eclogitic lower crust as a consequence of Triassic-Middle Jurassic subduction and thrusting. The late dikes probably originated from plagioclase-bearing intermediate granulites. Moreover, we suggest that late Mesozoic delamination or foundering of thickened eclogitic lower crust is also a more plausible mechanism for the petrogenesis of Early Cretaceous mafic-ultramafic intrusive rocks in the Dabie area, and probably involved partial melting of a mixed source comprising eclogitic lower crust that had delaminated or foundered into upper lithospheric or asthenospheric mantle peridotite. Asthenospheric upwelling in response to post-collisional delamination of lithospheric mantle was likely to have provided the heat source for the Cretaceous magmatism.     

Solubility of plutonium(VI) carbonate in saline solutions

Among the plutonium oxidation states found to form in the environment, mobile plutonium(VI) can exist under oxidizing conditions and in waters with high chloride content due to radiolysis effects. We are investigating the solubility and speciation of plutonium(VI) carbonate under conditions relevant to natural waters and brines such as those found near some geologic radioactive waste repositories. The solid Pu(VI) phase PuO₂CO₃(s) was prepared and its solubility was measured in NaCl and NaClO₄ solutions in a CO₂ atmosphere as a function of pH and ionic strength (0.1-5.6 m). The concentration of soluble plutonium in solution was calculated from spectroscopic data and liquid scintillation counting. Spectroscopic measurements also revealed the plutonium oxidation state. The apparent solubility product of PuO₂CO₃(s) was determined at selected electrolyte concentrations to be, log K_s,0 = −13.95 ± 0.07 (0.1 m NaCl), log K_s,0 = −14.07 ± 0.13 (5.6 m NaCl), and log K_s,0 = −15.26 ± 0.11 (5.6 m NaClO₄). Specific ion interaction theory was used to calculate the solubility product at zero ionic strength, .     

The effect of sulfur on the partitioning of Ni and other first-row transition elements between olivine and silicate melt

The effect of sulfur dissolved as sulfide (S²⁻) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S²⁻ were varied from zero to sulfide saturation, reaching 4100 μg g⁻¹ S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S²⁻ in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M²⁺, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S²⁻ nor of Mg#^ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S²⁻ depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10⁻³ (±1.3 × 10⁻³) K per μg g⁻¹ of S²⁻, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO₂ content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10⁻³. The ratio / is well constrained at 0.611 ± 0.016.     

A potentiometric study of the stability of aqueous yttrium-acetate complexes from 25 to 175 °C and 1-1000 bar

The stability of yttrium-acetate (Y-Ac) complexes in aqueous solution was determined potentiometrically at temperatures 25-175 °C (at P_s) and pressures 1-1000 bar (at 25 and 75 °C). Measurements were performed using glass H⁺-selective electrodes in potentiometric cells with a liquid junction. The species YAc²⁺ and were found to dominate yttrium aqueous speciation in experimental solutions at 25-100 °C (log [Ac⁻] < −1.5, pH < 5.2), whereas at 125, 150 and 175 °C introduction of into the Y-Ac speciation model was necessary. The overall stability constants β_n were determined for the reaction